Applied Energy: Contents Lists Available at

Applied Energy 231 (2018) 502–533
Contents lists available at ScienceDirect
Applied Energy
journal homepage: www.elsevier.com/locate/apenergy
A comprehensive review of carbon and hydrocarbon assisted water T

electrolysis for hydrogen production
⁎
HyungKuk Jua, Sukhvinder Badwalb, Sarbjit Giddeya,
a
CSIRO Energy, Private Bag 10, Clayton South, Victoria 3169, Australia
b
BADWAL Hydrogen Energy, PO Box 318, Endeavour Hills, Victoria 3802, Australia
H I GH L IG H T S G R A P H I C A L A B S T R A C T
• Carbon/hydrocarbon assisted water

electrolysis reviewed for clean hy-
drogen production.
• technologies
Reviewed different electrochemical
using carbon fuels under
development.
• This technology has been progressed
to different levels of maturity for dif-
ferent carbon sources.
• This route of hydrogen production can
lower the electric input and CO 2
emissions from the carbon sources.
A R T I C LE I N FO A B S T R A C T
Keywords: Hydrogen is mainly produced by natural gas reforming, which is a highly efficient process with low feedstock
Electrolyser costs. However, the rising interest in clean technologies will increase the demand for hydrogen, meaning that
Coal other sources will need to be explored. Although coal is currently the major source of power generation, its
Methanol demand appears to be declining due to the rise in electricity generated from renewable energy sources and the
Ethanol
worldwide quest for low-emission power generation. Coal reserves worldwide are abundant, but new technol-
Natural gas
Alcohol
ogies would be needed to produce hydrogen from this feedstock. Coal gasification is one well-established
technology for this purpose, but it is inefficient and produces high CO2 emissions. An alternative technology that
has been investigated over the past few decades is carbon assisted water electrolysis. The basic process is water/
steam electrolysis, with part of the energy required for the electrolysis provided by the chemical energy of coal,
Abbreviations: ACFC, air-carbon fuel cell; AEM, anion exchange membranes; CAWE, carbon/coal assisted water electrolysis and carbon/hydrocarbon assisted water
electrolysis; CHP, combined heat and power; COD, chemical oxygen demand; COR, carbon-water oxidation reaction; DCFC, direct carbon/coal fuel cells; DHA, 1,3-
dihydroxyacetone; DMSO, dimethylsulphoxide; EAWE, ethanol assisted water electrolysis; FE, Faradaic efficiency or coulombic current efficiency; GC, gas chro-
matography; GDC, gadolinium-doped ceria; GDL, gas diffusion layer; HER, hydrogen evolution reaction; HHV, higher heating value, liquid water; HMF, hydro-
xymethylfurfural; HOR, hydrogen oxidation reaction; LHV, low heating value, steam water; LLNL, Lawrence Livermore National Laboratory; LMA, liquid metal
anode; LSM, Sr-doped lanthanum manganite; MAWE, methanol assisted water electrolysis; MEA, membrane electrode assembly; NDIR, non-dispersive infrared
detector; NG, natural gas; OCV, open circuit voltage; OER, oxygen evolution reaction; ORR, oxygen reduction reaction; PEM, proton conducting membrane and
proton exchange membrane; PEMFC, polymer electrolyte membrane fuel cell; PSEM, proton-conducting solid electrolyte membrane; PTFE, polytetrafluoroethylene;
SCAFC, steam-carbon-air fuel cell; SCFC, steam-carbon fuel cell; SMR, steam methane reforming; SOE, solid oxide electrolyte; SOEC, solid oxide electrolysis cell;
SOFC, solid oxide fuel cell; SOM, small organic molecules; SPEEK, sulfonated polyetheretherketone; TOC, total organic carbon; WGS, water gas shift; YSZ, yttria
stabilized zirconia
⁎
Corresponding author.
E-mail address: [email protected] (S. Giddey).
https://doi.org/10.1016/j.apenergy.2018.09.125
Received 25 May 2018; Received in revised form 20 August 2018; Accepted 10 September 2018
Available online 21 September 2018
0306-2619/ © 2018 Elsevier Ltd. All rights reserved.
H. Ju et al. Applied Energy 231 (2018) 502–533
which reduces the overall electrical energy input. In addition to coal, the process can also use other carbon
sources, such as biomass, alcohols or gaseous hydrocarbons. Several studies have investigated this electro-
chemical route of hydrogen production, employing different electrolytes in a wide temperature range (room
temperature to 850 °C) under different process conditions. This paper presents a comprehensive review of carbon
assisted water electrolysis, associated materials used and the challenges for the development of the technology at
the commercial scale.
1. Introduction reduced and hydrogen can be generated at distributed or end-use sites

as required by emerging power-generation technologies, such as fuel
Solutions for global energy challenges are being sought by moving cells.
towards eco-friendly technologies for a sustainable future. In an effort Carbon/hydrocarbon assisted co-electrolysis has the potential to
to reduce dependence on fossil fuel based energy sources, there has offer a less energy-intensive and relatively clean method of using the
been substantial activity using renewable energy sources (e.g. solar, chemical energy in various sources of carbon, such as low-rank coals,
wind, hydro, ocean and geothermal). However, many such energy alcohols, methane, NG and even biomass, where pure CO2 produced
sources require substantial initial investment, and the cost of electricity can be easily sequestered without the need for separation. In this ar-
generation can be high. Moreover, the intermittency of renewable en- ticle, we comprehensively review different low and high temperature
ergy sources and their dependence on environmental conditions places electrochemical technologies currently under development, which use a
a strong emphasis on the need for cost-effective, large-scale storage range of electrode and electrolyte materials such as aqueous, polymer
solutions. electrolyte membrane and solid oxide electrolyte (SOE) membrane
Hydrogen is an excellent energy storage medium, the use of which cells. The review also covers:
in fuel cells for stationary, transport and portable power applications
offers several advantages. These include high efficiency, low green- • Various types of carbon sources (coal, methanol, ethanol, glycerol,
house and pollutant (NOx, SOx, and particulates) emissions at the point ethylene glycol, cellulose, NG, methane and CO) used to assist the
of use, economies of scale (being modular in nature), and distributed water electrolysis process
and combined heat and power (CHP) generation. The majority of hy- • The electrochemical reactions involved and electrode kinetic lim-
drogen produced at present (about 60 million tonnes per annum) is itations
used for ammonia production, in oil refineries to generate a lighter oil • Thermodynamic properties, such as free energy and enthalpy
fraction, and to a smaller extent in the chemical and pharmaceutical change of reactions and theoretical cell voltages required
industries, space exploration and power generation. Most of this hy- • The energy input required for the electrolysis process with different
drogen is produced either by natural gas (NG) reforming with an effi- types of carbon sources and under different process conditions
ciency of around 70–75%, or by coal gasification, which is about
45–65% efficient [1–5] and has high CO2 emissions. Generally, these We also summarise and discuss the results obtained by various in-
processes are suitable for large scale hydrogen production in central vestigators in terms of cell designs, materials used, current densities
plants, which also offer a favourable cost structure. Only a small per- obtained at given voltages, and electric energy savings in the electro-
centage of worldwide hydrogen production is via water electrolysis. lysis process. The review concludes with a discussion of the outlook for
Although suitable for distributed hydrogen production at demand technical challenges and new opportunities in this field.
centres, the process is very energy intensive, requiring 6–7 kWh electric
input per m3 of hydrogen produced (65–80 kWh kg−1 at 25 °C and 2. Fuel sources to assist with water electrolysis
1 atm), and the capital cost and the cost of production are very high
[6–8]. The fuels that can be used to provide chemical energy to assist with
Coal is currently used to meet around 40% of total global electricity the electrochemical splitting of water include coal (raw or processed to
demand and is forecast to remain a major source for power generation remove sulfur and ash impurities), carbon from biomass sources, me-
for many more decades, due to its low cost and vast reserves [9]. thane, methanol, ethanol and some other organic materials, such as
However, due to the low efficiency of its conversion to electricity (ty- dimethyl ether (DME) and ethylene glycol. In terms of cost, coal or
pically 35–40%), it can contribute significantly to the CO2 and other carbon from biomass are the most effective fuel sources available in
pollutant emissions. Although carbon capture and storage (CCS) tech- large quantities, and costs increase for hydrocarbon fuels.
nologies have the potential to reduce CO2 emissions to the atmosphere, Carbon fuels can be used in both low and high temperature elec-
their large-scale deployment to capture even a small percentage of the trolysis systems. Methanol and ethanol are more suitable for low tem-
32 billion tons per annum of CO2 generated globally and the further perature (< 80 °C) electrolysis systems, while methane is more suited
power generation efficiency losses resulting from this process means a for high temperature electrolysis cells. Methane is a major constituent
range of solutions are required. of NG (typically > 92%) and is available in reticulated form in most
The electrochemical oxidation of solid carbon has been under in- developing countries. Alcohols and carbon are easily transportable
vestigation for many decades for power generation; for example, in fuels; thus the water electrolysis process to generate hydrogen can be
direct carbon/coal fuel cells (DCFC) for efficient conversion of coal to carried out at distributed or demand centres. Obviously, coupling of the
low-emission electricity [10–16]. New electrochemical technologies are electrolysis process with renewable energy for low temperature elec-
also currently under development that combine water electrolysis with trolytic processes would offer environmental benefits, with electricity
the use of coal or hydrocarbon fuels to assist with the electrochemical input provided by solar photovoltaic or wind, for instance. Similarly,
reactions and reduce the overall energy consumption [17–21]. Ther- for high temperature electrolytic processes in addition to renewable
modynamic and operational analysis of these systems suggest that energy waste thermal energy from industrial processes or solar thermal
about 60% of the energy required for water electrolysis can be provided plants can offer further environmental sustainability.
by coal or other hydrocarbon (methanol, ethanol, NG) fuels in the form Coal, despite being the most obvious and low-cost option to assist
of chemical energy, thus substantially reducing the electric input with water electrolysis, is composed of complex aromatic clusters with
[20–28]. Furthermore, if the process can be coupled with a renewable inorganic constituents containing a large range of species which varies
energy source, the intensity of CO2 emissions can be significantly significantly for different coals. Fig. 1 is an example of molecular model
503
Fig. 1. Molecular representation of bituminous coal structure with heteroatoms simulated by Narkiewicz and Mathews. Figure reproduced with permission from
[29].
of a bituminous coal structure containing highly functional, high mo- vehicles. The energy input to produce ethanol compared with its energy
lecular weight organic and inorganic matter [29]. The impurities in content varies significantly depending on the source and the process
coal are important to support its utilisation in combustion and gasifi- used for its production [40]; the energy balance is very favourable for
cation processes, and for the long-term stability of electrochemical sugarcane. About 90 billion litres of methanol is produced per annum
cells. Generally, the sulfur in coal is categorised as present both in in- for use in chemical production and as a transportation fuel. It is typi-
organic (generally sulfides and sulfates) and organic forms, and pyrite is cally produced from syngas (a mixture of CO and H2). Any fossil fuel
the major contaminant in coal. The removal of inorganic sulfur con- (coal, NG) or biomass resource (wood, agriculture waste, forest residue)
tamination can be carried out by well-established coal preparation that can be converted to syngas via gasification, can be used as a
techniques, but the removal of organic sulfur is still an issue [30–32]. feedstock for methanol synthesis. In a secondary process, syngas is
The concept of solid carbon assisted water electrolysis (CAWE) in converted to methanol via a catalytic process [41,42]. Although most
acidic media for hydrogen production was first proposed and in-
vestigated by Coughlin and Farooque from 1979 to 1982 [33–37] and
involved a series of experiments in an electrochemical cell shown
schematically in Fig. 2. The authors also used this technique to in-
vestigate sulfur removal from coal. They found that the mineral matter,
other impurities and functional groups in coal can interfere with and
influence electrochemical use of carbon both positively and negatively,
and concluded that this requires careful investigation.
Another major source of carbon fuel is biomass. Carbon is produced
by partial combustion (or pyrolysis) of a range of naturally occurring,
fuel rich, carbonaceous biomass materials, such as forestry and agri-
cultural residues, grasses, wood chips and wood shavings. The initial
product obtained is then activated by chemical or a physical activation
process to yield high surface area and porous carbon [38,39]. Due to
different starting materials and activation processes used, the properties
(e.g. pore size, volume and distribution, surface area) of activated
carbon thus produced and to some degree, impurity levels can vary
significantly. Activated carbons have substantial market for use as ad-
sorbents to remove organic constituents from air and water, in in-
dustrial processes (e.g. treatment of gases, removal of trace metals,
removal of volatile inorganic and organic compounds) and as a support
for noble metal catalysts. They can also be used as a fuel in the carbon
assisted electrolysis process to generate hydrogen [39].
Both ethanol and methanol can be produced using biomass. More
Fig. 2. Schematic drawing of the first electrochemical cell arrangement for
than 85 billion litres of ethanol is produced annually worldwide, mainly
hydrogen production from carbon/coal slurry in acid media [33]. Both anode
through fermentation process from biomass sources such as sugarcane, and cathode compartments consist of a Pt gauge 52 mesh immersed in 3.7 M
corn, beetroot, switch grass and other food plant or forest residue. It is H2SO4 at 23 °C with respective areas of 96.5 and 158 cm2. Figure redrawn from
widely considered as a blended renewable fuel for transportation [33].
504
methanol is currently produced from steam reforming or partial oxi- times. In PEM based electrolysis process, water is circulated in the
dation of NG, bio-methanol can be produced from destructive pyrolysis anode (positive electrode) chamber. On application of DC voltage to the
of wood. Renewable methanol can also be produced from hydrogen, electrodes, an oxygen evolution reaction (OER) occurs at the anode,
generated via electrolysis of water coupled to a renewable energy generating protons and electrons. The protons are transported through
source (solar photovoltaics or wind), and the CO2 captured from fossil the electrolyte membrane to the cathode, resulting in a hydrogen evo-
fuel power plants or industrial processes [41]. lution reaction (HER) at the cathode (hydrogen electrode), which also
Methanol and ethanol both have a high hydrogen content of ∼13 wt involves the consumption of electrons. The associated electrode reac-
% and are in liquid state at ambient temperatures. Therefore, both fuels tions and cell voltages (at 25 °C and 1 atm) for a PEM-based electrolysis
are considered as good means of transporting large quantities of hy- process are given in Table 2.
drogen for fuel cells [41]. The energy density of methanol is In PEM-based system, a solid-state PEM such as Nafion® (DupontTM,
6.20 kWh kg−1 (4.90 kWh L−1) LHV compared with 8.0 kWh kg−1 perfluorosulfonic acid membrane) and sulfonated polyetheretherketone
(6.32 kWh L−1) LHV for ethanol [40,43]. are commonly used as electrolytes. The catalysts used for the electrodes
are noble metals such as Ir, Ru, IrO2 and RuO2 for the anode, and Pt
3. Fundamentals of conventional and carbon assisted water black supported on carbon as the cathode. The typical operating tem-
electrolysis perature range for acidic water solution and PEM based systems is
20–80 °C. Fig. 4(a) shows the schematic of the electrochemical cell and
3.1. Basic principles the associated electrode reactions. This technology is at an advanced
stage of development, with many companies selling commercial units
In the electrolysis process, water is decomposed into hydrogen and now in the MW class capable of producing hydrogen in excess of 30 bar
oxygen when an electrical current is passed through an electrolytic cell. [6–8,44]. The costs of these units are still high but the lifetimes being
Typically, the cell consists of an electrolyte, an anode and a cathode. A quoted are in excess of 80,000 h. PEM electrolysis cells are typically
number of cells are connected in series (called an electrolyser) to pro- operated at cell voltages of 1.8–2.2 V with current densities up to 1 A
duce quantities of gases. Different types of electrolysers can be dis- cm−2 and temperatures below 100 °C [44]. Further, these systems have
tinguished based on the type of electrolyte used in the cell and the advantage in terms of their operability with varying or intermittent
operating temperature regime. Fig. 3 shows a tree diagram depicting load.
various types of low and high temperature conventional electrolysis and Alkaline solution based electrolysis offered the use of relatively
CAWE systems, while Table 1 summarises further details of the cell cheaper materials for electrolysis cells and the plant compared with
materials used and operating conditions for these systems. The rest of acidic solution based system, and was adopted early and at a large scale
this section describes the basic principles of the major types of elec- [7,44]. This technology is the most developed at commercial scale, with
trolysers. units available in the multi-MW class [6–8]. KOH solution with con-
centrations up to 30% is the preferred electrolyte used for these sys-
3.1.1. Acidic/alkaline solution and membrane based water electrolysis tems. The electrodes are separated by a diaphragm that keeps the gases
Water electrolysis to produce hydrogen and oxygen was first dis- evolved on the respective electrodes separate from each other, but al-
covered in acidic water solutions, but due to severe corrosion related lows exchange of hydroxyl ions and water between the electrodes. The
issues that need relatively expensive materials, this method of electro- advantage of alkaline based electrolysis is the lower cost of the elec-
lysis attracted less attention than alkaline based electrolysis. However, trode materials, due to the use of non-noble metal catalysts such as Ni
electrolysis based on a proton conducting membrane or proton ex- based materials (Ni, Ni oxide, Co oxide and Ni alloys on the steel).
change membrane (PEM), which is mildly acidic in nature and has si- However, these suffer from lower current densities, due to high elec-
milar electrode reactions, has gained remarkable popularity in recent trolyte resistance, low capability to operate at high pressures and on
Fig. 3. Tree diagram depicting the various routes of carbon/hydrocarbon assisted water electrolysis.
505
Table 1
Operating parameters and cell materials used for different electrolysis technologies [1,6,7,20,44,105,175,176].
Alkaline electrolysis PEM electrolysis SOEC electrolysis CAWE in PEM CAWE in SOEC
Operating temp./°C < 100 < 100 500–1,000 < 100 700–1,000
Operating cell voltage/V 1.7–2.4 1.8–2.2 1.0–1.6 0.5–1.2 < 1.0
Current density/mA cm−2 > 500 > 2,000 > 1,500 < 300 < 500
Anode Mn, Fe, Co, Ni and Ir, Ru, IrO2 and RuO2 LSM-YSZ, CGO, LSCF and BSCF Pt, PtIr and PtRu Pt, Ni, Ag and Sn
its metal oxide
Cathode Ni alloy and Pt Pt/C and Pt Ni-YSZ, SDC and LSM-YSZ Pt/C and Pt Pt, Ni and Ni-YSZ
Electrolyte KOH, NaOH and Nafion system YSZ, ScSZ and doped-CeO2 systems for O2− Nafion system Zirconia based solid
NaCl solution (perfluorosulfonic acid conducting ceramics and doped-CeO3, doped- and porous oxide electrolyte (YSZ)
membrane) ZrO3 systems for H+ conducting ceramics fritted glass
BSCF = Ba-doped strontium cobalt ferrite; CAWE = carbon/hydrocarbon-assisted water electrolysis; CGO = Gd-doped ceria; LSM = Sr-doped lanthanum manganite;
LSCF = La-doped strontium cobalt ferrite; PEM = polymer electrolyte membrane; SDC = Sr-doped ceria; SOEC = solid oxide electrolysis cell; YSZ = yttria-stabilised
zirconia.
varying load, and a greater chance of mixing of gases, resulting in lower solution/PEM and alkaline solution/AEM is shown schematically in
Faradaic efficiencies (FE) and safety concerns. This has recently led to Fig. 4(e) and (f), respectively, and the associated reactions at the anode
the development of anion-exchange membranes (AEM) for alkaline and cathode are described in Table 2 (at 25 °C and 1 atm). Note that the
water electrolysis. There are already two commercial membranes reversible voltages of the overall electrolysis reactions involving carbon
available in the market: A201 membrane (Tokuyama Co., Japan) and are significantly lower (0.21 V for CO2 and 0.52 V for CO) than in
Selemion AMV (Asahi Glass Co., Japan) – with several other groups conventional electrolysis (1.23 V).
developing different types. The basic principle of water electrolysis To date, most studies on carbon assisted electrolysis have been
based on alkaline solutions and AEM is shown schematically in conducted in acidic solutions [33–37,46–54], with some in alkaline
Fig. 4(b), and the associated electrolysis reactions and cell voltages (at solutions [55–57] and some employing PEM as a separator or electro-
25 °C and 1 atm) are shown in Table 2. AEMs have lower ionic con- lyte [58–67]. None of the studies employed AEM. The operating con-
ductivities than PEM, and often electrolyte solutions are added to im- ditions were mostly room temperature to below 100 °C and atmospheric
prove conductivity. For example, in the AEM based electrolysis cell, pressure, with only few studies carried out at temperatures up to 160 °C
KOH is added to water for circulation in the anode chamber. Alkaline and above atmospheric pressures (∼10 bar) [67,68].
electrolysis cells are typically operated at cell voltages of 1.7–2.4 V with In the liquid hydrocarbon assisted water electrolysis, alcohols and
current densities up to 0.5 A cm−2 and temperatures below 100 °C. liquid hydrocarbons such as methanol, ethanol, formic acid, glycerol
and bio-hydrocarbons mixed with water provide part of the energy in
3.1.2. Solid oxide electrolyte membrane based steam electrolysis the form of chemical energy for the electrolysis process. Fig. 4(g) shows
High temperature electrolysis (of steam) not only helps increase the a schematic of the basic principle of the electrolysis process for alco-
reaction kinetics of the electrolysis reactions and reduce overvoltages, hols. Most of these studies have been conducted using PEM (some have
but also allows solar energy or waste heat from power plants and other used AEM) and at operating temperatures lower than 100 °C
industrial processes to be embedded into the process. One technology [22–24,69–88]. The catalysts used are similar to those used for PEM
still at an early stage of development is based on the use of an oxygen based direct liquid fuel cells. Table 3 provides the detailed electro-
ion conducting ceramic membrane, in which the electrolysis process chemical reactions that occur at the anode and cathode of the alcohol/
occurs at high temperatures (> 500 °C) [6]. The steam supplied to the bio-hydrocarbon/organic acid assisted co-electrolysis cells and the as-
cathode in the electrolysis process is dissociated into hydrogen and sociated reversible voltages in each case (discussed in more detail in
oxygen ions (O2−), leading to HER at the cathode. The oxygen ions are Section 5.1).
transported through the ceramic membrane to the anode, resulting in
oxygen evolution and the generation of two electrons, as shown sche-
matically in Fig. 4(c). The electrochemical cell used in this process is 3.1.4. High temperature solid carbon and hydrocarbon/CO gas assisted
called a solid oxide electrolysis cell (SOEC). The electrochemical reac- steam electrolysis
tions and the associated cell voltages (at 827 °C and 1 atm) for the In oxygen-ion conducting ceramic membrane (or SOEC) based
oxygen ion conducting ceramic electrolyte membrane based electrolysis CAWE (Fig. 4(h)), carbon and steam are supplied to the anode and
are summarised in Table 2. In principle, the SOEC operation is the re- cathode, respectively. In this configuration, one side of the cell acts as a
verse process of solid oxide fuel cell (SOFC) operation. The reversible direct carbon fuel cell (DCFC) and the other as a water electrolyser. The
voltage for the overall reaction at 827 °C is around 0.97 V, and as ex- corresponding electrochemical reactions that occur at the anode and
pected is lower than that at 25 °C (1.23 V) mentioned for the PEM based cathode are described in Table 2. Furthermore, in a PSEM based CAWE
system. This system can also use proton-conducting electrolytes, such as (Fig. 4(i)), carbon and steam are both fed to the anode, and hydrogen is
Sr or Ba-doped cerates and Zr-based materials [6,45]. The electro- produced at the cathode. In most of the studies on CAWE in a SOEC
chemical reactions for the proton-conducting solid electrolyte mem- system, yttria-stabilised zirconia (YSZ) has been used as the electrolyte;
brane (PSEM) based electrolysis process are the same as for the PEM Ni-YSZ, lanthanum strontium manganese oxides (LSM)-YSZ or Pt as the
shown schematically in Fig. 4(d). cathode; Ag, Sn, Pt or Ni-YSZ as the anode; and the operating tem-
perature range has been 600–1000 °C [89–97].
3.1.3. Low temperature carbon/liquid hydrocarbon assisted water In the hydrocarbon/CO gas assisted co-electrolysis, fuel gases such
electrolysis as NG or CO are used to assist high temperature steam electrolysis in
The CAWE process involves feeding solid carbon particles or carbon SOECs. Steam is supplied to the cathode and fuel gas to the anode
powder dispersed in water (carbon slurries) to the anode. The carbon in (Fig. 4(j)). YSZ was used as the electrolyte in these studies, which were
the solution participates in the electrolysis reaction, producing CO2 conducted in the temperature range of 700–900 °C. The electrochemical
and/or CO as the gaseous product on the anode side rather than oxygen reactions associated with this type of electrolysis are shown in Table 2
evolution reaction. The cathode reaction is the hydrogen evolution (at 827 °C). Limited studies have investigated fuel gas assisted water
reaction. The overall principle for the CAWE process for acidic electrolysis [25–27].
506
Table 2
Summary of the electrochemical reactions and the thermodynamic cell voltages for different type of electrolysis.
3.2. Thermodynamics and efficiency water gas shift (WGS) reaction. The chemical reactions associated with
SMR and WGS reaction are as follows [1,2,98,99]:
3.2.1. Water electrolysis
CH4 + H2O → CO + 3H2 ΔH at 25°C = +206 kJ mol−1 (2)
The maximum energy obtainable as work from a chemical reaction
−1
is determined by the Gibbs free energy change (ΔG) of the reaction CO + H2O → CO2 + H2 ΔH at 25°C = −41 kJ mol (3)
given by:
The well-known steam–carbon reaction (one of the important re-
ΔG = ΔH – TΔS (1) actions for coal gasification) produces H2-rich syngas from a variety of
carbon sources [34,35,100]:
where ΔH is enthalpy change and ΔS is entropy change. For the reaction
to be spontaneous, ΔG must be negative for the reaction (negative C + H2O → CO + H2 ΔH at 25°C = +31.14 kJ mol−1 (4)
thermodynamic potential).
As mentioned in the introduction, the common hydrogen produc- The chemical Eqs. (2) and (4) are endothermic, as indicated by the
tion technology involves steam-methane reforming (SMR) followed by enthalpy change values. To move the reaction forward for hydrogen
production, additional heat energy is required (i.e. the process needs to
507
Fig. 4. Schematic configuration of the fundamental operating principles of different types of electrolysis. Low temperature (a) polymer electrolyte membrane (PEM)
electrolysis cell; (b) alkaline electrolysis cell; high temperature solid oxide electrolysis cell (SOEC) based on (c) oxygen-ion and (d) proton conducting electrolytes;
low temperature carbon/coal-assisted water electrolysis (CAWE) in (e) PEM-based and (f) alkaline based cell; (g) low temperature liquid hydrocarbon assisted water
electrolysis; high temperature CAWE in SOEC based on (h) oxygen-ion and (i) proton conducting electrolytes; and (j) high temperature hydrocarbon/CO gas-assisted
water electrolysis. AEM = anion-exchange membrane; PSEM = proton-conducting solid electrolyte membrane (Sr/Ba–ZrO3/CeO3-based materials).
508
Fig. 4. (continued)
Table 3
Summary of the electrochemical reactions and the associated thermodynamic values for liquid hydrocarbon fuels assisted water electrolysis at 25 °C.
509
Fig. 5. Thermodynamic values of total energy (ΔH), electrical (ΔG) and thermal
(TΔS) demands for water electrolysis as a function of temperature at atmo-
spheric pressure. Thermodynamic values are taken from CRC Handbook of
Chemistry and Physics [123].
Fig. 6. Thermodynamic values of reversible cell voltage (E°rev) and thermo-

be carried out at high temperatures, in excess of 700 °C). neutral voltage (E°the) for water electrolysis as a function of temperature at
The electrolysis of water (H2O → H2 + ½O2) is an endothermic re- atmospheric pressure. Thermodynamic values are taken from CRC Handbook of
−1
action with ΔHat 25 °C = +285.83 kJ mol and ΔG at Chemistry and Physics [123].
−1
25 °C = +237.14 kJ mol . Fig. 5 shows the variation in these values as
a function of temperature. The figure also shows the entropy term (Eq.
Note that at thermo-neutral voltage of the cell, no exchange of heat
(1)) as a function of temperature. The figure reveals there is only a
is required between the cell and the surroundings. Fig. 6 gives the re-
small change in the total energy demand (enthalpy change ΔH) for
versible and thermo-neutral voltage values calculated respectively from
water electrolysis (< 100 °C) and steam electrolysis (> 100 °C) with
standard ΔG and ΔH for conventional water electrolysis process, as a
temperature. However, the ΔG that represents the electrical energy
function of temperature. As discussed earlier, the figure shows that no
input for the reaction decreases significantly with increasing tempera-
hydrogen generation occurs in the region below the Eorev. Thermal en-
ture. A significant drop in enthalpy change at 100 °C represents the heat
ergy is required in the region between the Eorev and Eothe for the elec-
of water evaporation.
trolysis process, i.e. a situation more favourable for electrolysis at a
The entropy term (TΔS), which represents the thermal input re-
high temperature where thermal input is provided in addition to elec-
quired for the reaction, increases with temperature. This means that for
tric input. The process becomes feasible above the Eothe (the minimum
an electrolysis process carried out at higher temperatures, for instance
applied cell voltage is ∼1.48 V at 25 °C), and the system, apart from the
in the case of an oxygen-ion conducting ceramic electrolyte membrane
electrolysis process, generates heat above this voltage.
(in SOEC system), the electrical input would be significantly reduced, as
the thermal input will be also contributing to the required energy for
the reaction. The thermal input for the reaction could come from a 3.2.2. Carbon/coal-assisted water electrolysis
range of sources, including waste heat from nuclear power plants (fu- As mentioned in Section 3.1, the participation of carbon in the
ture fast breeder reactors), thermal power plants, solar-thermal or in- electrolysis reaction results in lower reversible cell voltages, and is a
dustrial waste heat. Steam electrolysis at higher temperatures requires consequence of part of the electrical energy requirement being met by
lower cell voltages (electric input), with part of the energy provided by the chemical energy of carbon in the electrolysis process. However, the
thermal input, thus improving the overall electric efficiency of the reversible voltage of such a process is dependent on whether the carbon
process compared with low temperature (PEM or alkaline solution oxidation occurs to form CO2 (four-electron process) or CO (two-elec-
based) electrolysis processes that require most of the energy input as tron process), as summarised in Table 2. The reversible and thermo-
electric power [7,44,101]. neutral voltages for the electrolysis reactions (CAWE) given in Table 2
When the electrochemical reaction occurs in the cell, the relation- for four- and two-electron processes were calculated from their re-
ship between the standard Gibbs free energy change of the reaction ΔG spective ΔG and ΔH values, and are plotted as a function of temperature
and reversible voltage of the cell, Eorev, can be expressed as follows: in Fig. 7(a) (low temperature systems, such as PEM/AEM based elec-
−ΔG = nFE°rev (5) trolysis) and 7(b) (high temperature systems, such as SOEC).
Table 2 also shows that in terms of E°rev for the overall reaction, the
E°rev = −ΔG/nF (6) CAWE process (E°rev at 25°C = 0.21 V, n = 4) requires one-sixth of the
energy required for conventional water electrolysis (E°rev at
The reversible voltage of the electrolysis cell is the theoretical o
25°C = 1.23 V, n = 2) at room temperature. In terms of Ethe, the carbon
minimum voltage required to provide the electrical input for the water
participation in the electrolysis reaction decreases this value from 1.48
electrolysis reaction. However, this is only possible if the thermal part
to 0.46 V (less than one-third). Thus, it is possible to operate the elec-
of the energy (TΔS in Eq. (1)) is supplied from the surrounding en-
trolyser at a much lower cell voltage (correspondingly lower energy
vironment, which leads to cooling of the cell, and eventually the elec-
consumption) by using carbon in the electrolysis process. However, due
trolysis process ceases. Therefore, to continue electrolysis, the thermal
to overpotential losses in the electrochemical reactions at the respective
part of the energy for the reaction has to be supplied, and hence a
electrodes and ohmic losses within the electrodes, electrolyte and cur-
higher cell voltage than the reversible value is required. This cell vol-
rent collectors the operating voltage for the electrolysis is expected to
tage is called thermo-neutral voltage (Eothe) and is determined from the
be significantly higher than the Eothe. The thermo-neutral voltage is the
enthalpy change (ΔH) of the electrolysis reaction as follows:
actual voltage that must be supplied to the cells to start the electrolysis
E°the = −ΔH/nF (7) process. Therefore, even if the free energy requirement is satisfied by
operating the cell at voltages between E°rev and E°the (endothermic
510
Fig. 7. Thermodynamic values of reversible cell voltage (E°rev) and thermoneutral voltage (E°the) for carbon/coal assisted water electrolysis (CAWE) as a function of
temperature. (a) Comparison between water electrolysis and CAWE below 100 °C (HHV, liquid water); water electrolysis for E°rev (blue dash-dot-dot) and E°the (blue
dash); CAWE 4-electron reactions for E°rev (red solid) and E°the (red dot); CAWE 2-electron reaction for E°rev (green dash-dot-dash) and E°the (green dash). (b)
Comparison between steam electrolysis and CAWE from 100 to 900 °C (LHV, steam); Water electrolysis for E°rev (blue); CAWE 4-electron reaction for E°rev (red);
CAWE 2-electron reaction for E°rev (green). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
reaction zone), the electrical energy supplied is not sufficient for

splitting water, and external energy (heat source) would be essential
[6,35,37]. In contrast to low temperature electrolysis processes, the
operation of water splitting at higher temperatures is more favourable
in terms of thermodynamics and reaction kinetics. For instance, an
increase in temperature from 25 to 800 °C reduces not only the elec-
trical energy input (ΔG) required (reduction in E°the by ∼ 50%), but
also results in lower polarisation losses due to faster reaction kinetics.
The total electric power requirement, therefore, can be reduced by
using external waste heat from sources such as conventional coal, NG
and nuclear power plants [6,45,102–104]. Another observation from
Table 2 is the reduction in the thermo-neutral voltage at higher tem-
peratures for both conventional electrolysis (1.48 V at 25 °C to 1.29 V at
827 °C) and CAWE (0.46 V at 25 °C to 0.26 V at 827 °C). This is due to
the thermal energy input available at higher temperatures for the Fig.8. The electrolysis activity within the electrochemical potential windows
electrolysis process, as mentioned earlier. for water electrolysis (WE) and carbon/hydrocarbon assisted electrolysis
(CAWE) in acid medium at 25 °C and 1 atm. Conventional water electrolysis is
In terms of electrochemical kinetics of the redox reactions, the high
represented by the hydrogen evolution and oxygen evolution reactions (HER/
overpotential is necessary for desirable current density, due to the
OER), while the CAWE process is represented by the carbon–water oxidation
sluggish OER kinetics at the anode. This means that the anode reaction reaction (COR) and hydrogen evolution reaction (HER). A polymer electrolyte
for OER or carbon–water oxidation reaction (COR) processes has a very membrane (PEM) fuel cell can perform in a reversible mode by hydrogen oxi-
low exchange current density (j0), and the overall electrolysis process is dation and oxygen reduction reactions (HOR/ORR).
governed by slow kinetics. For example, the j0 for OER (j0, OER = 10−6
to 10−12 mA cm−2) is about three to six orders of magnitude lower than
time. The current efficiency of hydrogen production is expected to be
for HER (j0, HER = 10−3 mA cm−2) [7]. Although both water and COR
close to 100% if there is no short circuiting in the electrolysis cell, and
processes lead to a high anodic overpotential of electrolysis cells to
all the current passed through the cell contributes to water dissociation
achieve desirable hydrogen production rates (cell current density
to produce hydrogen. According to Faraday’s law, the power con-
of > 1 A cm−2) due to slow kinetics, the major advantage of the CAWE
sumption, Pi, for a water electrolysis process can be expressed as fol-
approach is that the anode overpotential can be dramatically reduced to
lows:
below 0.8 V, as illustrated in Fig. 8. The j−V curves representative of
the Butler–Volmer kinetics law are presented for different types of
Energy consumption, kWh m−3 = Vcell x (nF/3600) x (1/24.47)
electrolysis in acid medium at 25 °C and 1 atm. In particular, the re-
versible voltages (E°rev) of the overall electrolysis reactions involving = 2.19 x Vcell (8)
carbon/hydrocarbon are significantly lower (E°rev, carbon = 0.21 V) than
the conventional electrolysis (E°rev, water = 1.23 V). However, the CAWE where one molar volume of an ideal gas at 25 °C and 1 atm is considered
process can be expected to have similar issues with slower kinetics (j0, to be 24.47 L mol−1, n is the number of electrons involved in the HER
−5
mA cm−2) [72] and high overpotential (n = 2) and F is Faraday constant of 96,485 C mol−1. The minimum
methanol in electrolysis > 1 × 10
losses, depending on its electrochemical reforming/decomposition re- energy consumption in water electrolysis based on the thermo-neutral
action mechanism, molecular formula/weight and anode electro- voltage value of 1.48 V is calculated to be 3.24 kWh m−3
catalysts. (79.33 Wh mol−1) H2 at 25 °C and 2.83 kWh Nm−3 (69.15 Wh mol−1)
H2 at 827 °C. However, as mentioned earlier, due to the other losses in
the conventional electrolysis cell components, the cell operating vol-
3.2.3. Power consumption tage will be higher than the thermo-neutral voltage.
The power consumption (electric energy consumption) in an elec- Typically, the electrical energy requirement in conventional elec-
trolysis cell per 1 m3 of hydrogen produced can be calculated from the trolyser is 4.2–5.5 kWh m−3 H2 for the stack and 6.7–7.6 kWh m−3 H2
cell voltage and the current passed through the cell for a fixed period of for a system [6,105]. Fig. 9 illustrates the theoretical electric energy
511
Fig. 9. Diagram of the energy consumption for water and carbon/hydrocarbon assisted electrolysis (CAWE) for hydrogen production at low temperature (25 °C) and
high temperature (827 °C), calculated by Eq. (8): Vcell × 2.19 kWh m−3. Electrical energy consumption is calculated from the reversible cell voltage (E°rev) and total
energy consumption from the thermo-neutral voltage (E°the). The calculation for actual operation takes into account the cell resistance for both conventional water
electrolysis and CAWE. The voltage loss is considered to be 0.45 V (0.45 Ω cm2 at 1 A cm−2). Other parameters used in the calculation are: H2 molar volume
0.02447 m3 mo1−1 (25 °C and 1 atm) and density = 0.082 kg m−3.
requirements to produce 1 m3, 1 kg and 1 mol of hydrogen for con- 4. Carbon/coal assisted water electrolysis via aqueous
ventional water electrolysis and CAWE at a low temperature (25 °C) and electrochemical cells
high temperature (827 °C) at 1 atm. The values given in the figure are
electrical energy requirements based on ΔG and thermo-neutral voltage 4.1. Acidic media based system
(ΔH). The actual power consumption for an electrolysis cell operating at
reasonably high current densities (i.e. hydrogen generation rates) is One of the earliest studies on coal assisted electrolysis employing
also given assuming a typical cell area specific resistance of 0.25 Ω-cm2. aqueous electrolyte was by Coughlin and Farooque [33–37]. In a series
The figure shows that when using carbon in the anode reaction, the of experimental investigations, coal, char and lignite were used in
total electric energy consumption (based on thermo-neutral voltage) in acidic medium (H2SO4 solution). The experiments were conducted in a
the electrolysis process is 1.01 kWh m−3 (24.66 Wh mole−1) H2 at 25 °C simple beaker cell, with isolation between the anode and cathode
(HHV), which is less than one-third of the energy required for con- provided by a porous fritted glass. This allowed the generation of pure
ventional electrolysis. This means that based on the thermo-neutral hydrogen in a separate chamber and the prevention of inhibition re-
voltage, a CAWE can be operated by using only about 30% of the actions caused by impurities in the coal, such as sulfur, tar and ash. In
electrical input required for conventional water electrolysis at near most instances the cathode was a Pt mesh, and anode was Pt mesh,
room temperature. The situation further improves by operating the graphite rods or felt. The authors successfully demonstrated the onset
carbon assisted electrolyser at a higher temperature, for example at potential of HER at mild temperatures (20–115 °C) and potentials of
827 °C, where only 20% of the electrical input is required compared around 0.8 V (E°rev at 25 °C = 0.21). However, the coal oxidation rate
with the corresponding conventional electrolysis at 25 °C. Fig. 9 also recorded was very low, as reflected by the current densities
reveals that at practical hydrogen generation rates, more than half of (< 5 mA cm−2) due to high ohmic resistance of the electrochemical cell
energy consumption in the CAWE process could come from the che- employed. A simplified estimation of a scaled-up system, based on
mical energy of carbon, the anode reaction products being mainly pure 0.36 g cm−3 concentration of the coal slurry at an operating potential of
CO2 that can be easily sequestered. However, it is worth emphasising (i) 1 V, revealed that a system volume of 1.8 × 105 m3 could produce
the sluggish electrochemical and/or chemical oxidation kinetics of solid 100 tons hr−1 hydrogen at 39 °C by applying current of 32.5 mA
carbon, (ii) the mass-transport limitations due to the structure and [33–36]. Gas production was also analysed using gas chromatography
complex composition of carbon/coal, and (iii) the surface functional (GC). Almost pure hydrogen gas was detected at the cathode (hydrogen
groups, crystalline structure and impurities in coal, the effect of which electrode) with close to 100% Faradaic efficiency (FE; coulombic or
is not yet clear [13,20,35]. current efficiency), while a mixture of mainly CO2 and CO (about 9:1 by
512
volume, respectively) was identified at the anode using Pt and graphite Murphy and Bockris [108] studied the anodic oxidation of carbon
felt. It was suggested that a lower CO concentration was observed using by employing slurries of lignite, grass and household waste. The elec-
Pt anode due to higher electrocatalytic activity that promoted further trolytes used were H2SO4, H3PO4 and NaOH at 80–130 °C. The limiting
CO oxidation to CO2 [36]. During the electrochemical oxidation of coal current densities measured by cyclic voltammetry, with unwashed lig-
in these experiments, the coal oxidation and gas production rates de- nite at 1 V were around 10 mA cm−2, and were confirmed to be due to
creased with time, thereby increasing the required oxidation potential. the iron species leached out from coal. The steady-state current den-
The authors revealed that the reactivity loss might be attributed to the sities achieved for hydrogen evolution at 1 V were in the range of
formation of oxygen-containing functional groups, thereby preventing 1–5 mA cm−2. Investigations using washed coal slurries revealed that
electron transfer. Carboxyl groups are suggested to be the predominant the current density is three times greater when coal particles are al-
functional groups formed on the coal surface [34]. The carboxyl groups lowed to make contact with the anode. This is explained on the basis of
or carboxylated fragments can lead to formation of carbon oxide gases, coal/electrode collisions resulting in an increased dissolution of organic
aliphatic hydrocarbons and tar-like substances by a Kolbe-type reaction compounds from coal by mechanical abrasion. The authors suggest that
mechanism [33–35,106,107]: current densities can be increased to 200–400 mA cm−2 by forced
stirring of the coal slurry, increasing temperature (up to 180 °C) and
RCOO− + R’COO− → 2CO2 + RR’ + 2e− (9)
pressure (up to 10 bar), improving electrocatalysis and reducing pH.
− −
RCOO → CO2 + R’ + e (10) Baldwin et al. [46] studied voltammetric and electrolysis behaviour
of several coal mixtures (anthracite and bituminous) and coal-derived
where R’ is alkyl free radicals, and R and R’ are two different alkyl liquids in aqueous and organic solvents. The oxidation of aqueous coal
fractions. The activation energy measured for carbon (lignite) oxidation slurry started at ca. 0.64 V, while higher overpotential was observed in
rate in the temperature range 25–110 °C was estimated to be dimethylsulfoxide (DMSO) and acetonitrile solvents. The oxidation
9–13 kcal mol−1 in the oxidation potential range of 0.8–1.3 V [34]. current was attributed primarily to the oxidation of Fe2+ (produced by
Coughlin and Farooque also investigated the effect of process vari- catalytic oxidation of coal by Fe3+ ions leached from pyrite (FeS2) in
ables on coal oxidation rates [33–35]. The oxidation rates increased to the coal) to Fe3+. Dhooge and Park [47–50] describe in more detail the
different extents with an increase in cell voltage (0.7–1.2 V), slurry mechanism of the electrocatalytic oxidation of coal slurry. They report
concentration (12–300 g L−1), temperature (25–90 °C) and coal particle a similar observation to Baldwin et al., that when acid-washed coal
surface area (40–200 µm size range). The type of coal and its source also (with 3.6 M H2SO4 for ∼100 h) was tested; near zero oxidation current
had a significant effect on oxidation rates due mainly to the large was observed. This suggests that the coal slurry was catalytically oxi-
variability between different coals in terms of organic chemistry and dised by the existence of Fe3+ ions leached out from the coal into so-
inorganic species and their chemical form. Another variable studied lution. In the presence of Fe3+ ions, the reaction mechanism proposed
was the coal in contact with the anode and isolated from the anode; by several investigators [46,49] is as follows:
oxidation rates were an order of magnitude higher in the former case.
Measurements of the gas volumes generated at cathode (H2) and anode in the solution: C + 4Fe3+ + 2H2O → CO2 + 4Fe2+ + 4H+ (11)
(CO2 and CO mainly) revealed a high cathode to anode gas ratio of −
at the anode: Fe 2+
→ Fe 3+
+e (12)
about 8 at the beginning that eventually decreased with time to about
3+ 2+
4. This has been suggested to be initially due to the build-up of groups The Fe /Fe redox couple present in the coal slurry increases the
on the coal surface, such as eCOOH, eCHO and eCH2OH. Once a carbon oxidation rate. The CAWE process can be described as follows:
steady-state saturation of the coal surface was reached, further carbon (i) in the first stage the formation of surface oxides with changing coal
oxide products were produced as gases, such as CO2 and CO. This is surface structure and the removal of the mineral impurities occur and
reflected in the CO2 production efficiency, which initially started at (ii) in the second stage, the CO2 evolution reaction predominantly oc-
about 25%, but increased to around 50% with time [33,34]. curs due to the dissolved carbonate species (HCO3−, CO32−) present in
Okada et al. [51] re-examined the studies carried out by Coughlin the coal [47,50].
and Farooque [33,34] with anthracite and lignite coal slurries in H2SO4 To investigate the role of dissolved iron species and the effect of
solution. HER started at around 0.6 V and the limiting current density desulfurisation during coal electrolysis, Lalvani et al. [32,109] con-
obtained was 5–10 mA cm−2 at 80 °C. A similar current density was ducted electrochemical tests using a three-electrode arrangement and a
obtained in the presence of Fe2+ ions, but without any coal in the so- three-dimensional anode cell (made of heaped coal particles). Their
lution. The potential regions for the electrolysis reaction (0.7–1.2 V), preliminary experiments indicated that by coal electrolysis in acidic
initial current densities and the cathode current efficiencies (close to media, up to 40% of the total sulfur and a small quantity of nitrogen can
100%) were measured, and the results were similar to those reported by be removed from the coal. This is simultaneously accompanied by
Coughlin and Farooque. However, in contrast to the HER (cathodic leaching out of iron species in the acid electrolyte and the production of
current) efficiency of near 100% observed by both studies, the mea- hydrogen with FE over 95%. They also suggest that the Fe2+/Fe3+
sured CO2 evolution efficiency was only 5–10%. The latter value is redox couple acts as an electrocatalyst, as shown in the following re-
significantly lower than the 25–50% measured by Coughlin and Far- action mechanism:
ooque. The authors also observed that the coal slurries prepared in
FeS2 + Fe2(SO4)3 + 4H2O → 6FeSO4 + 4H2SO4 (13)
H2SO4 after sufficient washing of coal produced a current density of
only about 0.1 mA cm−2. This may be due to the removal of significant 2S + 6Fe2(SO4)3 + 8H2O → 12FeSO4 + 8H2SO4 (14)
inorganics (Na, K, Ca) that catalyse the oxidations reactions. The cur-
rent density with pure carbon powder under the same conditions as for Kusunoki and co-workers [110–112] have been actively involved in
coal was also very low (ca. 0.1 mA cm−2), but the FE of CO2 reached the area of coal desulfurisation and electrolysis. To examine the feasi-
80% in this case. The higher CO2 production current efficiency from bility of a large-scale cell in the CAWE, Kusakabe et al. demonstrated a
carbon compared with coal has been explained to be due to the pre- hybrid process of chemical desulfurisation combined with water elec-
sence of carboxyl, nitrogen and sulfur-containing molecules on coal trolysis using a flow-through packed-bed electrode cell [111]. They
surface that result in other by-products rather than CO2. The authors propose that chemical desulfurisation of coal can be achieved by
believe that coal oxidation at the anode involves two processes: (i) di- leaching the pulverised coal in acidic solutions (HCl or H2SO4) con-
rect collisional reaction of slurry particles with electrode and (ii) dis- taining Fe3+ ions (leached out from coal and/or added). This results in
solved impurity (Fe2+/Fe3+ redox and desorbed material) undergoing the formation of elemental sulfur and sulfates, followed by the elec-
oxidation. trolysis of coal filtrate in the flow-through cell. Fig. 10(a) and (b) shows
513
Fig. 10. Schematic drawings of (a) flow-through packed bed with Pt-plated Ti pellets with anolyte and catholyte circulated through each chamber, and (b) hybrid
process of CAWE combined with coal desulfurisation. Figure redrawn from [110,111].
the block diagram of the hybrid process and schematic of the flow- compared with 0.8 V in all other cases. The current densities measured
through cell, respectively. The chemical and electrochemical reactions with graphite slurry at 1.6 V were 10 times those measured by Okada
associated with the hybrid process are as follows. et al. [68], thus demonstrating the effect of the collision of graphite
Desulfurisation and coal oxidation: particles with the anode surface in the flow-through cell in the present
case. The current densities measured with coal slurry and filtrate were
FeS2 + 2Fe3+ → 3Fe2+ + 2S (15)
similar, but lower in the case of washed coal. Coal slurries with Fe3+
FeS2 + 14Fe 3+
+ 8H2O → 15Fe 2+ +
+ 12H + 2H2SO4 (16) added to 20-fold of the amount initially present in the coal resulted in
an order-of-magnitude increase in current densities compared with coal
Coal + 4Fe 3+
+ 2H2O → CO2 + 4Fe 2+ +
+ 4H + Others-oxidised/con- slurry in the absence of Fe3+. On the basis of these studies, the authors
sumed coal (17) postulate that anodic reactions in the coal slurry comprise the oxidation
Electrolysis reactions: of Fe2+ ions dissolved from coal and the reduction of Fe3+ by chemical
reactions with reducing compounds in coal. In addition, water-soluble
at the anode: Fe2+ → Fe3+ + e− (12) organic compounds in coal can partially oxidise to produce CO2 and
− CO. The study also highlighted the effect of collisions between the coal
at the cathode: 2H + 2e → H2
+
(18)
particles and anode electrode, which increased the rate of coal oxida-
The electrolysis cell used in Kusakabe et al.’s investigation consisted tion. Their suggested reaction mechanism is in reasonably good
of Pt-deposited Ti plates as anode and cathode, separated by a cation- agreement with that of Lalvani et al. [32,109].
exchange membrane (Nafion 415) [111]. The space between each Unlike the above studies, Taylor et al. [113] argue that CO2 evo-
electrode and the membrane was packed with graphite felt to increase lution from leached macromolecules of well-washed coals arises only at
the electrode surface area. The graphite felt in the cathode chamber was high anode voltages (> 2.8 V) with very low FE of CO2, with oxygen
electroplated with Pt to reduce hydrogen evolution overpotential losses. evolution as the main anodic reaction. However, this anodic potential is
Pyritic sulfur was removed (chemical desulfurisation) in a solution of much higher than the OER potential. Thus it is expected that the
1 M HCl and ca. 0.9 M Fe3+ at 90–110 °C in this flow-through packed- electrochemical coal oxidation is most likely mainly replaced by water
bed electrolysis system [111,112]. The coal filtrate used in the elec- electrolysis to produce oxygen.
trolysis process was prepared by treating pulverised coal in a solution of Carbon and carbonaceous materials (cellulose) assisted water elec-
4 M H2SO4 and 0.5 M Fe3+ at 110 °C for 2 h. The filtrate was circulated trolysis at a somewhat higher temperature (> 120 °C) and pressure
through the anode packed bed at 50 °C for the electrolysis experiments. (150 psi) than the previous studies was attempted by Clarke et al. [67]
The pyritic sulfur removal reported from these experiments for two to investigate the effect of these test conditions on the process. The
types of coals was 87–100%. The current densities achieved with Illi- Fe2+/Fe3+ redox couple was also used as a mediator. The limiting
nois No.6 coal filtrate were significantly high (100 mA cm−2 at 1 V), current densities achieved at 1 V with coal slurries (100 mesh,
due to the presence of graphite felt with no deactivation of felt after up 0.33 g ml−1) made with 2.5 M H2SO4 at 180 °C (150 psi) were
to 20 h of electrolysis; the power consumption for hydrogen generation 30 mA cm−2 with coal slurry alone, 150 mA cm−2 with added 0.13 M
was half that of conventional electrolysis. ferric ions and 200 mA cm−2 with added 0.25 M ferric ions. However,
In another study by Kusunoki and co-workers [110], the anode current density degraded after the initial period, due to sluggish dec-
chamber of the flow-through cell described above was packed with Pt- arboxylation of the thermally stable carboxylated surface of the coal
coated Ti pellets (5 mm long × 5 mm diameter pellets, instead of gra- particles. Clarke et al. concluded that two kinds of by-products were
phite felt) in contact with the Pt-coated Ti plate. This increased the produced during the CAWE process: soluble, thermally stable, low-
surface area of anode and created more collisions between the coal molecular-weight humic and fulvic acid substances, and heavily car-
particles in the coal slurry and the anode surface. The cathode chamber boxylated carbon fines. The economics of the CAWE under high tem-
was left unfilled. The slurries of different coals and activated carbon in perature and pressure as investigated by these authors will depend on
4 M H2SO4 were circulated through anode chamber at 50 °C, with a the reduction in power input to the system for hydrogen generation,
superficial velocity of around 10 cm s−1. The electrolysis investigations and the value of by-products formed in the process.
were carried out with 4 M H2SO4 alone, coal slurries made with dif- Thomas et al. [106,114] selected four different types of Alberta
ferent coals (Miike, Taiheiyo, Yallourn), washed Yallourn coal, acti- coals and studied the kinetics of the Fe3+ mediated electrochemical
vated carbon and purified graphite with added Fe3+. The electrolysis oxidation of coal in 1 M H2SO4 at 90 °C. They found that coal activity
process (H2 evolution) started at 1.6 V for H2SO4 electrolyte alone, for oxidation increases as the fixed carbon content (rank of coal) of coal
514
increases. The kinetic analysis of the current vs time data revealed two
rate constants corresponding to initial and later stages of coal oxidation;
this was explained in relation to the different organic functional groups
present on the coal surface. The authors suggested that the nature of the
functional groups, such as hydroquinones, phenols, aromatic amines
and organosulfur compounds, on the external surface of the coal would
be a more dominant oxidation factor in short-term periods (< 10 h) of
electrolysis, while the accessibility of Fe3+ ions in the internal pore
surface and within the solid coal matrix would be more important for
further oxidation of coal. This was also confirmed by measuring the CO2
generation current efficiencies, initially observed to be around 40%
after ca. 3 h of electrolysis (mainly due to oxidation of the coal surface)
and 70–80% after ca. 22 h (mainly due to the oxidation of coal medi-
ated by Fe3+ present in internal pore surfaces and within the solid coal
matrix).
After a relatively short hiatus, the strategy of using carbon in water
electrolysis was taken up again by researchers in 2005 due to the
growing demand for hydrogen as a renewable source of energy and the
increasing environmental consideration given to clean coal technology.
Yin et al. [115] fabricated multilayer nanoporous Ti/TiO2 films as a
catalyst support using an electrochemical etching method and in-
vestigated the catalytic activity of Pt, Ru, RuO2, IrO2 and their alloys
intercalated and deposited on the Ti/TiO2 film pores. These multilayer
structures showed the current density and amount of hydrogen pro- Fig. 11. Synergistic effect of K3Fe(CN)6 catalyst in HCl electrolyte for electro-
duction improved around twofold compared with those with pure Pt chemical oxidation of coal. Figure redrawn from [117].
and Pt-coated Ti electrodes. The best performance was achieved with
Pt–Ru supported on nanoporous Ti/TiO2 films, producing a current assume that the efficiency of CAWE process could be measured by
density of about 4 mA cm−2 at 1 V from coal slurry (< 6 μm particles at hydrogen generation as opposed to the CO2 generation efficiency con-
0.12 g L−1 concentration) prepared in 0.5 M H2SO4 at 85 °C. The FE sidered by some previous investigators. In the presence of Fe2+/Fe3+
achieved for H2 and CO2 gases were 98% and 10%, respectively. In ions in coal slurries (0.12 g ml−1 concentration in 5 M H2SO4), current
another study of carbon assisted electrolysis by Yin et al. [116], elec- densities as high as 62.7 mA cm−2 (dropped to 30 mA cm−2 in 8 h) at
trodes were prepared by dip coating a Ti sheet with inks containing Pt, 1 V and 163 mA cm−2 (dropped to 80 mA cm−2 in 8 h) at 2 V were
Ru or Ir individually or in combination followed by thermal decom- achieved at 100 °C. However, there was no significant effect on cell
position. The Ti/IrO2 electrode had the best performance of the elec- voltage without Fe ions. In addition, Hesenov et al. observed that the
trodes tested. organic compounds dissolved from coal into aqueous anolyte were
To increase the coal electrolysis rate, Yin et al. [116] used various strongly adsorbed on the Nafion membrane separator surface, and that
redox liquid catalysts such as Fe3+, K3Fe(CN)6, KBr and V2O5. The this membrane fouling hindered further migration of protons to the
better performance observed when using redox liquid catalysts was cathode.
explained on the basis of these catalysts bridging the coal particles and Seehra et al. [54] compared the HER rate for various carbon ma-
the solid electrode surface. The best performance obtained was with terials using an H-cell with anode and cathode chambers separated
Fe3+ due to Fe3+/Fe2+ dynamic transformation. Researchers from the from each other by glass frit, and employing 3.4 M H2SO4 as the elec-
same institute (Yu et al. [117]) also studied the effect of different trolyte (carbon slurries concentration ∼0.08 g ml−1) at room tem-
electrolytes (H2SO4 and HCl), and further investigated the effect of li- perature. The carbon sources used were: carbon GX203, Black Pearl
quid catalyst K3Fe(CN)6 on the electro-oxidation of coal in HCl. The (BP2000), single and multi-carbon nanotubes, graphite and coal. Using
results showed that HCl was more suitable for coal oxidation than nano-crystalline carbon (BP2000) with a high surface area
H2SO4, due to the Cl− anion interacting more strongly with coal par- (1500 m2 g−1) and high electrical conductivity, about a 10-fold in-
ticles. When K3Fe(CN)6 liquid catalyst was added into the coal slurry crease in HER rate was observed compared with carbon GX203 (SA
with HCl as electrolyte, the current densities were three times greater 1000 m2 g−1) at 1.12 V.
(ca. 10 mA cm−2 at 1.3 V). This catalytic mechanism seems to be a two- The physicochemical properties of carbon/coal have been also in-
step, indirect reaction. The dynamic transformation of [Fe(CN)6]3−/[Fe vestigated by other researchers [33,34,37,51,112]. The effect of ad-
(CN)6]4− redox proposed by the investigators is shown in Fig. 11 [117]: ditive catalysts was also studied using FeSO4 and Ce(SO4)2 in 3.7 M
H2SO4 [54]. By adding Fe ions to the BP2000 slurry, the energy re-
in the solution: 4[Fe(CN)6]3− + H2O + C → 4[Fe(CN)6]4− + 4H+ + other
quired for hydrogen generation at 0.72 V reduced to 30%. Gong et al.
coal intermediates (19)
[59] studied the effect of different kinds of coal slurries (lignite, bitu-
at the anode: [Fe(CN)6]4− → [Fe(CN)6]3− + e− (20) minous and anthracite coals, graphite) and catalyst additives in slurries
(FeSO4, Fe2(SP4)3, NiSO4, CoSO4) on cell voltage as a function of time.
Hesenov et al. [61,62] investigated the effects of various experi- They employed cyclic voltammetry in an electrolysis cell using 1.5 M
mental conditions, such as geometric area of the membrane, electrolyte H2SO4 as the electrolyte and Nafion N115 membrane as a separator
concentration, cell potential and coal type, as well as the relationship between the cathode and anode chambers, as shown in Fig. 12(a). The
between anode and cathode gas evolution. They observed that the overall cell voltage for CAWE fell with a decrease in the coal rank
generation of CO2 was independent of the HER in an H-cell with Nafion (lignite < bituminous < anthracite < graphite), which was ex-
117 membrane, because coal was indirectly oxidised in the electrolyte plained as being related to the surface functional groups present on the
media (see Eqs. (9) and (10)) and may convert into other organic matter coal surface. Further, the effect of presence of catalytic ionic species in
during the electrolysis. This was confirmed by analysing the total or- coal slurry on the cell voltage was Co2+ < Ni2+ < Fe2+ < Fe3+. In
ganic carbon (TOC) with a non-dispersive infrared detector and gas another study, Gong et al. [60] compared the cell voltages required for
analysis by GC connected to a thermal conductivity detector. They CAWE with raw and demineralised lignite coals. The electrolysis cell
515
Fig. 12. Schematic drawings of (a) ultrasonic bath system for CAWE and (b) mechanism for formation of total organic carbon in CAWE. Figure reproduced with
permission from [57,60].
used in this study was similar to the one in previous work [59]; how- pyritic sulfur in coal could be leached out as sulfate or elemental sulfur.
ever, the solution was kept stirred to improve mass-transfer with ul- These reactions can be summarised as follows.
trasonic wave energy. The authors demonstrated that due to the cata- In the solution:
lytic effect of ionic species present on the coal surface, the required cell
FeS2 + Fe2(SO4)3 + 4H2O → 6FeSO4 + 4H2SO4 (13)
voltage was lower for raw lignite than for demineralised lignite coal.
Moreover, in another study by Gong et al. [57], CAWE kinetics of three 2S + 6Fe2(SO4)3 + 8H2O → 12FeSO4 + 8H2SO4 (14)
types of coals (raw coal, coal washed in HCl and coal washed in HF) in
1 M NaOH solution was investigated by monitoring the TOC in the C + 4Fe + 2H2O → CO2 + 4Fe
3+ 2+ +
+ 4H + oxidised/consumed
electrolysis solutions. The effect of ultrasonic wave energy on the TOC coal/carbon (21)
was also investigated; ultrasonic waves are expected to affect TOC due C + 2Fe 3+
+ H2O → CO + 2Fe 2+ +
+ 2H + oxidised/consumed coal/
to the breaking of the coal structures and facilitation of mass transfer in carbon (22)
the solution. However, the activation energy values for CAWE were
found to only slightly change from 28.37 to 27.61 kJ mol−1. The TOC in At the anode: Fe2+ → Fe3+ + e− (12)
the electrolyte solution after electrolysis decreased with the presence of 3+ 2+
The standard equilibrium potential of the Fe /Fe redox reaction
mineral content in coal (raw coal > HCl-washed coal > HF-washed
is 0.77 V, which is within the experimental onset potential range of
coal), and this effect was more pronounced when using ultrasonic wave
0.5–1.0 V for CAWE [32,47,123]. At actual operating voltage, Fe2+
energy. Fig. 12(b) shows the mechanism of formation of TOC by CAWE
could be spontaneously oxidised at the electrode/electrolyte interface
in NaOH media as described by the authors using an unreacted
to Fe3+, and produce electrons, while the Fe3+ ions are reduced to
shrinking-core model. The main controlling step was thought to be the
Fe2+ again by carbon species in solution. The reactions (21), (22) and
chemical-oxidation reaction occurring between coal particles and the
(12) can also occur simultaneously. For this reason, in previous studies,
oxidising media, such as metal ions (Fe2+/Fe3+) as electron transfer
a sharp decline in the current density and hydrogen evolution rate have
mediators and the physisorbed/chemisorbed active oxygen, but further
been observed at voltages > 1 V, probably due to the faster con-
investigation is required to confirm this view. Chen et al. [118] in-
sumption of Fe2+ ions by reaction (12) compared with their re-
vestigated coal desulfurisation using ionic liquid-assisted coal water
generation by reactions (21) and (22). Thus, the kinetics of electro-
electrolysis in KNO3 by applying a constant current. However, their
chemical oxidation of both coal and Fe species need to be further
report mainly focused on desulfurisation of coal using methylimidazole-
examined. The current efficiency of the process should be analysed by
cation (Br−, BF4−, and Cl−) ionic liquids.
monitoring CO/CO2 generation rates to relate these to coal oxidation
In summary, the most common approach for acid-based CAWE is to
[54,65,124,125]. However, it is still difficult to provide a distinct evi-
use carbon/coal slurry mixed with 0.5–5 M H2SO4 solution in the
dence that Fe3+ ions react with carbon to regenerate Fe2+ ions in the
temperature range of 25–120 °C with Fe ions to facilitate solid carbon
CAWE process.
oxidation. The various additives investigated are: metal ion redox
The direct electrochemical conversion of solid coal/carbon at the
couples (Ce4+/Ce3+, V5+/V2+, Mn3+/Mn2+, I3−/I−, and Fe(CN)63−/
anode interface is thought to be intrinsically sluggish, as demonstrated
Fe(CN)64−) [49,54,109,116,117], metal halides (NaCl, NaBr, CeCl2,
by the low rates of CO2 generation. The main causes of this can be
and KBr) [32,109,116] and various anolytes (HCl, NaCl, HNO3, H3PO4,
summarised as (i) the lack of physiochemical contact sites at the anode
HClO4, and DMSO) [36,49,109]. Table 4 provides the details of the
for the reaction, (ii) poor dispersion of coal/carbon particles in the bulk
investigations carried out using different types of solid fuels and system
of slurries, (iii) continuous formation of passive oxide surface at the
configurations at low temperature in acid media, along with the best
coal/carbon anode, and (iv) the sluggish reaction kinetics of coal oxi-
performance achieved in each investigation. As proposed in the studies
dation compared with the oxidation of other coal impurities (e.g. other
reviewed above, the mechanism of CAWE – essentially, the electro-
organic matter, minerals). Thus, CAWE in aqueous electrochemical cells
chemical oxidation of coal or carbon with or without mediation by
can be mainly attributed to the indirect electrochemical oxidation
catalytic additives (i.e. metal ions) in acid media – can be described by
pathway via the redox couple of the dissolved metal ions as an elec-
a four or two-electron pathway (Table 2), as discussed below
trochemical mediator (see Table 4 for electrolyte additives). From the
[32,47–49,51,52,59,59,61,111,112,119–122].
work reviewed above on acidic solution electrochemical cells, we
In the acid electrolyte solution, Fe3+ ions are leached from coal
conclude that to date, relatively low current density (around
particles and coal/carbon can be also oxidised indirectly – see also Eqs.
50 mA cm−2) values have been reported for systems operating at <
(11), (12), (15)–(17), (19) and (20). Complex coal structures could be
100 °C under atmospheric pressures. High temperatures and pressures
broken down and surface functional groups changed; for example,
seem to favour this process, with current densities reaching
516
Table 4
Summary of CAWE performance using different types of fuels and system configurations at low temperature in acid media.
H. Ju et al.
Coal used Anolyte (supporting Additive Anode Anode Separator Cathode Cell Onset Cell Best performance (near Ref.
electrolyte) area/cm2 configuration potential/V temp./°C 0.8 ∼ 1.2 V)
Coal, lignite, 0.1–0.56 M H2SO4 Pt mesh 6.5and PFG Pt mesh BC 0.8–1.2 40–80 1.55 mA cm−2 at 1.2 V [34]
activated 96.5
charcoal, and
char
Coal, lignite, and 3.7–5.6 M H2SO4 Pt mesh 6.5 PFG Pt mesh BC 0.78 23–114 1.4 mA cm−2 at 0.83 V, [33]
char 23 °C
Coal, lignite, and 3.7–5.6 M H2SO4 Pt mesh 6.5and PFG Pt mesh BC 0.78 23–114 < 5 mA cm−2 at 0.9 V, [35]
char 96.5 114 °C
Lignite 4.1–5.6 M H2SO4, H3PO4, Graphite rods and felt, and Pt 104 PFG Pt mesh BC ∼0.85 40–114 < 5 mA cm−2 at 0.9 V, [36]
and trifluoromethane mesh 114 °C with graphite felt
sulphonic acid
monohydrate
Coal, lignite, and 5.6 M H2SO4 Pt mesh 96.5 PFG Pt mesh BC 0.84 110–114 1.4 mA cm−2 at 1 V, [37]
peat 114 °C with 10–30%
consumed fuels
Coal Various conditions with FeCl3, NaCl, Pt mesh, packed graphite 5.5, 10, PFG Pt mesh PB, and 3-D 0.67 22–80 40 mA cm−2 at 1.64 V, [32]
HCl, H2SO4, NaOH, and K2Cr2O7, and NaBr particles, and graphite felt 96.5, and anode cell (3ES) 80 °C with graphite felt in
HNO3 385 100 ml of 15% HCI + 5%
H2SO4
Coal Various conditions with Pt mesh 4 PFG Pt mesh BC (3ES) 75 325 mA cm−2 at 1.64 V, [109]
HCl, NaCl, CuCl2, 75 °C in 15% HCl + 5%
Ce2(SO4)3, and H2SO4 H2SO4
Anthracite, lignite, 1 and 4.15 M H2SO4 Pt plate and foil 3.55 and PFG Pt gauze BC and H-cell 0.6 25–80 5–10 mA cm−2 at 0.8 V, [51]
pure carbon, and 14 (3ES) 80 °C in 4.15 M H2SO4
517
washed slurries (FECO2 10%) with coal
Coal and liquefied 0.1 M LiClO4 in water, Pt mesh 6 medium PFG Pt mesh H-cell (3ES) 0.64 At room 1.3 mA cm−2 at 1.24 V [46]
coal DMSO, and acetonitrile temp.
Coal and activated 3.6 M H2SO4 Fe3+ and Ce4+ Pt K2SO4 SD Separated two 0.67 2 mA cm−2 at 1.04 V [47]
carbon cells (3ES) (FECO2 15–30%)
Coal H2SO4, H3PO4, HCl, and CeCl3, Fe2(SO4)3, Pt foil 10 K2SO4 SD Au-plated Separated two 20–70 3 mA cm−2 at 1 V (vs. [49]
HClO4 and FeSO4 bronze screen cells (3ES) NHE), 70 °C in 1.0 M
H2SO4 + 0.2 M Fe3+
(FECO2 100%)
Coal 0.1 M H2SO4 0.1 M Fe2(SO4)3 BC (3ES) 85–95 3 mA/g at 0.7 V, 85 °C [52]
Coal, activated 4 M H2SO4 Dissolved Fe Pt/Ti plate CEM Pt plate FPB with Pt/Ti 0.8 30–50 ∼10 mA cm−2 at 1 V, [110]
carbon, and pellets 50 °C
graphite
Coal 4 M H2SO4 Fe2(SO4)3, and Pt/Ti plate 100 N415 Pt/Ti plate FPB with 50–110 100 mA cm−2 at 1 V, 50 °C [111]
FeSO4 graphite felt (FECO2 100%)
Lignite, anthracite, H2SO4 Pt mesh 60 PFG Pt mesh BC (3ES) ∼0.5 60 6.6 mA cm−2 at 1 V with [113]
carbon black, coal
and bituminous
coal
Lignite, char, and 5% H3PO4 Au or Pt sheet Not used Pt sheet BC (3ES) ∼0.5 25–165 20 mA at 0.8 V, 165 °C [68]
graphite with lignite
Coal and petroleum H2SO4 Fe Ti Nafion SS Fluidization and ∼0.4 180 (150 200 mA cm−2 at 1 V with [67]
coke flow psi) 0.25 M Fe in 2.5 M H2SO4
channel
Bituminous and sub 1 M H2SO4 FeSO4·7H2O Pt foil Glass frit Pt gauze BC (3ES) ∼0.7 90 120 mA at 1 V, 90 °C with [106,114]
bituminous coal 15 mM FeSO4
Coal 0.5 M H2SO4 Ti/TiO2Pt–Ru, Ti/TiO2Pt, Pt, PFG Pt foil H-cell ∼0.4 85 5 mA cm−2 at 1 V, 108 °C [115]
and TiO2 with Ti/TiO2Pt–Ru (1:2)
(FEH2 ∼ 98%)
(continued on next page)
Applied Energy 231 (2018) 502–533
Table 4 (continued)
Coal used Anolyte (supporting Additive Anode Anode Separator Cathode Cell Onset Cell Best performance (near Ref.
H. Ju et al.
electrolyte) area/cm2 configuration potential/V temp./°C 0.8 ∼ 1.2 V)
Coal 1 M H2SO4 Fe3+, K3Fe(CN)6, Ti/Pt, Ti/RuO2, Ti/IrO2 and 4 PFG Pt foil H-cell (3ES and ∼0.4 75 1.6 mA cm−2 at 1 V with [116]
KBr, and V2O5 Ti/IrO2–RuO2 circulation) Fe3+
Coal 1 M HCl and 1 M H2SO4 K3Fe(CN)6 Ti/IrO2 9 PFG Pt H-cell ∼0.6 80 5 mA cm−2 at 1 V [117]
(circulation)
Activated carbon 3.7 M H2SO4 Pt plate 6.8 PFG Pt coil Double H-cell 0.2 At room ∼1.5 mA cm−2 at 0.8 V [53]
(3ES) temp.
−2
Activated carbon, 3.7 M H2SO4 FeSO4 and Ce(SO4)2 Pt plate 6.8 PFG Pt coil Double H-cell ∼0.4 At room ∼23.5 mA cm at 1 V [54]
CNT, graphite (3ES) temp.
powder, and coal
Coal 1–5 M H2SO4 100 mM Fe2+ and Pt 1 N117 Pt BC (3ES) 40–100 ∼60 mA cm−2 at 1 V, [61]
100 mM Fe3+ 80 °C with 5.0 M H2SO4
Coal 1 M H2SO4 100 mM Fe2+ and Pt 1 and 6 N117 Pt BC (3ES) and H- 40 ∼20 mA cm−2 at 1 V [62]
100 mM cell
Fe3+
Lignite H2SO4 PbAg 9 N115 Cu Ultrasonic bath 30 ∼78 mA cm−2 at 3 V [60]
Lignite, bituminous H2SO4 Fe2+, Co2+, and PbAg 9 N115 Graphite Water bath 1.99 ∼56 mA cm−2 at 3.54 V [59]
coal, anthracite, Ni2+ (3ES)
and high pure
graphite
Coal and graphite 1 M H2SO4 Fe3+/Fe2+ Pt, Pt–Ru, Pt–Ir, and Pt–Rh 2.1, 3.78, N117 Platinized Pt/ BC and U- 0.2 40 35 mA cm−2 at 0.8 V for [58]
foils 2.8 and Ti foil shaped cell coal with PtIr(4:1) and
2.61 100 mM Fe3+/100 mM
Fe2+
Coal and graphite 1 M H2SO4 100 mM Fe2+ and Rh, Pt–Rh, Pt–Ir, and Pt–Ir–Rh PM Pt/carbon Sandwich 0.8 80 25 mA cm−2 at 1.2 V for [63]
100 mM Fe3+ (5 mg cm−2)/carbon fiber/Ti fiber/Ti mesh (circulation) coal–graphite slurry with
518
mesh PtIr (FECO2 ∼ 30%)
Coal 1.5 M H2SO4 100 mM Fe2+ and PtIrRh/carbon fiber/Ti mesh 4 N117 Pt/carbon Sandwich 0.85 40–80 50 mA cm−2 at 0.85 V, [64]
100 mM Fe3+ fiber/Ti mesh (circulation) 80 °C (FECO2 ∼ 50%)
−2
Coal 4 M H2SO4 100 mM Fe2+ and Pt (6 mg cm ) and PtIr PM Pr and PtIr/ Sandwich 0.8 80–108 32 mA cm−2 (0.1 A) at [65]
100 mM Fe3+ (5.3 mg cm−2)/carbon fiber/ carbon fiber/ (circulation) 0.8 V, 108 °C
Hastelloy mesh Hastelloy mesh (FECO2 ∼ 57%)
Coal 4 M H2SO4 FeSO4·7H2O and [65] 2 PM [65] Sandwich -0.2 100–108 50 mA cm−2 at 0.8 V, [66]
Fe2(SO4)3·7H2O (circulation) 108 °C (FECO2 ∼ 70%)
Carbon black 1 M H2SO4 IrPt-Ti-mesh 50 N115 Pt/C on carbon Zero-gap cell ∼0.4 20–50 ∼15 mA cm−2 at 1.2 V, [28]
paper (circulation) 50 °C
2+
Carbon black 1 M H2SO4 100 mM Fe and IrPt-Ti-mesh 9 N115 40 wt% Pt/C Zero-gap cell 0.55 70 52 mA cm−2 at 1 V, 70 [125]
100–500 mM Fe3+ on Toray 120 (circulation) with 100 mM Fe2+ ion
3ES = three electrode system; BC = beaker cell; CEM = cation exchange membrane; FECO2 = Faradaic efficiency was calculated by CO2; FEH2 = Faradaic efficiency of H2; FPB = flow-through packed bed; N = Nafion;
NHE = normal hydrogen electrode; PFG = porous fritted glass; PM = polyethylene membrane; SA = salt bridge; SS = stainless steel
Applied Energy 231 (2018) 502–533
250 mA cm−2, but this raises serious material-related issues for acidic
[126]
[55]
[56]
[57]
Ref.
process conditions. The long-term stability of current density is also a
major concern, due to factors such as passivity of coal particle surfaces,
consumption of catalytic additives, and build-up of the soluble and
∼150 mA cm−2 at 1 V , 90 °C with

insoluble organic by-products in electrolyte solutions. Other inherent
Change of total organic carbon

∼5 mA cm−2 at 1.44 V , 25 °C
issues with the aqueous system are the (i) long path of ion migration
between the two electrodes contributing to the cell’s high ohmic re-
∼56 mA cm−2 at 1.44 V
ultrasonic in 1 M NaOH
sistance, (ii) role of reaction interface at the anode being as yet un-
optimised, and (iii) porous glass frit and polymer membrane acting only
Best performance
(FEH2 ∼ 98.6%)
as a separator for gas evolution, which limits the proton diffusion be-
concentration
3ES = three electrode system; BC = beaker cell; FECO2 = Faradaic efficiency was calculated by CO2; FEH2 = Faradaic efficiency of H2; PB = Pyrex beaker; PFG = porous fritted glass.
tween the two chambers.
4.2. Alkaline solution based system
Cell temp./
Only a few studies have investigated CAWE using alkaline electro-
25–90
50–90
10–90
lytes, such as NaOH and KOH. The main advantage of alkaline solution-
75
based CAWE is the easy formation and dissolution of the oxidation
°C
products from coal, such as humic, carbonic, acetic and several benzene
carboxylic acids [50,55]. Wapner and Lalvani [55] reported that the
potential/V
generated OH* radicals in the alkaline solution can play an important
Onset
role in the electrochemical oxidation of coal, by attacking coal mole-
∼0.5
cules via hydrogen abstraction and/or by addition to the aromatic
rings. Table 5 summarises some results from alkaline solution-based
Cell configuration
Ultrasonic bath
CAWE reported in the literature [55–57,126]. The current densities
achieved in these studies have been low, even at cell voltages as high as
BC (3ES)
BC (3ES)
BC (3ES)
1.4 V. Recently, Ge et al. [126] studied the mechanism of CAWE (coal,
demineralised coal, graphite) using a well optimised electrolysis cell
Summary of CAWE performance using different types of fuels and system configurations at low temperature in alkaline media.
with H2SO4, NaOH and HCl electrolytes; the peak current density
Pt gauze
achieved was 150 mA cm−2 with NaOH electrolyte at 90 °C. They
Cathode
Pt mesh
concluded that the rate of CAWE depends on the activity of carbon
Fe
Pt
material. They also observed that the indirect oxidation of coal via the
OH* radical was dominant at a low concentration of coal slurry
Porous Teflon
(0.1 mol L−1). However, the formation of oxidising radicals from acid
Separator
and alkaline electrolytes in the CAWE process and its indirect oxidation
Nafion
PFG
n/a
mechanism has not yet been confirmed. There is little information on
frit
the durability of the CAWE operation in alkaline media and the reaction
Anode area/
mechanism of OH* radical oxidation with carbon particles or coal sur-

face impurities.
12.74
cm2
4
9
5. Carbon/coal assisted water electrolysis via solid electrolytic

Graphite rod
routes
Pt gauze
Anode
5.1. Polymer electrolyte membrane based system

Fe
Pt
Additive
A wide variety of process conditions have been explored in aqueous

based CAWE to improve the reaction kinetics of carbon oxidation.
However, the primary limitations to using solid coal/carbon in liquid
1 M H2SO4, NaOH and
electrolyte-based systems are high electrolyte ohmic losses and poor ion
Anolyte (supporting
transfer from one electrode to the other due to the large separation
between the electrodes, as described in Section 4. One possible alter-
native to overcome this problem is to use a zero-gap cell configuration,
electrolyte)
1 M NaOH
1 M NaOH
which consists of gas-diffusion electrodes as the anode and cathode on

NaOH
both sides of a solid polymer electrolyte membrane (i.e. Nafion), known

HCl
as a membrane electrode assembly (MEA). This strategy has proved

very successful in reducing energy losses and increasing current effi-
Bituminous coal, de-ashed bituminous
ciency in other electrochemical systems, such as fuel cells [127,128],

coal and high purity graphite
water electrolysers [129,130] and electrocatalytic CO2 conversion cells

[131–133].
Botte and co-workers [58,63–66,134] recently studied the electro-
chemical oxidation of coal slurries using different noble metal catalysts
in the presence of Fe2+/Fe3+ redox couple. In these investigations,
carbon fibre wrapped around a Hastelloy or Ti mesh was used as a
substrate for the anode catalysts, as shown in Fig. 13(a). A number of
Coal used
noble metal catalysts (Pt, Pt–Ru, Pt–Ir, Pt–Rh) plated on the carbon
Table 5
fibre were evaluated in coal slurries (0.02 g ml−1) in the temperature

Coal
Coal
Coal
range of 40–108 °C. The Pt–Ir catalyst showed the best performance for
519
Fig. 13. Schematic configuration of (a) the procedure for the preparation of the catalyst/carbon fibre bundle/Hastelloy gauze and (b) the overall continuous CAWE
assisted electrolysis testing system. Figure reproduced with permission from [65].
the conversion of coal–graphite slurry. The experiments were con- density. This is 50% lower than the power required for conventional
ducted in a sandwich configuration of the electrochemical cell, with a water electrolysis.
proprietary polyethylene membrane as a separator and by maintaining In a recent study, Jin et al. [66] from the same group systematically
a regular flow pattern of the coal slurry over the electrode reaction investigated the effect of the concentration of Fe ions in coal slurry on
surface, as illustrated in Fig. 13(b). In this gap cell configuration, the electrolysis operation at a constant current. The experiments were
electrodes are merely touching and not bonded to the separator mem- conducted with coal slurries consisting of 20 mg ml–1 coal in 4 M H2SO4
brane (polyethylene or Nafion). The synergistic effect of the Fe ions in at 108 °C. Fig. 14(a) shows the effect of Fe ion concentration on cell
the coal slurry was demonstrated in terms of longer electrolysis time at voltage as a function of time, clearly revealing that electrolysis can be
stable cell voltages and under galvanostatic conditions. The authors sustained for a longer time at cell voltages below 1 V with higher
also attempted to break down the intrinsic reaction barriers of solid concentrations of Fe ions. The authors propose a possible reaction
carbon via increasing reaction temperature, which was explained on the mechanism for electro-oxidation of coal in the presence of Fe2+/Fe3+,
basis of surface films having a greater tendency to dissolve at higher as shown in Fig. 14(b). Fe3+ ions seem to play the role of a catalytic
temperatures. The FE of CO2 increased from 2.15 to 57.29% with an mediator in this process. The following six steps of electrochemical
increase in temperature from 40 to 108 °C [65]; however, the coal oxidation mechanism were hypothesised, although the reaction me-
conversion increased only from 0.2 to 3.2%. In these experiments, only chanism has not been fully confirmed for the electro-oxidation inter-
a small fraction of coal was consumed, even above 100 °C. The coal FE action between anode surface, coal particles and anolyte in the presence
of 91.15% was attributed mainly to coal oxidation due to the optimised of Fe2+/Fe3+ ions:
concentration of Fe ionic species in the solution, which means ∼8% of Step I: In the liquid coal slurry, Fe3+ ions are adsorbed on the coal
HER was attributed to the Fe2+ ions leaching out of the coal, as shown surface.
in Fig. 14(a). The energy consumption of the coal-assisted electrolysis Step II: The adsorbed combination of coal-Fe3+ ads transports to the
process in the presence of Fe ionic species in the coal slurry was anode interface.
22 Wh g−1 H2 (1.98 kWh Nm−3), corresponding to 32 mA cm−2 current Step III: The electro-adsorbed Fe3+ ads on the coal surface acts as a
Fig. 14. (a) Performance curves of coal slurries with various concentrations of Fe ions at 100 mA at 108 °C and (b) schematic of the predicted mechanism for the coal
electrochemical oxidation coupled with Fe2+/Fe3+ redox system. Figure redrawn from [66].
520
requirements for the process at high temperatures [6]. Recently, there

has been some interest in combining CAWE and SOEC for hydrogen
production, to capture the advantage of lower cell voltages required
due to the participation of carbon as well as higher operating tem-
peratures. Gopalan and co-wokers [89–92] proposed liquid Ag and Sn
as a consumable feed dispersed as a molten anode, with YSZ electrolyte
and Ni-YSZ cathode. The carbon rod was inserted into the liquid metal
anode (LMA) as a reductant and current collector, and the cathode side
was provided with a gas mixture of H2-H2O (steam) or H2, depending
on the operation mode. This system could be operated in two different
modes, like a reversible SOFC-SOEC: (i) in an electrolysis mode, to
generate hydrogen from coal particles with steam; and (ii) in a power
generation mode, to generate electricity from the hydrogen generated
during the electrolysis cycles. This high temperature CAWE with LMA
Fig. 15. CAWE performance using a polymer electrolyte membrane-based was operated at > 850 °C by feeding coal and hydrocarbon at the anode
electrolysis cell operated with and without the presence of Vulcan XC-72 in 1 M and steam into the cathode chamber. The oxygen ions (O2−) trans-
H2SO4 solution. Figure reproduced with permission from [28]. ported from the cathode through the solid electrolyte membrane react
with carbon at the electrolyte/anode interface or in the liquid metal
bridge between the coal and the anode. phase as follows:
Step IV: Fe3+ ads is reduced to Fe2+ to become adsorbed on the at cathode/YSZ interface: H2O (steam) + 2e− → H2 + O2− (23)
anode surface, and simultaneously coal particles are oxidised to CO2
−
and/or other intermediate species, such as CO or hydrocarbons [67]. at YSZ/LMA interface: O 2−
→ [O]LMA + 2e (24)
Step V: The anode-Fe2+ ads ions are oxidised at the anode to release at LMA/carbon interface: [O]LMA + R → RO (CO or CO2) (25)
into the solution as a regenerating mediator to form Fe3+ ions.
Step VI: During this process, passive films may grow on the coal overall: H2O + C → H2 + CO (26)
surface, preventing further oxidation by stopping the adsorption of
Gopalan et al. [92] suggested that the final product at the anode
Fe3+ ions and/or forming stable structures by combining with the ad-
could be mostly CO rather than CO2 at very high operating tempera-
sorbed Fe3+ ions [63,64].
tures and the overall reaction (26) is spontaneous in this condition. The
In another study, Giddey et al. [28] employed an MEA (electrodes
authors demonstrated the feasibility of this approach by feeding the
bonded to the electrolyte membrane) to investigate the benefits of
electrolyser with waste materials, such as high-density polyethylene. By
carbon assisted electrolysis. The MEA consisted of Ir black-coated, Pt-
applying a potential of 1.5 V, they achieved a current density of
sputtered Ti mesh as the anode, Pt/C catalyst coated on carbon paper as
0.3 A cm−2, producing 10 cc min−1 cm−2 (0.7–0.9 kWh Nm−3 of H2) of
the cathode, and a Nafion N 115 membrane as the electrolyte. The
high-purity hydrogen at the cathode as well as syngas at anode (mixture
investigations used 1 M H2SO4 solution with Vulcan XC 72 carbon
of CO, CO2 and H2).
powder. The current densities achieved ranged between 12 and
A steam-carbon fuel cell (SCFC) design has been proposed by Gür
15 mA cm−2 at 1.0–1.4 V at a cell temperature of 50 °C, as shown in
and co-workers [93–95,135,136] for the spontaneous and simultaneous
Fig. 15. The authors suggested that this type of solid electrolyte system
production of hydrogen and electric energy with open-circuit voltage
offers several advantages over aqueous electrolytes, such as the po-
(OCV) achieved in the range 0.1–0.6 V based on the H2/steam molar
tential to stack cells, achieve higher current densities and produce pure
ratio in the inlet stream to the cathode chamber. This new approach
CO2 for sequestration (CO2 and H2 are produced in separate chambers).
was extended from their air–carbon fuel cell (ACFC) reactor, one of the
Recently, Ju et al. [125] reported their findings on CAWE in a PEM-
categories of DCFC, which was operated by connecting a fluidised bed
based (Nafion 115) zero-gap electrolysis cell with continuous circula-
of coal gasifier with an anode-supported tubular SOFC [12,137]. In
tion of carbon slurry in the anode chamber. Average current densities of
another study, they modelled a coupled steam-carbon-air fuel cell
about 55 mA cm−2 were achieved for up to 1 h at 70 °C and at a con-
(SCAFC) that combines an ACFC and a SCFC with the carbon anode
stant voltage of 1 V using 10 wt% carbon slurry (Vulcan XC-72 carbon
chamber shared between the two type of cells, and that also separates
black) with 100 mM Fe2+ ions added as an electrocatalytic mediator.
the two dense solid electrolyte membranes (YSZ) of each cell, as de-
The presence of Fe3+ (even up to 500 mM) as an additive species had a
scribed in Fig. 16 [95]. The whole cell design of the SCAFC can be
negligible effect on CAWE, possibly due to the poor activity of carbon
expressed as:
and the absence of any involvement of Fe3+ ions in the electrolysis
reactions. The main reason suggested for the performance degradation O2(g)/Pt/YSZ/Pt/ C(s),CO,CO2 /Pt/YSZ/Pt/H2O(g),H2 (27)
of the electrolysis cell over time was the physical blocking of the re-
action interface by deposited carbon particles from the slurry. The ORR at the cathode/electrolyte (ACFC) and the HER (steam
reduction) at the cathode/electrolyte (SCFC) can be written as:
ACFC: O2,air + 4e− → 2O2− (28)

5.2. Solid oxide electrolyte membrane-based system
−
SCFC: H2Osteam + 2e → H2 + O 2−
(29)
The CAWE process is a potentially attractive, less energy-intensive
alternative to current technologies for hydrogen production. Using the The anode reaction for the both ACFC and SCFC in the shared anode
zero-gap cell system for CAWE at low temperatures seems to show some chamber would be the oxidation of CO produced by the Boudouard
promise, with 50% of the electric energy required (2.19 kWh m−3) reaction as:
compared with conventional electrolysis (> 4.1 kWh m−3). However, shared carbon chamber: 2CO + 2O2− → 2CO2 + 4e− (30)
breaking or decomposing complex physiochemical structures of coal
and CeC bonds, and the formation of passive films on coal surface and Boudouard reaction: Csolid + CO2 → 2CO (31)
other by-products with little value, are still major issues.
The model based on the above design predicted high efficiencies
Hydrogen production by steam electrolysis using high temperature
of > 76% for both, producing electric power and hydrogen at the same
SOEC is currently under development due to the low electric energy
521
Fig. 16. Schematics of a steam–carbon–air fuel cell. (a) The air–carbon fuel cell is shown on top and the steam–carbon cell is shown at bottom; the cell configuration
can be represented by O2/LSM/YSZ/Ni/C, CO, CO2/Ni/YSZ/Ni/H2O. (b) Button cell configuration. Figure reproduced with permission from [95].
time. Two planar cells were fabricated, one for ACFC operation and the voltage. The results indicate that CAWE can be realised at voltages
other for SCFC operation [95]. The electrolyte and anodes used for both around 0.7–1.0 V lower than those for steam electrolysis in the current
cells were YSZ and Ni cermet, respectively. The cathodes used for the density range of 0.2–0.3 A cm−2. Based on this work, the authors expect
air and steam-side electrodes were LSM-YSZ and NiO-YSZ, respectively. that CAWE can occur with only 30% of the electric energy requirements
Fig. 16(b) shows the schematic of the cell test arrangement. The two of conventional water electrolysis, and that the remaining energy will
cells were connected in series or parallel and operated at 900 °C. With be in the form of the carbon fuel’s chemical energy and the thermal
no power drawn from the coupled arrangement of cells, the voltage of input.
the steam–carbon cell could be held at −0.2 V, producing a current Table 6 summarises the various investigations performed for carbon
density of 270 mA cm−2 for both cells. The modelling of this kind of assisted electrolysis at high temperature, showing cell details, fuel used
arrangement revealed that if efficiency is the aim, a maximum cell ef- and the performance in terms of current density. A high temperature
ficiency of > 78% can be realised with a hydrogen production rate of CAWE process based on SOEs is still at an early stage of development,
1.22 kg m−2 day−1 and electric power density of 45 mW cm−2. This with challenges including durability of anode catalyst, system config-
corresponds to a cell voltage of 0.8 V for ACFC and −0.5 V for SCFC. uration, degradation in performance and techno-economics of the
The results indicate that the coupled SCAFC can realise a sixfold in- process. The technology also seems to be dependent on enabling tech-
crease in hydrogen production rates with only a twofold increase in nologies, such as DCFCs and coal gasification with CO2.
active cell geometry.
Ewan et al. [96] report the comparison of three different high
temperature electrochemical systems: DCFC, electrolysis cell (SOEC) 6. Hydrocarbon assisted water electrolysis
and CAWE using a YSZ electrolyte-supported button cell. The electrodes
used were bi-layers of Ni–YSZ/Ni–gadolinium-doped ceria (GDC) for 6.1. Low temperature liquid hydrocarbon assisted water electrolysis
anode, bi-layers of LSM/LSM–GDC for air cathode and Ni cermet for
steam cathode. The fuel used was char from pyrolysed biomass. The literature review above has highlighted a range of issues with
Fig. 17(a) shows the schematic of the cell test arrangement used by the carbon/coal-assisted electrolysis that still need to be resolved, and
investigators; Fig. 17(b) shows the voltage current characteristics for substantial effort and time may be needed to develop the technology to
the electrolysis and carbon assisted electrolysis cells at 700–800 °C and a commercial scale. With this in mind, another avenue of hydrogen
the contribution of carbon to the water electrolysis as a reduction in generation is being explored, which is based on the use of alcohols as a
source of hydrogen and energy to support the electrolysis process. The
Fig. 17. (a) Schematic of CAWE cell and the

associated reactions; (b) comparison of the
electrochemical performance for electrolysis.
Curves A, B and C are for a conventional solid
oxide electrolysis cell system and D, E, and F are
for a CAWE system at 700, 750, and 800 °C, re-
spectively. Figure reproduced with permission
from [96].
522
LSM = Sr-doped lanthanum manganite; ηth-H2 = theoretical hydrogen generation energy efficiency; SCAFC = coupled steam-carbon-air fuel cell (directly coupled to a Boudouard gasifier); SOFC = solid oxide fuel cell;
method is called organic solution assisted water electrolysis, or alcohol
[89]
[90]
[91]
[97]
[94]
[93]
[95]
[96]
Ref.
assisted water electrolysis. Scientists at NASA’s Jet Propulsion
Laboratory [22] employed an MEA consisting of PtRu catalyst de-
at 3.1 V, 1,000 °C (40% H2O at cathode)
Pmax: 8 mW cm−2 at 40.5 mA cm−2, 900 °C with button

posited on a carbon paper as the anode, Pt or Pd catalyst deposited on
cathode (generating both hydrogen and electricity)

25 mA cm−2 at -0.14 V, 900 °C with H2O flow at
300 mA cm−2 at 1.5 V (50% H2O-H2 at cathode)
270 mA cm−2 at -0.2 V, 900 °C (generating both

carbon paper as the cathode, and Nafion membrane as the electrolyte.
cell (generating both hydrogen and electricity)

at 3.1 V (40% H2O at cathode)
Methanol water solution was circulated on the anode side of the cell.
Current densities as high as 800 mA cm−2 at a cell voltage of about
0.5 V were reported. The authors suggested that the cost of hydrogen
production using methanol assisted water electrolysis (MAWE) may be
about half that of conventional water electrolysis, even when including
the cost of methanol.
hydrogen and electricity)

200 mA at 0.4 V, 900 °C
Since then, there have been more attempts in this direction, with the
use of methanol [69–78,138–147], ethanol/bio-alcohol [23,24,79,87,
Best performance
148–152], formic acid [81–83], glycerol [84,85,153–156], ethylene

−2
−2
ηth-H2: 83.7%
400 mA cm
400 mA cm
glycol [86] and biomass/high-molecular-weight hydrocarbon

[157–160] in the co-electrolysis of water (also referred to as CAWE and
electrochemical reforming). Table 3 summarises the electrochemical
reactions associated with different organic solutions, and thermo-
Cell temp./°C
dynamic values (ΔG, ΔH, E°rev, and E°the) of the cell reactions. Among
900–1,000
700–1,000
800–900
600–900
700–800
all the liquid hydrocarbons in the Table, the electrolysis reaction em-
1,000
1,000
ploying formic acid is the simplest, with only two electrons involved in
the reaction. The free energy being negative and the reversible cell
voltage (−0.17 V) being low for this reaction indicate the spontaneous
−0.2 at 1,000 °C (40%
Open-circuit voltage/V
nature of this reaction. However, in terms of cost effectiveness, high

0.1–0.6 (depend on
−0.2 (40% H2O at
hydrogen-bonding organic compounds, such as cane sugar and bioe-

H2O at cathode)
thanol, are also suitable for clean production of hydrogen. Several in-
vestigations have been made into MAWE employing PEM as the elec-
H2O/H2)
cathode)
-0.195
trolyte (mostly Nafion 117), to study the effect of methanol molar

0.26
concentration (1–10 M), type of anode catalyst with various catalyst

loadings (1–4 mg cm–2) and cell temperature (room temperature to
Steam-carbon cell (fixed-bed) with
Steam-carbon cell (fixed-bed) with
below 80 °C) on current densities and corresponding cell voltages.

Liquid anode SOFC (plate type)
Of the different liquid hydrocarbons investigated, methanol is a

high-energy-density liquid fuel (6 kWh kg−1, LHV) with 12.6 wt% hy-
Summary of CAWE performance using different types of fuels and system configurations at high temperature.
drogen content and is an attractive energy-storage and energy-transport

button and tube cells
Cell configuration
medium. The complete reaction of 5.34 kg of methanol can produce

1 kg hydrogen. Sasikumar et al. [71] carried out MAWE with an MEA
Button cell
button cell
consisting of 40 wt% PtRu/C as anode catalyst and 20 wt% Pt/C as

SCAFC
cathode catalyst, with three different thicknesses of Nafion membrane

to study the effect of methanol concentration, cell temperature, cell
voltage and membrane thickness. The best cell performance obtained
was a current density of 1.67 A cm−2 at 1.2 V using Nafion N112
Ni/zirconia
membrane with 4 M methanol concentration at 80 °C. In a recent study,

LSM-YSZ
Cathode
GIST and SK Innovation [73] report their findings on the optimisation

Ni-YSZ
Ni-YSZ
Ni-YSZ
Ni-YSZ
cermet
of operating conditions for MAWE in terms of current efficiency and

Pt
Pt
methanol loss. Pt and Pt–Ru black catalysts sprayed onto plain carbon
paper (for better wettability) were used as the anode, and Pt black on
t = thickness of solid electrolyte; YSZ = yttria-stabilised zirconia.
10.5% YSZ (t. 1.3 mm)
Teflonised, micro-porous carbon paper (5% wet proofing for easy re-
8% YSZ (t. 3 mm) and
Stabilised zirconia (t.
lease of H2 gas bubbles) was used as the cathode. Although the onset
6% YSZ (t. 2 mm)
6% YSZ (t. 2 mm)
YSZ (t. 0.3 mm)
YSZ (t. 0.1 mm)
voltage for methanol electrolysis was lower for the Pt–Ru catalyst than
YSZ (t. 1 mm)
for the Pt catalyst, the latter offered lower overvoltages at higher cur-
Electrolyte
150 μm)
6% YSZ
rent densities. The current efficiency values were similar in both cases,
with Pt catalyst having a value of 60–80% at current density of
0.3 A cm−2 at 0.67 V with 1 M methanol solution at 70 °C. This corre-
sponds to an energy consumption of 17.8 kWh kg−1 (1.46 kWh m−3)
compared with 51.55 kWh kg−1 (4.23 kWh m−3) for conventional
Ni/zirconia
electrolysis, thus showing a 65% saving on electric energy input. Pham

Ni-YSZ
cermet
Anode
et al. [74,75] investigated the effect of poly-tetrafluoroethylene (PTFE)

Ag
Sn
Sn
Sn
Pt
Pt
treatment of the anode gas-diffusion layer (GDL) and the size of sphe-
rical metal particles in the porous, sintered, spherical-metal-powder
(consumable
(consumable
(consumable
(consumable
flow field used for MAWE. Hydrogen production was improved by re-
Carbon source used
ducing the amount of PTFE treatment of the anode GDL, which was
carbon
Activated carbon
Activated carbon
suggested to be due to better electrical conductivity and wettability of

Biomass char
the GDL. The researchers concluded that more hydrophilic GDL may be
Activated
Coal rods
Coal rods
Coal rods
Coal rods
feed)
feed)
feed)
feed)
favourable for methanol transport to the anode catalyst and membrane

Table 6
interface, leading to lower applied voltage and higher FE of methanol-

assisted electrolysis to H2. The smaller spherical particles (350–500 μm)
523
in the porous flow field on the anode side led to improved performance,
due to better interfacial contact with the anode support.
Sethu et al. [78] investigated a Pt-catalysed membrane using the
non-equilibrium impregnation reduction method for direct deposition
of Pt on to the membrane for MAWE. The cell was assembled by putting
carbon cloth with a special pore design (GDL) on both sides of the Pt-
catalysed membrane. Graphite plates with parallel grooves were used as
bipolar plates for reactant distribution and current collection. A five-
cell methanol electrolyser stack with 50 cm2 active area of each cell was
assembled. At 50 A with a stack voltage of 3.95 V (at average single cell
voltage of 0.79 V), the stack produced 102 L h−1 H2 gas at 50 psi
pressure (4 M methanol at 80 °C). This corresponds to an energy con-
sumption of 1.89 kWh Nm−3 and shows about a 60% saving in electric
energy input to the electrolyser. The stack was operated at 1 A cm−2
current density for 2500 h and showed a very stable performance, with
negligible change in the stack voltage (3.95 V).
Recently, Ju et al. [147] investigated MAWE under different process
conditions using a variety of Pt–based catalysts (Pt/C, Pt/C–SnO2, Pt/
C–CeO2, PtRu/C, PtRu/C–SnO2 and PtSn/C) using an optimised cata-
lyst-spraying method in a PEM-based zero-gap electrolysis cell. The Fig. 19. Schematic diagram for potential mechanism of electrocatalytic oxi-
objective of this investigation was on-site/on-demand hydrogen gen- dation of ethanol on PtSn binary catalyst in the ethanol-assisted water elec-
eration with renewable energy to reduce the footprint of the latter, as trolysis process. Figure reproduced with permission from [148].
shown in Fig. 18(a). The normalised current densities with respect to
noble metal catalyst loading achieved at 0.8 V were in the order PtRu/ acetic acid) chemisorbed on the anode electrocatalyst active sites. The
C > Pt/C–SnO2 > PtRu/C–SnO2 > Pt/C > PtSn/C > Pt/C–CeO2, other possible sources of cell degradation, such as the swelling of the
as shown in Fig. 18(b). The authors suggest that the methanol oxidation Nafion membrane or a crossover of the ethanol from the anode to the
reaction in MAWE occurs by an indirect electrochemical oxidation in- cathode, were ruled out. The peak current density obtained with
volving the adsorption of OH– species on the secondary element (Ru or ethanol was 0.25 A cm−2 at 1.1 V with 6 M ethanol at 80 °C [23]. This
SnO2) of the catalyst. The Pt catalyst enhances the electro-oxidation of corresponds to an electric energy consumption of 2.62 kWh Nm−3.
COads or intermediate molecules on the Pt surface via a bifunctional In another study on EAWE by Lamy et al. [24], three Pt–based
mechanism [76,138]. In the optimum conditions of MAWE, the in- anode catalysts (Pt/C, PtSn/C and PtSnRu/C) were investigated to re-
vestigators achieved > 600 mA cm−2 current density at less than 1 V at duce the anode overvoltage of ethanol oxidation. Significantly high
60 °C with near 100% Faradic efficiency. reaction rates were observed at cell voltages under 0.9 V at room
Of the different options for sources of hydrogen, ethanol or bioe- temperature (20 °C) with Sn and Ru-modified Pt catalysts, resulting in a
thanol are very attractive due to their well-established supply chain current density of 100 mA cm−2. This is equivalent to a 220 cm3 h−1
from various natural biomass sources (corn, crops, agricultural waste hydrogen production rate while consuming less than 2.3 kWh Nm−3
and wood waste), relatively high hydrogen to carbon ratio (six H electrical energy. Recently, Ju et al. [148] reported their investigation
atoms), and ease of storage and transportation safety [79,88,148]. into an EAWE cell with Pt/C and PtSn/C as anode catalysts. Current
Recently, Caravaca et al. reported the use of ethanol [23] and 23.1% w/ densities of > 200 mA cm−2 were achieved at less than 0.75 V at 70 °C,
w bioethanol (waste from the wine industry) [79] in an ethanol-assisted clearly demonstrating the faster ethanol oxidation kinetics due to
water electrolysis (EAWE) cell. The MEA used in this investigation higher temperatures. The electric power input for the electrolysis was
consisted of a PtRu/C anode (3 mg cm−2), a proton conducting mem- 1.62 kWh m−3, a saving of > 50% electrical energy input compared
brane (Sterion) of 185 μm thickness, and 20 wt% Pt/C cathode with conventional water electrolysis cells. The authors propose a
(0.5 mg cm−2). The optimum reaction conditions were found to be plausible ethanol electro-oxidation mechanism in EAWE, based on the
4–6 M ethanol (or bioethanol) at 80 °C. Long-term tests on the elec- Faradaic conversion of ethanol and mass balance of the by-products
trolysis cell and subsequent regeneration tests confirmed that the de- identified/quantified using 1H nuclear magnetic resonance spectro-
activation behaviour of the cell could be attributed to a strong poi- scopy and gas analysis as illustrated in Fig. 19. The figure shows that
soning effect of reaction intermediate species (CO, acetaldehyde and the ethanol oxidation reaction leads to incomplete oxidation of ethanol
Fig. 18. (a) Schematic concept of methanol-assisted water electrolysis (MAWE) system integrated with renewable energy for clean hydrogen production. (b) MAWE
performance with 2 M methanol at 60 °C using Pt/C, PtRu/C, PtSn/C, Pt/C–SnO2, Pt/C–CeO2 and PtRu/C–SnO2 as anode catalysts. Water electrolysis performance
using IrPt catalyst on Ti mesh at 70 °C is also given for comparison. Figure reproduced with permission from [147].
524
to produce acetaldehyde and acetic acid. These reactions are strongly performance looks encouraging, but the long-term stability of the cell
dependent on the reaction potential and the properties of electro- was not studied.
catalysts, and the reaction pathway can lead to the formation of sec- Recently, Chen et al. [87] have reported their work on alcohol-as-
ondary intermediates in the presence of other metals (Sn, Pb, Bi and Ru) sisted electrolysis by employing an anion-exchange polymer membrane
with Pt catalyst [161–166]. However, the complete oxidation of ethanol (alkaline medium). Pd nanoparticles deposited on 3-D titania nanotube
generating 12 electrons via a one-step reaction is significantly limited arrays were used as an anode and Pt/C deposited on carbon cloth as a
under low temperature electrolysis conditions (< 100 °C) due to poor cathode for the cell. The organic solutions tested were ethanol, ethylene
catalytic activity to break the CeC bonds [23,166]. For these reasons, glycol, glycerol and 1,2-propanediol at temperatures from 25 to 80 °C,
previous EAWE results show lower current densities, as well as lower FE and 2 M NaOH was used as the supporting electrolyte. The peak current
of ethanol conversion to hydrogen as determined by CO2 evolution. density achieved with 2 M ethanol + 2 M NaOH at 80 °C was
Further, the reaction intermediates lead to faster cell degradation in 1.95 A cm−2 at 0.9 V. All organic solutions tested at 80 °C produced
EAWE than in MAWE. 1 A cm−2 current density at around 0.7 V, which corresponds to electric
Similarly, Osa et al. [138] have performed various liquid hydro- power input to the cell in the range ∼24 kWh kg−1 (∼1.97 kWh m−3)
carbon (methanol, ethanol and ethylene glycol)-assisted, PEM-based compared with 51.55 kWh kg−1 (4.23 kWh m−3) for conventional
electrolysis studies with a bimetallic Pt7Sn3/C catalyst (1.5 mg cm−2) at electrolysis. However, the alkaline based electrolysis cell required
temperatures in the range of 60–90 °C. MAWE showed the highest around 10 kg of NaOH for the production of 1 kg of hydrogen [138].
performance among the alcohols, due to easier electrocatalytic oxida- Deng et al. [157,158] studied a PEM-based electrolysis cell with
tion of simple carbon molecule (C1). Thus, to meet hydrogen produc- lignin to cogenerate valuable small organic molecules as well as hy-
tion cost targets (e.g. US Department of Energy cost of US$3–3.7 kg−1), drogen by using aqueous polyoxometalate solution as a catalyst and
several factors must be addressed, such as lower ethanol/bioethanol charge (electron–proton) carrier. They report that the electric energy
production cost, a high-quality product, and significantly higher consumption can be as low as 0.69 kWh Nm−3 H2 at 0.2 A cm−2, re-
ethanol conversion efficiency with a durable catalyst (good CO toler- quiring only 16.7% of the energy consumption of water electrolysis.
ance and promote C–C bond scission) [79,138,148]. This is an interesting approach for using notable liquid hydrocarbons in
A few studies have investigated formic acid-assisted electrolysis by a PEM-based electrolysis cell for the cogeneration of both hydrogen and
either employing PEM electrolyte-based cells [81,83] or aqueous elec- conversion/reforming of high-molecular-weight chemical compounds
trolyte-based cells [82]; however, the operating current densities (glycerol, sugar, pentose, glucose, cellulose, lignin, ethylene glycol) to
achieved so far are < 100 mA cm−2. Formic acid-assisted electrolysis value-added small organic molecules products for industrial platform
using an Ir oxide-coated titanium oxide anode was first performed by applications (furfural, 5-hydroxymethylfurfural; HMF, sorbitol, 1,3-di-
Kiliç et al. [81] using a cell that was operated at maximum current hydroxyacetone; DHA, formic acid) [21,88,151–155,158–160,168,
density of 50 mA cm−2 at 50 °C. Complete oxidation of formic acid to 169]. For obtaining such value-added or industrially important che-
CO2 and water was achieved, as measured by the chemical oxygen micals, the selective or controlled oxidation of alcohols and C4eC6
demand removal efficiency (95%) of the electrolysis process. In alkaline polyols can be achieved without the need for the complete electro-
media (NaOH), Guo et al. [82] found a very low operating electrolysis chemical oxidation into CO2 or cleavage of the CeC bond
voltage of 0.3 V using Pt foil electrodes, but the current densities seem [21,88,153,169].
to be relatively low (6 mA cm−2 at 0.7 V) and failed to produce any Table 7 summarises the details of the cell materials, electrolysis
reasonable flow rates of hydrogen. Carbon-supported, Pd-based anode onset potentials and best performance obtained by various investigators
catalysts (Pd/C, PdAu/C and PdPt/C) were investigated in a PEM-based for alcohol assisted electrolysis with PEM-based electrolysis cells. Al-
electrolysis cell by Lamy et al. to reduce overvoltages and improve the though this process shows significantly higher potential than carbon/
stability of the process [83]. They were able to achieve relatively low coal-assisted electrolysis for hydrogen generation due to high current
operating voltages of between 0.2 and 0.4 V at 100 mA cm−2 using Pd- densities achieved by some investigators with lower electric power
based electrocatalysts. However, the performance stability of the elec- input per kg of hydrogen produced, several issues still need to be ad-
trolysis process was an issue, as shown by the increase in cell voltages dressed. These include (i) high noble metal (i.e. Pt, Ir) catalyst loadings,
with time. The proposed reason for this was the fast deactivation of Pd (ii) degradation of membrane with organic solution crossover problems,
catalysts due to poisoning by the adsorbed species, such as formate, (iii) poisoning of the anode catalyst by reaction intermediate species or
formic acid and CO [83,167]. impurities in the original organic solution, (vi) relatively sluggish ki-
Some researchers are also exploring the use of biomass-derived netics of electrochemical oxidation of high molecular weight organic
compounds, such as glycerol [84,85,153–156] and ethylene glycol compounds at the anode, and (vii) the availability and cost of alcohol
[86], for electrochemical reforming using PEM-based electrolysis cells. and organic solutions as feedstock compared with the value added to
The anode catalysts used for the glycerol electrolysis cells were Pt on the hydrogen produced.
Ru–Ir oxide [84] and Pt–Ru on carbon support [85]. The current den-
sities achieved at voltages in the range 0.4–0.7 V were 5–10 mA cm−2 6.2. High temperature hydrocarbon/CO gas assisted steam electrolysis
at 70–80 °C. These current densities indicate slow reaction kinetics for
glycerol due to the 14 electrons involved in the complete oxidation to An alternative approach being investigated for reducing the electric
CO2. Investigations into the stability of the electrolysis process over a input to high temperature steam electrolysis for hydrogen production is
period of 150 min resulted in 50% reduction in current densities at 1 V by feeding steam to the cathode and a reducing gas (NG, CH4 or CO) to
(80 °C), showing possible poisoning of the anode catalyst [85]. Al- the anode chamber of a high temperature (700–900 °C) electrolysis cell
though it was claimed that glycerol-assisted electrolysis can decrease [25–27]. Lawrence Livermore National Laboratory (LLNL) [25] con-
the electric power input by 66% for hydrogen production, the operating structed a bench-scale SOE-based reactor to study the hydrocarbon/CO
current densities of around 10 mA cm−2 are too low for any practical gas assisted co-electrolysis process in 2003, as shown in Fig. 20(a).
significance. de Lucas-Consuegra et al. [86] studied ethylene glycol- Single YSZ electrolyte-based cells were investigated with a mixture of
assisted electrolysis with a Sterion based PEM, and Pt–Ru/C and Pt/C as H2/H2O on cathode side and reducing gas on the anode side. They
the anode and cathode catalysts, respectively. The energy efficiency considered two different NG oxidation conditions in the anode
obtained from the electrolysis system was 57% at 80 mA cm−2 current chamber: (i) partial oxidation to CO and H2 (hydrogen can be generated
density. This corresponds to an electric power consumption of at both electrodes in the system), and (ii) total oxidation to produce
1.53 kWh Nm−3 hydrogen. The peak current densities achieved were CO2 and steam. The complete oxidation of methane is expected to
around 250 mA cm−2 at 0.8 V with 6 M ethylene glycol at 90 °C. This produce the lowest cell voltages during electrolysis. LLNL has focused
525
Table 7
Summary of low temperature, liquid hydrocarbon fuels assisted water electrolysis performance based on a polymer electrolyte membrane (proton and anion-exchange membranes) system.
H. Ju et al.
Feed solution Anode Anodearea/cm2 Anode Membrane Cathode Feed rate Onset Cell temp./ Best performance (near Extended test Ref
electrode potential/V °C 0.8 ∼ 1.2 V)
MeOH Metal black or Me/C Nafion 0.3 5–120 800 mA cm−2 at [22]
(1–4 mg cm−2) < 0.6 V
MeOH 60 wt% PtRu/C (2.5 mg cm−2) 6.25 Carbon paper N117 Pt-WC/C and Pt/C 12 sccm (cir.) ∼0.25 30–90 200 mA cm−2 at 0.32 V, [69]
(TGP-H-060) (1.5 mg cm−2) 90 °C with 2 M MeOH
MeOH Pt 23 N117 Pt 5 sccm 350 mA cm−2 at 0.6 V 60 min [70]
with 17 M MeOH
MeOH 40 wt% PtRu/C (3 mg cm−2) 25 PI film/ N112, N115, N117 20 wt% Pt/C 0.4 30–80 500 mA cm−2 at 0.62 V, [71]
platinized Ti (0.5 mg cm−2) 80 °C with 4 M MeOH
mesh (N117)
MeOH Pt–Ru/C (4 mg cm−2), Pt/C 2 N117 Pt/C (2 mg cm−2) Batch type 23–75 200 mA cm−2 at 1 V (vs. 500 min [72]
(4 mg cm−2), PtRu black SHE), 75 °C with 16 M
(4 mg cm−2), and Pt black MeOH
(2 mg cm−2)
MeOH Pt black (3 mg cm−2), and PtRu 9 Carbon paper N115 Pt black ∼0.3 30–70 300 mA cm−2 at 0.67 V, 600 min: < 0.8 V [73]
black (3 mg cm−2) (SGL 25AA, (3 mg cm−2) 70 °C with 2 M MeOH
no wet proof) (Pt black)
MeOH 50 wt% PtRu/C (1 mg cm−2) 25 Carbon paper N117 50 wt% Pt/C 10 sccm ∼0.35 30–60 200 mA cm−2 at 0.5 V, [74]
(TGP-H-90) (1 mg cm−2) 60 °C with 2.6 M MeOH
MeOH 50 wt% PtRu/C (1 mg cm−2) 25 Carbon paper N117 50 wt% Pt/C 10 sccm 0.35 30 200 mA cm−2 at 0.65 V [75]
(TGP-H-90, (1 mg cm−2) with 8.5 wt% MeOH
no wet proof)
MeOH PtRu/C (Pt:Ru = 2:1) 7.29 FAA-2 60 wt% Pt/C ∼0.3 30–70 50 mA cm−2 at 1 V, [76]
(0.5 mg cm−2) (0.5 mg cm−2) 70 °C with 1 M MeOH
MeOH 80% Pt:Ru/C 4 Carbon paper N212 and 40% Pt/C 12 M KOH 60 10 mA cm−2 at 1 V with [77]
526
Pt-Ce polyethersulfone 12 M MeOH
Fe-Cu-Cr-Ce-Pt
MeOH Pt 50 Graphite N117 Pt ∼0.3 80 1,000 mA cm−2 at 2,500 h [78]
plate 0.79 V with 50 psi CC 1 A cm−2:
< 0.8 V
MeOH PtRu/C (Pt:Ru = 1:1) 5 N117 Pt/C (2 mg cm−2) 2 sccm (cir.) ∼0.25 (at 25–85 100 mA cm−2 at 0.963 V 20 min: < 0.8 V [139,140]
(4 mg cm−2) 85 °C) at 70 °C
MeOH PtPd (Pt:Pd = 7:3) (2 mg cm−2) 10 Graphite N117 40% Pt/C 1.9 A cm−2 at 1 V at [141]
plate (1 mg cm−2) 80 °C with 4 M MeOH
MeOH 40%Pt-20%Ru/C (3 mg cm−2) 30 TNT powder N117, ePTFE- 20% Pt/C cir. ∼0.3 60 400 mA cm−2 at 1 V at 120 min CC [143]
in ePTFE Nafion-TNT (t. (0.5 mg cm−2) 60 °C with 2–3 M MeOH 100 mA cm−2: <
substrate 30 μm) 0.6 V
MeOH 40%PtRu/C (3 mg cm−2) 5 Carbon cloth SPES 20% Pt/C cir. ∼0.4 30–80 550 mA cm−2 at 1 V at 35 h CC 0.5 A cm−2 : [145]
(0.5 mg cm−2) 80 °C <1V
−2
MeOH PtRu/C (3 mg cm ) 30 Carbon cloth N117 Pd nanoparticles 50 sccm ∼0.35 35–60 400 mA cm−2 at 1 V at 26 h CC [146]
or 20% Pt/C cir. 60 °C with 2 M MeOH 150 mA cm−2:
(0.5 mg cm−2) < 0.65 V
MeOH 40 wt% Pt/C, 40 wt% PtRu/C, 9 Carbon paper N115 40 wt% Pt/C 200 sccm cir. ∼0.4 30–60 440 mA cm−2 at 0.8 V at 4 h CC [147]
20 wt% PtSn/C, 40 wt% Pt/C- (SGL 25AA, (0.5 mg cm−2) 60 °C with 2 M MeOH 150 mA cm−2:
SnO2 (Pt:SnO2 = 3:1), 40 wt% no wet proof) using PtRu/C < 0.6 V
Pt/C-CeO2 (Pt:SnO2 = 3:1), and
40 wt% PtRu/C-SnO2
(Pt:Ru:SnO2 = 1.5:1.5:1)
(2 mg cm−2)
EtOH PtRu/C (Pt:Ru = 2:1) 6.25 Carbon paper Sterion 20 wt% Pt/C 330 ml h−1 ∼0.4 40–80 ∼100 mA cm−2 at 0.8 V, [23]
(3 mg cm−2) (0.5 mg cm−2) 80 °C with 6 M EtOH
(continued on next page)
Applied Energy 231 (2018) 502–533
Table 7 (continued)
Feed solution Anode Anodearea/cm2 Anode Membrane Cathode Feed rate Onset Cell temp./ Best performance (near Extended test Ref
H. Ju et al.
electrode potential/V °C 0.8 ∼ 1.2 V)
1h
CV 0.9–1.1 V:
30–200 mA cm−2
Bio-EtOH PtRu/C (Pt:Ru = 2:1) 6.25 Carbon paper Sterion 20 wt% Pt/C 330 ml h−1 ∼0.3 60–80 33.6 mA cm−2 at 0.8 V, 6h [79]
(3 mg cm−2) (0.5 mg cm−2) 80 °C with 4 M EtOH CV 0.8 V:
30–80 mA cm−2
EtOH 30 wt% Pt/C, 30 wt% PtSn/C, 5 Carbon cloth N 117 30 wt% Pt/C 20 100 mA cm−2 at 30 min [24,80]
30wt% PtSnRu/C (2 mg cm−2) (0.5 mg cm−2) 0.8–0.9 V with 2 M EtOH CC 100 mA cm−2:
<1V
MeOH, EtOH, 20 wt% Pt7Sn3/C (1.5 mg cm−2) 6.25 Carbon paper Sterion 20 wt% Pt/C 60 ml h−1 ∼0.4 60–90 400 mA cm−2 at 1 V 10 h [138]
EG (0.5 mg cm−2) with 6 M MeOH CC 0.5 A cm−2:
<1V
EtOH, EG, G, Pd nanoparticles (1.7 mg cm−2) 25 3D TiO2 A201 40 wt% Pt/C 4 sccm with 2 ∼0.3 25–80 2,000 mA cm−2 at [87]
1,2-P nanoute (0.3 mg cm−2) M NaOH 0.92 V, 80 °C with 2 M
arrays EtOH + 2 M NaOH
EtOH 40 wt% Pt/C 9 Carbon paper N115 40 wt% Pt/C 200 sccm < 0.2 60–70 275 mA cm−2 at 0.1 V, 125 h [148]
20 wt% PtSn/C (Pt:Sn = 3:1) (SGL 25AA, (0.5 mg cm−2) cir. 70 °C with 2 M EtOH CV 0.9 V:
(2 mg cm−2) no wet proof) 50–145 mA cm−2
EtOH Pd mesh (1.93 mg cm−2) 6.25 A901 20 wt% Pt/C 100 sccm with > 0.4 70–90 700 mA cm−2 at 1.3 V 150 h (5 cycles) CC [150]
(0.5 mg cm−2) KOH or NaOH with 2 M EtOH + 1 M 160 mA cm−2:
KOH < 1.1 V
EtOH, EG, G, AuPd/C (0.75 mg cm−2) 4 Ni foam A201 Pt/C with 2 M KOH ∼0.4 60 400–535 mA cm−2 at [151]
1,2-P, etc. (0.4 mg cm−2) 1 V with EtOH, EG, G
EtOH, EG, G, Rh/C (1 mg cm−2) 5 Ni foam A201 40 t% Pt/C 30 sccm with > 0.3 60 492 mA cm−2 at 0.7 V 40 min [152]
1,2-P (0.4 mg cm−2) 2 M KOH with EtOH CC 125 mA cm−2:
527
< 0.65 V
FA TiO2/IrO2 mesh 16 N 111 and 117 Pt 150 sccm with 25–50 50 mA cm−2 2.5 h [81]
Na2SO4 CC 50 mA cm−2
−2
FA Pt foil 1 Pt foil NaOH + FA, ∼0.3 6 mA cm at 0.7 V with 60 min CC [82]
cir. 2 M FA 8 mA cm−2
FA 40 wt% PdAu/C, 40wt% Pt/C 5 Carbon cloth N 117 40 wt% Pt/C cir. ∼0.2 25 100 mA cm−2 at 30 min [83]
(2 mg cm−2) (2 mg cm−2) 0.2–0.4 V with 5 M FA
Glycerol 20 wt% Pt/Ru-Ir oxide 3.14 Au plated N 212 20 wt% Pt/C 4.2 L h−1 > 0.4 70 10 mA cm−2 at 0.65V 30 min [84]
(3 mg cm−2) porous Ti (3 mg cm−2) cir. with 2 M CC 5 mA cm−2:
sinters < 0.8 V with 8.5 M
Glycerol 45.6 wt% Pt/C N 117 6 sccm ∼0.2 60–100 6 mA cm−2 at 0.6 V, 150 min [85]
53.3 wt% PtRu/C (Pt:Ru = 3:2) 80°C with 15% CV 1 V:
< 15 mA cm−2
Ethylene glycol 60 wt% PtRu/C (Pt:Ru = 2:1, 3.14 Sterion 20 wt% Pt/C 1–5 sccm ∼0.3 90 ∼250 mA cm−2 at 0.8 V, [86]
3 mg cm−2) (3 mg cm−2) 90 °C with 6 M EG
Alcohols, Polyoxometalates (POMs) 1 Graphite felt N 115 Pt black 30 sccm > 0.5 80 or light 500 mA cm−2 at 4000 s [157]
cellulose, solution (4 mg cm−2) irradiation 0.6–1.2 V CV 0.5 V:
lignin, 50 mA cm−2
biomass
A201 (t. 28 μm), A901 (t. 10 μm) = anion exchange membrane from Tokuyama; CC = constant current density; cir. = circulation; CV = constant voltage; EG = ethylene glycol; EtOH = ethanol; FA = formic acid;
FAA–2 = anion exchange membrane from FuMa-Tech; MeOH = methanol; N = Nafion (N115: t. 127 μm, N117: t. 175 μm, N212: t. 51 μm); P = –propandiol; PI = polyimide; PTFE = poly-tetrafluoroethylene;
SPES = sulfonation polyethersulfone; sccm = cm3 min−1 (ml min−1); Sterion = 180 μm; TNT = titanate nanotubes
Applied Energy 231 (2018) 502–533
Fig. 20. (a) Lawrence Livermore National Laboratory (LLNL)’s bench-scale reactor for a 100-W electrolyser stack and (b) comparison of polarisation curves of HOT
ELLY steam electrolyser and LLNL’s natural gas assisted steam electrolyser. Fig. (a) redrawn based on [25] and (b) and (c) reproduced with permission from [25].
their work on the total oxidation reaction mode at 700 °C, as no addi- The methane conversion in this case was considered to be an indication
tional water shift reaction and CO clean-up would be required. of the extent of methane reforming in the anode chamber. It was re-
Fig. 20(b) compares the performance of the NG-assisted steam elec- ported that the OCV and corresponding current densities obtained with
trolysis (LLNL at 900 °C) with conventional steam electrolysis (‘HOT conversions between 10 and 80% of methane were 0.22 V
ELLY’ system at 1000 °C) [25]. The cell consisted of a NiO/YSZ anode- (0.25 A cm−2) and 0.07 V (0.05 A cm−2) at 700 °C, respectively. These
supported tube with a coated YSZ electrolyte thin film. The electrolysis results demonstrate the feasibility of CO gas assisted co-electrolysis, and
current density achieved at 0.5 V was 2.8 A cm−2 at 900 °C and the possibility of obtaining high hydrogen production rates without the
1 A cm−2 at 700 °C (see Fig. 20(c)). An analysis of the energy flow with need for applying external potential to the cell. It is worth mentioning
a heat exchanger revealed a system efficiency of up to 70% based on that the advantage of this route of hydrogen production compared to
primary energy input. The operating temperatures of 900 °C produced conventional steam reforming is that CO2 is generated in a separate
higher current densities, but led to carbon deposition on the anode. This chamber, and would be easy to sequester. Table 8 Summarises the high
situation can be partly avoided by feeding a higher proportion of steam, temperature, hydrocarbon/CO gas assisted steam electrolysis perfor-
but leads to lowering of the temperature due to the endothermic nature mance achieved by various investigators based on a solid oxide elec-
of steam reforming. Therefore, the authors suggested operating the cells trolysis cell system.
at temperatures near 700 °C.
Wang et al. [26,27] evaluated ceria based porous composite elec-
trodes (Cu–CeO2–YSZ, Cu–Co–CeO2–YSZ, Pd–CeO2–YSZ) with 8 mol% 7. Technology status, challenges and opportunities
YSZ (50 μm thick YSZ disc layered between 50 and 300 μm thick porous
YSZ layers). The reducing gases used in the anode chamber of the cell Hydrogen production from a carbon source, such as coal, alcohol,
were CO and CH4. The cell with Pd–CeO2–C–YSZ (anode)/YSZ/Co–- methane (NG) and biomass, using aqueous electrolytes or solid polymer
CeO2–YSZ (cathode) using humidified CH4 at 0.5 V was found to pro- electrolyte membranes at low temperatures and solid oxide electrolyte
duce the highest catalytic activity and current densities of 0.45 A cm−2 membranes at high temperatures could be a promising, practical tech-
at 700 °C [27]. The cell OCV values obtained were 21 mV for CH4 and nology for the world’s transition to a low-emission economy. Current
−74 mV for CO at 700 °C. The cathode (Co–CeO2–YSZ) gas supplied in progress in system efficiency and plant capacity for different hydrogen
this case was a mixture of 20% H2O/80% H2. In another study with the production technologies is illustrated in Fig. 21. However, the practical
above cell, Wang et al. [26] investigated the extent of CH4 conversion applications of these technologies would demand proven reliability and
using simulated gas compositions of gas mixture (CH4, CO2 and H2O). long-term sustainability.
Table 8
Summary of high temperature, hydrocarbon/CO gas assisted steam electrolysis performance based on a solid oxide electrolysis cell system.
Feed Anode Membrane Cathode/feed Onset potential/V Cell temp./°C Best performance Ref.
−2
Natural gas (NG) Ni-YSZ YSZ Ni-YSZ/steam/H2 −0.2 900 2.8 A cm at 0.5 V [22]
−0.2 700 1.0 A cm−2 at 0.5 V
Methane Pd-CeO2-YSZ YSZ Co-CeO2-YSZ/steam/H2 700 OCV 0.22 V, [69]
Current: 0.32 A cm−2
Methane/CO Pd-CeO2-YSZ YSZ Co-CeO2-YSZ/steam/H2 700 OCV 21 mV (CH4) [70]
OCV −74 mV (CO)
528
anode catalysts would have to be developed to avoid or minimise

poisoning due to intermediate compounds formed in the oxidation
process
• Apart from methanol and formic acid, the breaking of C–C bond in
other alcohols/polyols is still a challenge; thus the complete con-
version of these fuels into CO2 would be an issue unless either new
catalysts are developed for complete conversion, or the intermediate
products formed have an added value/application
• Crossover of the alcohols from cathode to anode chamber in the
polymer membrane cell results in loss of alcohol, so new membrane
materials less prone to alcohol crossover would need to be devel-
oped
• All alcohols are potentially toxic and their by-products might also
cause other hazardous problems; they could be potentially harmful
to the environment, corrosive to cell materials, and flammable due
to low vapour pressure [170,171], requiring materials, strategies
and regulations to overcome these issues
Hydrocarbon/CO gas assisted steam electrolysis
• High temperature operation increases the kinetics of the electrolysis

process and will require only non-noble metal catalysts, but can
Fig. 21. Efficiency comparison of various hydrogen production technologies as
cause various material-related issues that will require development/
a function of scale of hydrogen production. Information collected from refer-
ences [1–8,172–174]. AEM = anion-exchange membrane; CAWE = carbon/
improvement of cell materials
hydrocarbon assisted electrolysis; CSP = concentrating solar power; • Methane supply to the anode may cause carbon deposition based on
NG = natural gas; PEC = photoelectrochemical cell; PEM = polymer electro- the anode catalyst, temperature and methane-to-steam ratio
lyte membrane; SOEC = solid oxide electrolysis cell. • Methane oxidation to CO2 is the preferred reaction in the anode
chamber, rather than reforming, to realise the full benefit of re-
duction in electrochemical potential of the cell (thus power input for
7.1. Challenges for electrolysis
electrolysis); this may require a detailed study on optimisation of
anode catalysts and other process variables
Various fundamental and engineering challenges need to be further
studied and optimised to progress towards commercialisation of CAWE
7.2. Opportunities and potential for carbon sources in electrolysis
technology for hydrogen generation. These are summarised below for
different categories of CAWE.
Despite the challenges facing the development and commercialisa-
Solid carbon assisted water electrolysis
tion of this technology, there is enormous potential for various carbon
• System configuration and operating conditions, such as reaction sources to make electrolysis less energy intensive for hydrogen gen-
eration. This has been demonstrated by many investigators. For ex-
interface design between electrode and membrane, pre-mixing of
ample:
the carbon source, coal slurry feeding rates and design for con-
tinuous coal slurry feeding to the reactor.
• Methods of improving current density and long-term performance, • Current densities in the range of 100–200 mA cm −2
at cell voltages
around 1 V have been achieved for coal slurry-assisted electrolysis in
and minimising the cell component degradation that increases the
aqueous electrolyte cells with mediator redox couples, such as iron
required cell voltages to maintain certain current densities.
• Effect of physicochemical properties of coal and biomass – particle
•
species, as additives [67,111] (see Tables 4 and 5)
Activated carbon and biomass char assisted steam electrolysis em-
size, porosity and crystallinity, impurities, surface functional groups
ploying SOEC reduces cell voltages to less than 0.4 V to achieve
and passive layers formed on the surface of coal particles due to
current densities in the range of 200–300 mA cm−2 at temperatures
electro-oxidation.
• Properties of carbon slurry fed to the electrolysis cell, such as par-
•
700–900 °C [81,96], as shown in Table 6
Liquid hydrocarbon assisted water electrolysis can produce current
ticle dispersion, slurry viscosity and wettability.
densities close to or above 1 A cm−2 at cell voltages < 1 V (MAWE
• Suitability of anode and electrocatalyst materials for the type of coal
and EAWE) [22,78,87,147], as shown in Table 7
used for the electrolysis, and development of electrocatalysts tol-
erant to impurities in coal that also assist in the electro-oxidation of • A five-cell methanol assisted electrolysis stack has produced
1 A cm−2 current density for 2500 h with negligible change in the
coal.
• Role of additives, such as redox couples, to improve reactivity and
•
stack voltage (3.95 V) [78]
Methane (NG) assisted steam electrolysis using SOEC has produced
reaction kinetics to achieve high current densities as well as improve
current densities of 1 A cm−2 and 2.8 A cm−2 at 700 and 900 °C,
coal electro-oxidation.
• Significance of coal desulfurisation and other by-products formed in
respectively [25], as shown in Table 8.
the coal slurry electrolysis.
The high current densities achieved for various carbon/hydrocarbon
assisted water electrolysis processes at lower cell voltages compared
Liquid hydrocarbon assisted water electrolysis
with conventional electrolysis for hydrogen generation has also de-
• Various alcohols and liquid hydrocarbons can be considered as fuel monstrated electric energy input savings in excess of 50%.
for certain applications, and their use to produce hydrogen will need
8. Conclusion
to be further justified from energy as well as economic point of view
• Cell stability has been shown in literature to some extent, but new
Carbon/hydrocarbon assisted electrolysis has the potential to offer a
529
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Applied Energy 231 (2018) 502–533

Contents lists available at ScienceDirect

A comprehensive review of carbon and hydrocarbon assisted water T

• Carbon/hydrocarbon assisted water

1. Introduction reduced and hydrogen can be generated at distributed or end-use sites

Fig. 6. Thermodynamic values of reversible cell voltage (E°rev) and thermo-

reaction zone), the electrical energy supplied is not suﬃcient for

electrolyte) area/cm2 conﬁguration potential/V temp./°C 0.8 ∼ 1.2 V)

∼150 mA cm−2 at 1 V , 90 °C with

Change of total organic carbon

∼56 mA cm−2 at 1.44 V

4.2. Alkaline solution based system

mechanism of OH* radical oxidation with carbon particles or coal sur-

5. Carbon/coal assisted water electrolysis via solid electrolytic

5.1. Polymer electrolyte membrane based system

A wide variety of process conditions have been explored in aqueous

which consists of gas-diﬀusion electrodes as the anode and cathode on

both sides of a solid polymer electrolyte membrane (i.e. Naﬁon), known

as a membrane electrode assembly (MEA). This strategy has proved

ciency in other electrochemical systems, such as fuel cells [127,128],

water electrolysers [129,130] and electrocatalytic CO2 conversion cells

ﬁbre were evaluated in coal slurries (0.02 g ml−1) in the temperature

requirements for the process at high temperatures [6]. Recently, there

ACFC: O2,air + 4e− → 2O2− (28)

Fig. 17. (a) Schematic of CAWE cell and the

at 3.1 V, 1,000 °C (40% H2O at cathode)

Pmax: 8 mW cm−2 at 40.5 mA cm−2, 900 °C with button

cathode (generating both hydrogen and electricity)

270 mA cm−2 at -0.2 V, 900 °C (generating both

cell (generating both hydrogen and electricity)

hydrogen and electricity)

148–152], formic acid [81–83], glycerol [84,85,153–156], ethylene

glycol [86] and biomass/high-molecular-weight hydrocarbon

nature of this reaction. However, in terms of cost eﬀectiveness, high

hydrogen-bonding organic compounds, such as cane sugar and bioe-

trolyte (mostly Naﬁon 117), to study the eﬀect of methanol molar

concentration (1–10 M), type of anode catalyst with various catalyst

Steam-carbon cell (ﬁxed-bed) with

below 80 °C) on current densities and corresponding cell voltages.

Liquid anode SOFC (plate type)

Liquid anode SOFC (plate type)

Liquid anode SOFC (plate type)

Of the diﬀerent liquid hydrocarbons investigated, methanol is a

drogen content and is an attractive energy-storage and energy-transport

medium. The complete reaction of 5.34 kg of methanol can produce

consisting of 40 wt% PtRu/C as anode catalyst and 20 wt% Pt/C as

cathode catalyst, with three diﬀerent thicknesses of Naﬁon membrane

membrane with 4 M methanol concentration at 80 °C. In a recent study,

GIST and SK Innovation [73] report their ﬁndings on the optimisation

of operating conditions for MAWE in terms of current eﬃciency and

Stabilised zirconia (t.

6% YSZ (t. 2 mm)

YSZ (t. 0.3 mm)

YSZ (t. 0.1 mm)

electrolysis, thus showing a 65% saving on electric energy input. Pham

et al. [74,75] investigated the eﬀect of poly-tetraﬂuoroethylene (PTFE)

suggested to be due to better electrical conductivity and wettability of

favourable for methanol transport to the anode catalyst and membrane

interface, leading to lower applied voltage and higher FE of methanol-