Advanced Energy Materials - 2020 - McHugh - Decoupled Electrochemical Water Splitting From Fundamentals To Applications

Review
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Decoupled Electrochemical Water Splitting: From

Fundamentals to Applications
Patrick J. McHugh, Athanasios D. Stergiou, and Mark D. Symes*
rely on fossil fuels is of great importance.

Electrolytic water splitting to generate hydrogen and oxygen is one of the Renewable energy sources, such as wind,
most promising ways in which to harness intermittent renewable power solar, and tidal energy constitute argu-
sources and store the energy these provide as a clean-burning and sustainably the most promising of these clean
energy solutions, but suffer from the fact
able fuel. In recent years, this has led to an explosion in reports on electro- that they are intermittent.[6] Direct power
chemical water splitting, most of them focused on improving the efficiency supply from these sources therefore
of the electrochemical reactions themselves. However, efficient generation of cannot be relied upon to satisfy instan-
hydrogen and oxygen is of little use if these products cannot be kept sepa- taneous energy demands.[7] A means of
rate and the community is now coming to realize that there are considerable storing the energy generated by these
renewable sources is therefore essential if
challenges associated with maintaining adequate separation between H2 and
we are to depend more heavily on renew-
O2 during electrolysis driven by intermittent renewable sources. Decoupled ably generated power.[8]
electrolysis (whereby oxygen production occurs with reduction of a suitable Hydrogen (H2) is often proposed in this
mediator and hydrogen production is then paired with the reoxidation of this context as a promising “carbon neutral”
mediator) offers a solution to many of these challenges by allowing O2 and H2 energy carrier (i.e., fuel). In such a system,
to be produced at different times, at different rates, and even in completely renewably generated electricity is used to
electrolyze water to generate hydrogen
different electrochemical cells. In this review, an overview of recent progress and oxygen. The oxygen may be vented
in the field of decoupled electrolysis for water splitting is given and the poten- to the atmosphere whilst the hydrogen
tial that this approach has for enabling a range of other sustainable chemical is stored as a fuel. This hydrogen is then
processes is explored. subsequently oxidized (either by combus-
tion or in a fuel cell) to regenerate water
and to release energy. Hydrogen is not a
1. Introduction perfect fuel but it does have a number of attractive properties
such as its low toxicity, ability to be transported safely over long
1.1. Electrolysis for Storage of Renewable Energy distances via pipeline,[9] and its high energy density per unit
mass (three times greater than that of gasoline).[10] Moreover,
Currently, fossil fuels such as coal, oil, and natural gas remain sustainably sourced hydrogen could be used to reduce CO2 or
the world’s primary sources of energy. However, it is becoming N2 from the atmosphere to generate carbon-neutral fuels and
increasingly clear that greenhouse gases (such as CO2) that are commodity chemicals such as hydrocarbons and ammonia. In
formed during combustion of these fuels are linked to oceanic many ways then, hydrogen can be viewed as the key to a sus-
and global temperature rises,[1,2] shrinking ice sheets,[3] ocean tainable energy cycle.
acidification,[4] and extreme weather events.[5] As the global The process of water electrolysis can be considered in terms
population continues to rise, so too does global energy demand, of its two half-reactions: the hydrogen evolution reaction (HER)
and hence the development of energy solutions that do not and the oxygen evolution reaction (OER). These half-equations
differ somewhat depending on the pH at which the electrolysis
is carried out. At low pH, the HER and OER proceed as follows
P. J. McHugh, A. D. Stergiou, Dr. M. D. Symes
WestCHEM (all potentials are vs the standard hydrogen electrode, SHE)
School of Chemistry
University of Glasgow 2H+ + 2e − → H2 HER ( pH0, E = 0.00V ) (1)
Glasgow G12 8QQ, UK
E-mail: [email protected]
2H2 O → O2 + 4H+ + 4e − OER ( pH0, E = 1.23V ) (2)
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202002453.
Whereas, under alkaline conditions, the half-reactions occur
© 2020 The Authors. Published by Wiley-VCH GmbH. This is an open as below
access article under the terms of the Creative Commons Attribution
License, which permits use, distribution and reproduction in any 2H2 O + 2e − → H2 + 2OH− HER ( pH14, E = −0.83V ) (3)
medium, provided the original work is properly cited.
DOI: 10.1002/aenm.202002453 4OH− → O2 + 2H2 O + 4e − OER ( pH14, E = 0.40V ) (4)
Adv. Energy Mater. 2020, 10, 2002453 2002453 (1 of 21) © 2020 The Authors. Published by Wiley-VCH GmbH
16146840, 2020, 44, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/aenm.202002453, Wiley Online Library on [04/09/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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Hence there is a significant electrical energy requirement to The issue of separating the product gases of electrolysis
drive water electrolysis. Under standard conditions, a potential becomes more complex when using renewable energy sources,
difference of 1.23 V is the thermodynamic minimum required where the power inputs are often variable and/or low. In such
to electrolyze water. However, in order to overcome various cases, the low current densities that are achieved correspond
kinetic and resistance barriers (and so to drive appreciable to low rates of gas production, and these rates of gas produc-
currents to flow for the OER and HER), additional voltage is tion may in turn start to approach the rates of gas crossover for
required. This additional voltage is referred to as overpotential, some membranes, potentially leading to safety issues. A cur-
which is a sum of the various additional potentials relating to rent density of 10 mA cm–2 is considered a useful benchmark
concentration, ohmic resistances in the electrolyzer, and to the for solar-driven electrolyzers, as this is the approximate current
kinetic overpotentials for the individual HER and OER half- density expected of a water splitting device operating at 10%
reactions.[11] Of these overpotentials, the overpotential require- solar-to-fuels efficiency under “1 Sun” illumination (AM 1.5,
ment for the OER tends to dominate as the generation of O2 is 100 mW cm–2).[23] In this scenario, crossover of hydrogen into
a kinetically demanding four-electron, four-proton process.[12,13] the anodic chamber would be a real possibility and would be
The OER is therefore often held to be the main kinetic bottle- particularly hazardous, as the lower explosion limit of hydrogen
neck for the electrolytic generation of hydrogen from water. in oxygen is only 4 mol% H2 in O2.[24–27] Furthermore, even
if efficient and safe gas separation could be achieved, any
solar-to-hydrogen device in which the half-reactions of water
1.2. Conventional and Decoupled Electrolysis splitting remain coupled (as in a conventional electrolyzer,
see Figure 1) will suffer from the fact that the rate of the rela-
In its simplest form, water electrolysis will occur under the tively facile HER would still be limited by the more sluggish
influence of a direct current between two electrodes in a single OER. In this context, harnessing low pressures of hydrogen
compartment. This crude form presents many limitations, gas safely and efficiently from large solar-to-hydrogen arrays
the most deleterious of which is the lack of separation of the is nontrivial and remains an unsolved challenge.
product gases. From Equations (1)–(4), it can be seen that two To this end, recent advances have been made to “decouple”
moles of hydrogen are formed for every mole of oxygen gener- these processes using redox mediators. In simple terms, a
ated. These gas-evolving reactions occur simultaneously, poten- mediator with an appropriate redox potential can be employed
tially creating a highly explosive mixture.[14] Commercially, this such that the OER is coupled with the reduction of the medi-
is addressed via the use of membranes or diaphragms which ator, rather than the direct generation of hydrogen. Likewise, the
separate the cell into anodic and cathodic chambers. Large scale HER can be performed independently of the OER, by coupling
water electrolysis at high pH is carried out using a liquid alka- hydrogen generation to the reoxidation of the mediator, rather
line electrolyte (concentrated aqueous KOH solution), at low than to water oxidation (Figure 1). With each half-reaction occur-
temperatures (293–353 K) with an asbestos diaphragm.[15] In ring separately, the HER can be carried out at much improved
this setting, the anodic and cathodic pressures must be care- rates compared to that possible in conventional water electrol-
fully controlled to prevent gas permeation across the sepa- ysis. In addition, the ability to perform the HER and OER both
rator.[16–18] Recently, considerable progress has been made in in different spaces (“spatial separation”) and at different times
the development of solid polymer membrane electrolyzers (“temporal separation”) greatly increases flexibility for har-
where an anion or proton exchange membrane (e.g., Nafion) vesting hydrogen effectively and safely and significantly reduces
is employed within a compressed cell stack. Though relatively the need for any gas purification steps. The properties required
expensive, these cell configurations can operate at large pres- of an appropriate mediator are stability in both the oxidized and
sure differentials, at excellent operational current densities, reduced forms and a reversible redox couple with a potential
and without the need for caustic electrolytes. In these cells, the that resides between the onset potentials of the OER and HER.
product streams are kept separate as gas crossover rates across In line with the above description, decoupled electrolysis can be
the membranes are low (although crucially even these mem- defined as any process where the ultimate anodic and cathodic
branes are not entirely gas impermeable).[15,18–22] products of electrolysis are generated under at least one of the
Figure 1. A comparison of a) conventional versus b,c) decoupled water electrolysis under general acidic conditions.
following conditions: i) at rates that are not intrinsically linked and HER could be completely decoupled from each other in
to each other, ii) at different times to each other, or iii) in entirely both time and space and the relative rates at which hydrogen
different electrochemical cells to each other. and oxygen could be generated became coupled to the rate of
Since its inception in 2013,[28] the field of decoupled electrol- reduction or reoxidation of the polyoxometalate, rather than
ysis has advanced quickly. However, to the authors’ knowledge, to each other. This phosphomolybdic acid redox mediator was
only three short reviews have been dedicated to the subject to found to buffer the pH of the electrolyte very effectively during
date; the first being a brief perspective by Wallace and Symes,[29] proton release and proton consumption in Equations (5) and
the second being a short section in larger overview on water (6), suggesting that the polyoxometalate was accepting both
electrolysis by You and Sun,[30] and the third a minireview by Liu the electrons and protons from water oxidation. On account of
et al.[31] This area of research is fast moving, and none of the its ability to accept both electrons and protons in this manner,
aforementioned papers covers any of the literature from 2019 the term “Electron-Coupled-Proton Buffer” (ECPB) was
or 2020 to any significant degree. In this review, therefore, we coined to describe this and other redox mediators with similar
aim to provide a comprehensive and up-to-date assessment of capabilities.
this exciting and rapidly developing field as it stands at time of
writing, highlighting the opportunities for decoupled electrolysis 1
ECPB + H2 O → [ECPB( two −electron reduced)][H+ ]2 + O2 (5)
in energy storage, energy conversion, and chemical synthesis. 2
[ECPB( two −electron reduced)][H+ ]2 → H2 + ECPB (6)

2. Polyoxometalate Decoupling Agents
At the time, certain attributes that might make for effective
2.1. Phosphomolybdic Acid Electron-Coupled-Proton Buffers were stipulated. These attrib-
utes are perhaps best viewed as guidelines, rather than rigid
In 2013, Symes and Cronin introduced the concept of decou- requirements, and indeed, it is fascinating to see how numerous
pled electrolysis using the polyoxometalate phosphomolybdic successful decoupling strategies have since been developed
acid (H3PMo12O40).[28,32] This polyoxometalate (a water-soluble that flout one (or more) of these attributes. For example, it was
cluster of 12 molybdenum centers held together by a central originally proposed that useful decoupling agents would dis-
phosphate anion and numerous oxygen ligands) was used in play high solubility in water. However, the subsequent develop-
one compartment of a two compartment cell, with the two ment of solid state decoupling agents (vide infra) shows that
halves of the cell being separated by a semipermeable mem- water solubility is not a strict requirement. Likewise, an ability
brane (see Figure 2). Decoupled water electrolysis was then to buffer the pH effectively during water splitting would seem
achieved according to Equations (5) and (6). First, anodic water to be important for large-scale applications (e.g., to avoid pH
oxidation was performed yielding, O2, protons, and electrons. swings which might cause materials compatibility issues), but
However, instead of these protons and electrons combining to nevertheless examples of nonbuffering decoupling agents have
give hydrogen at the cathode, the counter electrode reaction also been demonstrated (at least on the lab-scale). Others of the
was instead the reduction and protonation of the polyoxometa- original guidelines remain (as yet) unchallenged: the require-
late (Equation (5)). This reduced and protonated polyoxometa- ment that the decoupling agent should have at least one revers-
late could be subsequently reoxidized, yielding electrons and ible redox couple which falls between the onset potentials of
protons which then formed hydrogen at the cathode (Equation the HER and OER, and that it should be stable in both the
(6)). As the reduced and protonated polyoxometalate was stable oxidized and reduced forms (in order to allow both the oxygen
with respect to reoxidation, it could be stored for weeks before and hydrogen evolution steps to be performed in a controlled
the hydrogen evolution step was performed. Hence the OER manner) seem to be common features of the decoupling agents
Figure 2. Decoupled water electrolysis using phosphomolybdic acid as the decoupling agent. Left: The oxygen evolution step where water oxidation
is coupled with the reduction of phosphomolybdic acid, which undergoes a color change from yellow to dark blue as it accepts electrons and protons.
Right: The subsequent hydrogen evolution step, where the phosphomolybdic acid is reoxidized.
that will be discussed in this review. It is also generally desir- for decoupled electrolysis of water, phosphomolybdic acid
able for the decoupling agent to consist only of abundant, low- allows complete separation of oxygen and hydrogen generation
cost elements and for its synthesis to be straightforward. in a stable and cyclable fashion, and therefore forms a useful
In this context, phosphomolybdic acid makes a very good benchmark against which to assess the decoupling agents and
choice as a mobile (i.e., able to be pumped or flowed around a decoupling strategies that have been reported since. Table 1
continuously operating system) decoupling agent and Electron- gives a summary of some of the key metrics of the decoupling
Coupled-Proton Buffer. It has a number of suitably positioned agents for water splitting that are discussed in this review.
redox waves,[33] is commercially available, and can be pre- One of the key claims made for decoupled electrolysis is
pared at concentrations in excess of 0.5 m simply by dissolving that it may enable more practical device designs for solar-to-
the solid in water at room temperature. It buffers the pH hydrogen systems when compared to the concept of vast, flat
extremely well during both the water oxidation and hydrogen arrays producing hydrogen and oxygen on either side of a
evolution processes as it converts between the fully oxidized gas-permeable membrane at a rate limited by the rather low
(H3PMo12O40) and two-electron-reduced (H5PMo12O40) forms power provided by solar irradiation. Indeed, the challenges of
and it is stable in solution in both these forms (including with harvesting low-pressure hydrogen from such a large array are
respect to reoxidation by air in the case of H5PMo12O40) for considerable, even in the absence of any oxygen crossover from
many weeks. When used as an Electron-Coupled-Proton Buffer the anodic chamber into the hydrogen to be harvested. The first
Table 1. Some key metrics of the decoupling agents for water splitting discussed in this review.
Mediator Redox Potential pH for Redox No. of Cycles Best Reported Faradaic Best Reported Faradaic References
(V vs SHE) Potential Tested Efficiency (HER) Efficiency (OER)
H3PMo12O40 +0.50, +0.65 0.3 5 100% 100% Symes and Cronin[28]
Bloor et al.[34]
Li et al.[38]
H4[SiW12O40] 0.0, –0.22 0.5 9 95 ± 7% 100% Rausch et al.[43]
Chisholm et al.[44]
Wu et al.[85]
H3PW12O40 +0.237, –0.036 0.42 – 44.6% – Macdonald et al.[46]
H4SiO4·12MoO3 +0.509 0.69 – – – Macdonald et al.[46]
H6ZnW12O40 –0.078 0.4 200 95.5% – Lei et al.[49]
–0.198
[P2W18O62]6– +0.3, 1 100 – – Chen et al.[50]
+0.1,
0 to –0.5
V(III)/V(II) –0.26 0 – 96 ± 4% – Amstutz et al.[51]
Ho et al.[53]
Ce(IV)/Ce(III) +1.48 0 – – 78 ± 8% Amstutz et al.[51]
3– 4–
Fe(CN)6 /Fe(CN)6 +0.77 7.2 – 99.88% – Goodwin and Walsh[55]
Ma et al.[86]
FcNCl +0.6 6.5 20 100% 100% Li et al.[56]
Hydroquinone sulfonate +0.65 0.7 20 98 ± 7% 91 ± 5% Rausch et al.[61]
AQDS +0.214 0 100 100% 100% Kirkaldy et al.[62]
NiOOH/Ni(OH)2 +0.55 14 100 100% 100% Chen et al.[64]
Landman et al.[66,74]
Dotan et al.[72]
FeOx +0.8 to +1.5 14 50 >90% >90% Jin et al.[75]
MnO2/MnOOH +0.15 14 10 ≈100% – Choi et al.[76]
Fe3O4/FeOOH – – – 100% – Palumbo et al.[77]
CoO – – – 100% – Nudehi et al.[78]
PTPAn +0.789 0.3 120 97.8% 97.8% Ma et al.[79]
+0.689
PTO +0.46 0.3 300 98.7% 98.7% Ma et al.[83]
+0.589
PANI +0.45 0.3 40 – – Wang et al.[84]
+0.91
a separate hydrogen-evolving cell where it could be reoxidized

at high current density, liberating hydrogen at the cathode for
compression and storage. The generation of hydrogen at such
a point-source electrolyzer, remote from the light harvesting
array, would dramatically increase the efficiency and safety of
hydrogen collection. Further economies could be realized by
combining multiple polyoxometalate-reducing photoarrays with
a single polyoxometalate reoxidation cell in order to maximize
any expensive components (e.g., hydrogen evolution electrocat-
alysts) used in this hydrogen generation cell.
A similar concept using phosphomolybdic acid as a decou-
pling agent in a light-driven scheme has been proposed by
Li et al.[38] In their setup, oxygen evolution was achieved upon
irradiation of mixtures containing a powder of the n-type semi-
conductor bismuth vanadate (BiVO4) and phosphomolybdic
acid. As with WO3, the bandgap of BiVO4 is well positioned to
Figure 3. The photoelectrochemical cell developed by Bloor et al.[34] for facilitate water oxidation and concomitant phosphomolybdic
the reduction of phosphomolybdic acid at a carbon cathode powered acid reduction.[39,40] After irradiation, the reaction mixture was
solely by visible light irradiation of a WO3 photoanode.
transferred to a two-compartment cell where, using Pt mesh
working and Pt wire counter electrodes, the reduced phospho-
steps in showcasing decoupling as a way around some of these molybdic acid formed in the photolytic step was reoxidized with
technical challenges were taken by Bloor et al., again using corresponding hydrogen evolution at the cathode. The Faradaic
phosphomolybdic acid as the decoupling agent.[34] In that study, efficiency of the HER using this method was found to be 98%.
a tungsten trioxide (WO3) photoanode was employed to per- Suspensions of other, well established n-type semiconductors,
form water oxidation within a photoelectrochemical cell, where such as Ag3PO4 and Fe2O3, were also assessed for use by this
the cathode reaction was reduction and protonation of phos- method; it was found that none were as efficient as BiVO4. One
phomolybdic acid (Equation (5)), rather than direct hydrogen issue encountered by the authors, as their semiconductor was
production (see Figure 3). The choice of WO3 (on a fluorine- mixed into their mediator solution, was that the characteristic
doped tin oxide substrate) as the photoanode was dictated by color change of phosphomolybdic acid from yellow to dark blue
its good stability in acidic electrolytes and for its reasonable which occurs upon its reduction inhibited the absorption of
(if perhaps unspectacular) visible light absorption properties. light by the semiconductor. Increasing the transparency of solu-
In undoped form, WO3 has a well-positioned valance band tions of phosphomolybdic acid was listed as future work that
edge for the oxidation of water at low pH, but the position of might increase the efficiency of the decoupled photolytic water
its conduction band is insufficiently reductive to allow WO3 to oxidation step. In this regard, it is useful to note that in the
drive the reduction of protons to hydrogen concomitant with setup described by Bloor et al., the polyoxometalate is confined
water oxidation.[35] However, photoanodes using WO3 should to the cathode compartment of the photoelectrochemical cell,
have the ability to drive water oxidation at the anode coupled whilst the semiconductor is confined to the anode, and hence
to the simultaneous reduction of phosphomolybdic acid at the the polyoxometalate does not attenuate the light reaching the
cathode, on account of phosphomolybdic acid’s more posi- photoanode.[34]
tive redox potential than hydrogen (around +0.65 V vs SHE at An interesting aside can be made at this point to consider
pH 0.5). Hence in the absence of phosphomolybdic acid, no the activity of phosphomolybdic acid and certain vanadium-sub-
photocurrent was recorded in a setup similar to that shown stituted phosphomolybdates as decoupling agents in hydrogen/
in Figure 3. However, upon illumination with AM 1.5 light at oxygen fuel cells (i.e., performing the reverse reaction to electro-
1 Sun intensity, photocurrents in excess of 1 mA cm–2 could chemical water splitting). Building on preliminary data reported
be achieved for oxygen generation at the WO3 photoanode by Shah and co-workers,[41] Matsui et al. studied the effective-
(coupled to phosphomolybdic acid reduction at the cathode) ness of a range of phosphomolybdates of the general formula
with no external potential bias. These current densities for the H3+xPVxMo12−xO40 (x = 0, 2, and 3) in terms of their ability to be
photocatalytic water oxidation process compared favorably with reduced by hydrogen and then subsequently oxidized by O2.[42]
photocurrents obtained at low pH (but using applied biases) The concept (Figure 4) relies on the oxidation of H2 gas at the
in other studies using WO3 photoanodes.[36,37] Importantly, no Pt/C anode of a proton exchange membrane fuel cell to gen-
hydrogen production took place during this photodriven water erate protons and electrons. In a conventional proton exchange
oxidation and phosphomolybdic acid reduction process, elimi- membrane fuel cell, these protons and electrons would com-
nating any concerns about gas crossover. As the reduced decou- bine with O2 at the cathode side of the cell to generate water,
pling agent is stable with respect to spontaneous reoxidation, releasing energy in the process. However, significant amounts
there is, therefore, the potential to trickle-charge the polyoxo- of Pt are required at the cathode to perform this oxygen reduc-
metalate solution at low current densities as oxygen is slowly tion reaction and the kinetics of oxygen reduction constitute a
evolved at the photoanode and allowed to vent to the atmos- significant bottleneck. By using a decoupled approach, Matsui
phere. The reduced polyoxometalate solution (once a desired et al. replaced the direct oxygen reduction reaction with reduc-
level of reduction has been reached) could then be pumped to tion and protonation of their phosphomolybdate ions, which
ecoupling agent. On a carbon electrode, both of these reduc-

d
tion reactions occur at considerably more positive potentials
than proton reduction (the current density for which is not
appreciable at potentials more positive than –0.6 V vs SHE).
This means that at a carbon cathode, it should be possible to
reduce silicotungstic acid by two electrons without any com-
peting hydrogen evolution. However, as the redox potentials
suggest, the two-electron-reduced silicotungstic acid is ther-
modynamically unstable with respect to reoxidized polyoxo-
metalate and hydrogen evolution and so should spontaneously
reoxidize (generating hydrogen at the same time) when in con-
tact with a suitable catalyst, without the need for any additional
Figure 4. A decoupled proton exchange membrane hydrogen/oxygen fuel electrochemical bias. This would eliminate the need for an elec-
cell using a liquid polyoxometalate-based decoupling agent.
trochemical polyoxometalate reoxidation/hydrogen evolution
step and hence make decoupling more effective.
occurred at a purely carbon cathode. The reduced and proto- To illustrate this concept, Rausch et al. electrolyzed water at
nated polyoxometalate solution was then flowed into a “regen- a Pt mesh anode in a two-compartment cell, whilst silicotung-
erator,” where bubbling with O2 caused the polyoxometalate stic acid was reduced at a carbon cathode in the other chamber
to be oxidized back to its original form (with cogeneration (Figure 5). Gas chromatography indicated a 100% Faradaic effi-
of water) for return to the fuel cell. In this way, the sluggish ciency for oxygen evolution under these conditions, with only
electrochemical oxygen reduction reaction could be decoupled trace amounts of hydrogen being detected in the electrochem-
from the hydrogen oxidation reaction, with the ultimate water- ical cell. Decoupling of the OER and HER was therefore highly
producing step taking place outside the electrochemical cell in effective. Electrolysis was continued until all the silicotungstic
a nonelectrochemical step. Temperature and pH were found acid had been reduced by two electrons, generating species akin
to be crucial factors for the optimization of the fuel cell. The to H6[SiW12O40]. This two-electron-reduced decoupling agent
optimal conditions found to be 80 °C and a basic pH achieved was then removed from the electrochemical cell and exposed to
by employing an equimolar ratio of sodium carbonate to poly- various catalysts in order to generate hydrogen spontaneously.
oxometalate. Under these conditions, the system was able to MoS2 and Ni2P were both found to be effective, but the best
generate a stable current density of 5.36 mA cm–2 at a terminal results in terms of depth of reoxidation and speed of hydrogen
voltage of about 0.7 V over the course of an hour. This approach generation were obtained using Pt on a carbon support. Indeed,
shows considerable promise for the development of new fuel per milligram of Pt used, the rate of hydrogen produced from
cell systems where Pt use is minimized and where current flow this decoupled system was 30 times faster than for a state-of-
(and hence power generation) can be optimized by decoupling the-art proton exchange membrane electrolyzer, which is attrib-
the electrochemical oxygen reduction reaction from the oxida- utable to the fact that the Pt/C catalyst in the decoupled system
tion of the hydrogen fuel. does not require an electrical connection and so can be used in
a 3D configuration, whilst in an electrolyzer the Pt/C electro-
catalyst must be in contact with a current collector and hence is
2.2. Silicotungstic Acid confined to a less catalytically optimal 2D plane.
In terms of electrochemical efficiency, some of the improve-
Decoupling the OER and HER from each other comes at an ments relative to coupled electrolysis that it was hypothesized
energetic cost. This is because the decoupling agent must be would be possible also seem to have been borne out: at a
reduced as the OER takes place and then reoxidized as the current density of 50 mA cm–2, the decoupled system using
HER occurs. If these steps are performed electrochemically,
then there are two additional sets of overpotential requirements
for the decoupling agent’s reduction and reoxidation over and
above those required for the OER and HER. In their original
decoupling paper, Symes and Cronin estimated that at a cur-
rent density of 100 mA cm–2, their decoupled system was only
87% as efficient as the analogous direct water splitting process
in a coupled arrangement.[28] Hence, strategies that minimize
the number of additional electrochemical processes should
help to increase the efficiency of decoupled electrolysis.
To this end, Rausch et al. explored the use of silicotungstic
acid (H4[SiW12O40]) as an alternative polyoxometalate-based
decoupling agent.[43] Compared to phosphomolybdic acid, the
Figure 5. The silicotungstic acid-mediated system reported by
first two redox waves of silicotungstic acid are significantly
Rausch et al.[43] Oxygen is produced via water oxidation alongside
more cathodic, with E½ values of +0.01 and –0.22 V (vs SHE) reduction of the mediator to H6[SiW12O40]. Subsequent hydrogen produc-
at pH 0.5. The position of this second wave in particular has tion is achieved spontaneously in a separate chamber upon introduction
significant implications for silicotungstic acid’s activity as a of a suitable catalyst, regenerating H4[SiW12O40].
silicotungstic acid as a mediator was found to be 16% more reduced. The reduced silicotungstic acid solution was then
efficient than a coupled electrolysis system making oxygen and fed from the cathode of the OER cell to the anode of the
hydrogen at the same time on a Pt anode and carbon cathode, HER cell, with the circuit of the HER cell left open to prevent
respectively. spontaneous reoxidation of the reduced silicotungstic acid
As suggested by the relative positions of the first redox wave (“charging” in Figure 6). Once a complete one-electron reduc-
of silicotungstic acid (+0.01 V vs SHE at pH 0.5) and the position of the silicotungstic acid in the catholyte loop of the OER
tion of hydrogen evolution onset on Pt at this pH (≈–0.03 V), cell was achieved (generating H5[SiW12O40]), the circuit of the
the spontaneous reoxidation of reduced silicotungstic acid on HER cell was closed. Galvanostatic electrolysis was then per-
a Pt catalyst reaches an equilibrium whereby the decoupling formed across both the OER and HER cells such that the rate
agent exists as a mixture of completely reoxidized H4[SiW12O40] at which H5[SiW12O40] was reduced to H6[SiW12O40] in the OER
and one-electron-reduced H5[SiW12O40]. Hence on the first cell matched the rate at which H6[SiW12O40] was reoxidized
usage of silicotungstic acid as a decoupling agent, the Faradaic to H5[SiW12O40] in the HER cell. In this way, the system was
efficiency for hydrogen generation is only 68%, as the poly- placed into steady state with silicotungstic acid cycling between
oxometalate remains somewhat reduced after contact with the H6[SiW12O40] and H5[SiW12O40] whilst oxygen and hydrogen
catalyst. However, in a system under continuous flow where were continuously produced at the anode of the OER cell and
the electrolyte is recycled, the Faradaic efficiency on subsequent cathode of the HER cell, respectively. Strictly speaking, it should
runs would increase as the polyoxometalate cycles between this not be necessary to supply any voltage to reoxidize H6[SiW12O40]
equilibrium position and its fully reduced H6[SiW12O40] form. to H5[SiW12O40] in the HER cell; however, in practice the appli-
Indeed, silicotungstic acid was found to be stable over 20 con- cation of a voltage was found beneficial for ensuring a stable
secutive redox cycles and so was suggested to be viable for use current density (and hence that steady-state was maintained).
in a continuous-flow reactor. Several key results were reported by the authors of this study.
Recently, the performance of silicotungstic acid for use First, a comparison was made between the charge passed in
in just such a continuous flow reactor based on a proton initially reducing the silicotungstic acid, relative to the charge
exchange membrane electrolyzer has been assessed by required to fully reoxidize the solution at the end of various
Chisholm et al.[44] In that setup, the decoupled HER and OER periods of steady-state operation. This information, meas-
steps were performed in two interconnected electrochemical ured across three different operational current densities, gave
flow cells (Figure 6). Both the OER and HER cells employed an indication as to how stable the system was during steady-
a Nafion-117 membrane, coated on one side with a catalyst. In state. At 100, 250, and 500 mA cm–2, the final reoxidation step
the OER cell, the anodic side was coated with IrO2, while in the required 105%, 93%, and 99% of the initial reduction charge,
HER cell the cathodic side was coated with Pt/C. respectively, thus demonstrating that the process was indeed
The operation of the continuous flow process was car- operating at a steady state to a high degree. Additionally, the
ried out as follows. In the OER cell, for both the anolyte and amount of hydrogen that could be detected in the catholyte
the catholyte, a fully oxidized solution of silicotungstic acid loop was recorded at these current densities. This indicated
(H4[SiW12O40]) in water was initially flowed through the cell. the extent to which the mediator was decoupling both half-reac-
Galvanostatic electrolysis (i.e., at a fixed current density) was tions of electrochemical water splitting. Using a 0.4 m silico-
then carried out, with oxygen being produced at the anode, and tungstic acid solution, at a cathodic flow rate of 500 mL min–1,
the silicotungstic acid solution on the cathode side becoming the authors reported decoupling percentages ≥99%.
Figure 6. Schematic of the continuous flow setup used by Chisholm et al.[44] During charging, the circuit on the HER cell remains open as the silico-
tungstic acid in the catholyte loop is reduced, with accompanying oxygen evolution at the anode of the OER cell. To place the cell into steady state
mode, the circuit on the HER cell is closed and a fixed current is applied such that the rate of reoxidation of the silicotungstic acid matches the rate of
its reduction in the OER cell. Hydrogen is then generated at the cathode of the HER cell.
More impressively, crossover of hydrogen into the oxygen acid and silicotungstic acid but found that the Zn2+ analogue,
stream from the anode of the OER cell was found to be sig- H6ZnW12O40, was able to undergo reduction by up to four
nificantly attenuated at various rather low current densities that electrons under the same conditions. There was no significant
might better reflect operation using low power and/or inter- change in pH during this reduction (or the subsequent electro-
mittent renewable energy sources. Indeed, at a current density chemical reoxidation), suggesting that H6ZnW12O40 is an effec-
of 25 mA cm –2, the decoupled system exhibited hydrogen- tive Electron-Coupled-Proton Buffer. When used as a decou-
in-oxygen levels of only 0.31%, whereas a conventional (coupling agent for electrochemical water splitting, H6ZnW12O40
pled) electrolyzer using analogous components was found exhibited excellent metrics; decoupling of the OER and HER
to have hydrogen-in-oxygen levels of 1.9% under the same was essentially total and over 200 cycles in a continuous flow
conditions. Given that guidelines for the allowable levels system, the mediator showed good stability and displayed a
of hydrogen-in-oxygen put an upper limit on this figure of Coulombic efficiency for each cycle well in excess of 90%.
0.4%,[45] the decoupled system has clear potential safety ben- As a final example of polyoxometalate decoupling agents for
efits over coupled systems at these low current densities. use in water splitting, we shall consider the use of the Wells–
Dawson polyoxoanion [P2W18O62]6– as reported by Chen et al.
in 2018.[50] Remarkably, this polyoxometalate was found to be
2.3. Other Polyoxometalates able to reversibly accept up to 18 electrons in aqueous solution
without significant cogeneration of hydrogen, provided the con-
In the decoupled water electrolysis systems discussed so far, centration of the polyoxoanion exceeded 0.1 m and provided
catalysis of the HER was largely performed using Pt-based that the pH was kept below 1 (presumably, the reduced polyox-
catalysts. Noting the scarcity of Pt, MacDonald and co-workers oanion is stabilized by a high proton concentration).
investigated the performance of two molybdenum (Mo2C and To investigate this polyoxometalate as a decoupling agent, the
MoS2) and two nickel phosphide (Ni2P and Ni5P4) catalysts authors assembled a dual electrochemical flow cell system as
for the HER in decoupled electrolysis.[46] These authors also shown in Figure 7. In one proton exchange membrane cell (the
expanded the library of polyoxometalate decoupling agents to “OER cell”), water was oxidized at a controlled current density
include phosphotungstic acid and silicomolybdic acid alongside at an IrO2 anode with concomitant reduction of [P2W18O62]6– at
silicotungstic acid and phosphomolybdic acid. The rationale the cathode. The reduced polyoxometalate then flowed to the
for these choices of decoupling agents was the differing posi- polyoxometalate holding tank, from where it could be directed
tions of their redox potentials. Accordingly, 1 m solutions of all back through the OER cell in order to reduce it further. Once
four decoupling agents were prepared and subjected to elec- the polyoxoanion had been reduced to the chosen degree, the
trochemical reduction by two electrons each. These reduced solution was then fed into the second electrochemical cell
solutions were then introduced to the Mo and Ni-based cata- (the “HER cell”) where reoxidation of the polyoxometalate could
lysts and the rates and extent of hydrogen evolution from these be carried out with concomitant cathodic hydrogen production
systems were compared. In the case of silicotungstic acid and from water. Comparison of the charge passed when reducing
phosphotungstic acid, spontaneous hydrogen evolution was the polyoxoanion with the charge obtained upon its reoxidation
detected using all four of the catalysts, with hydrogen evolu- indicated how reversible the charge storage process was. The
tion from silicotungstic acid showing superior rates and larger authors reported that at Li6[P2W18O62] concentrations of 0.1 m,
yields than those achievable with phosphotungstic acid, pre- 96% of the charge could be recovered, equating to around 17.2
sumably due to silicotungstic acid’s more negative reduction electrons recovered for every 18-electron reduction of each poly-
potentials. Meanwhile, and perhaps as might have been pre- oxoanion. The “lost” charge in this case can arise through two
dicted, no spontaneous hydrogen evolution was detected from
reduced phosphomolybdic acid or silicomolybdic acid solutions
with any catalyst (even Pt), as the redox waves for these reduced
species are all more positive than that for proton reduction to
hydrogen. Of the four nonprecious metal catalysts tested, the
fastest rates of hydrogen evolution were recorded using Ni5P4
and Mo2C, although these both generated H2 at inferior rates
relative to Pt/C.
In the examples discussed thus far, the decoupled processes
have relied on (at most) two-electron reduction and reoxidation
cycles of the polyoxometalate decoupling agent. However, one
of the most promising features of polyoxometalates as redox
mediators is that they can often reversibly accept and donate a
much greater number of electrons than this.[47,48] In 2019, Lei
et al. conducted a comparative study of three allied tungsten-
based Keggin polyoxometalates of the form [XW12O40] (where Figure 7. Schematic of the flow cell system employed by Chen et al.[50]
Oxygen and hydrogen are produced separately in two proton exchange
X = P5+, Si4+, or Zn2+), in order to ascertain the effect of the
membrane cells. These reactions are decoupled by the reduction and
central heteroatom on the redox properties of the clusters.[49] reoxidation of [P2W18O62]6–. The polyoxometalate can be held in the
By reductive bulk electrolysis, the authors confirmed the two- holding tank and recycled to the OER cell until a desired level of reduc-
electron nature of the reductions of both phosphotungstic tion has been achieved.
mechanisms: i) spontaneous reoxidation of the 18-electron- generate hydrogen on demand, depending on the requirements
reduced polyoxometalate on contact with trace oxygen in the of the user.
system and ii) low levels of spontaneous hydrogen evolution
from the 18-electron-reduced polyoxometalate in the presence
of metallic impurities. Although reduction of the polyoxoanion 3. Transition Metal Redox Mediators
was found to be possible up to a total of 32 electrons per polyox-
oanion, the Coulombic efficiency based on recovered electrons 3.1. Vanadium Salts
decreased markedly beyond 18-electron reduction, indicating
that anions of greater than this 18-electron reduction level were Decoupled electrolysis systems inspired by redox flow batteries
not stable with respect to spontaneous hydrogen evolution. In have also been developed using more conventional flow battery
contrast, the stability of this decoupling agent under multiple electrolytes. In 2014, Amstutz et al. reported a system for the
successive 18-electron reduction and reoxidation cycles was decoupled electrolysis of water using a vanadium-based catho-
found to be excellent. Over 100 cycles, the Coulombic efficiency lyte and cerium-based anolyte.[51] To mediate water electrolysis,
of the reduction/reoxidation process was found to be over 95%, a solution containing a V(III) salt in sulfuric acid was reduced
demonstrating the viability of this polyoxometalate cluster to a V(II) solution at a graphite felt electrode. The position of the
as an effective mediator for continuous flow decoupled water V(III)/V(II) redox couple (–0.26 V vs SHE under the conditions
electrolysis. When the 18-electron-reduced decoupling agent used) is negative of the proton reduction couple, and so (just
was exposed to powdered Pt/C, spontaneous hydrogen evolu- as with the silicotungstic acid systems discussed above[43,44]),
tion occurred at a rate of 3500 mmol of H2 per hour per mg of exposure of this V(II) solution to hydrogen evolution catalysts
Pt, significantly in excess of the rate of hydrogen evolution in should give rise to spontaneous (nonelectrochemical) hydrogen
a conventional proton exchange membrane electrolyzer (where generation. Hence, when this V(II) solution was directed into
typical values are on the order of 50–100 mmol of H2 per hour an external catalytic reactor, the HER occurred over an Mo2C
per mg of Pt). catalyst with a Faradaic yield of up to 96% (Equation (7) and
The ability of [P2W18O62]6– to reversibly accept and donate Figure 8).
such a large number of electrons prompted an investigation
into its potential to act as an energy storage medium in its own 2V 2+ + 2H+ → H2 + 2V 3+ (7)
right, rather than solely as a mediator for the production of
hydrogen. Accordingly, a redox flow battery was constructed in 4Ce 4 + + 2H2 O → 4Ce3+ + 4H+ + O2 (8)
which solutions of [P2W18O62]n– served as the negative electro-
lyte and a mixture of HBr/Br2 served as the positive electrolyte. Similarly, at the anode of the flow-battery type system, an
At a [P2W18O62]n– concentration of 0.5 m, a practical discharge acidic solution of Ce(III) was oxidized to Ce(IV). The position
capacity density of 230 Ah L–1 was achieved with a Coulombic of the Ce(III)/Ce(IV) redox couple under these conditions is
efficiency approaching 100% and an energy density (for the more anodic than that for water oxidation, meaning that (in the
polyoxometalate solution) of 225 Wh L–1. This energy density is presence of a suitable catalyst), Ce(IV) should be able to oxidize
around four to five times that of currently available vanadium– water to generate oxygen, becoming reduced back to Ce(III)
vanadium redox flow batteries, suggesting that such decoupling in the process (Equation (8)). In practice, Amstutz et al.
agents could find utility in devices that can either store renew- achieved this catalytic water oxidation reaction over RuO2
ably generated energy (when operating as flow batteries) or nanoparticles. The Faradaic yield for the OER (78% ± 8%)

Figure 8. Schematic of the Ce-V redox flow battery system employed by Amstutz et al.[51] where valves allow for on-demand H2 or O2 production via
routing of the electrolytes to external catalytic reactors.
was somewhat less than optimal, which was attributed to a compression and storage efficiencies) was also demonstrated:
side reaction (previously reported in the literature[52]) whereby at pressures of up to ten atmospheres, hydrogen could be pro-
Ce(IV) reacts with (and degrades) the RuO2 catalyst as it is duced at Faradaic efficiencies approaching 60%.
reduced back to Ce(III). The authors suggested that this issue To ascertain the extent to which the bipolar membrane would
could be avoided by adapting the electrolyte to an all-vanadium allow extended operation, the rates of ion crossover across the
system (where the OER would then be mediated by the reduc- bipolar membrane were recorded by monitoring the vanadium
tion of V(V) to V(IV)). As with the [P2W18O62]n– system,[50] this salt concentrations in the anolyte, using inductively coupled
device configuration allowed both for conventional operation as plasma mass spectroscopy, after the cell was subjected to a cur-
a redox flow battery (the electrolyte could be charged and dis- rent of 10 mA cm–2 for 24 h. It was determined that the current
charged with electrical energy, cycling between V(II) and V(III) density corresponding to V(III)/V(II) leakage over this time was
at one electrode and between Ce(IV) and Ce(III) at the other), negligible (0.226 µA cm−2), although the effects of this leakage
and for the conversion of energy to hydrogen, offering consid- over longer stretches of operation is yet to be determined. This
erable flexibility for renewable energy usage to the operator. test also indicated that the presence of the V(III)/V(II) species
Ho et al. have also made use of the V(III)/V(II) redox couple did not negatively affect the selectivity of the bipolar mem-
in their solar-driven approach to decoupled water electrolysis.[53] brane. Furthermore, the authors demonstrated that the system
The authors noted that there were numerous examples of could be powered directly by renewable energy by coupling it to
earth-abundant OER electrocatalysts, with optimal stability a photovoltaic module: using only the power supplied by this
when used at alkaline pH.[54] However, the V(III)/V(II) couple photovoltaic under solar irradiation, hydrogen was produced
for HER generation is only soluble at low pH. By employing a at a Faradaic efficiency of 80% and a solar-to-hydrogen energy
bipolar membrane, a large pH differential between the anode conversion efficiency of 5.8% was achieved. This represents
and cathode compartments of their electrochemical cell could a significant milestone in demonstrating the practicality of
be maintained, allowing the OER side to be at high pH whilst decoupled electrolysis for solar-to-hydrogen conversion.
the HER side was at very low pH (Figure 9). This dual elec-
trolyte system consisted of an anodic chamber with a Ni mesh
oxygen evolution electrode in concentrated KOH (2.5 m) and 3.2. Iron Complexes
a cathodic chamber using a Pt foil electrode in sulfuric acid
(2.0 m). At the Ni anode, OH– was oxidized yielding elec- In 2017, Goodwin and Walsh introduced a novel approach to
trons, water and oxygen; these electrons travelled through the spatially decouple the OER and HER, which made use of the
external circuit to the cathode, where they reduced V(III) ions Fe(CN)63–/Fe(CN)64– redox couple and a closed bipolar elec-
to V(II). Once charged, the V(II) solution was then transferred trode.[55] Bipolar electrodes are conducting components which
to a separate reactor where, when stirred with an Mo2C catalyst, can promote both anodic and cathodic reactions simultane-
hydrogen was produced on-demand. The Faradaic efficiency of ously; these electrodes are further denoted as “closed” when
the hydrogen production step using this cell was investigated their poles are in two separate solutions. In their setup,
at different depths of charge of the vanadium solution: when Goodwin and Walsh employed two carbon cloths connected by
this solution was reduced to 27%, 55%, and 96% of its charging a wire as the closed bipolar electrode, which bridged between
capacity, the amount of hydrogen collected corresponded two separate two-compartment cells (Figure 10). Inside each two-
to Faradaic efficiencies of 87%, 87%, and 83%, respectively. compartment cell, one end of the closed bipolar electrode was
Hydrogen generation under elevated pressures (important for submerged in a solution of K3Fe(CN)6/K4Fe(CN)6 in 0.1 m KOH.
Figure 9. Diagram of the setup used by Ho et al.[53] where alkaline oxygen evolution is coupled with the reduction of V(III) to V(II) in a dual electrolyte,
two-compartment cell separated by a bipolar membrane and powered by a solar-driven photovoltaic. The V(II) species can then be charged into a
catalytic reactor, producing hydrogen and regenerating V(III).
electrochemical cell was saturated with O2 at pH = 0 (under

which conditions the oxygen reduction reaction has a redox
potential of +1.23 V), whilst the other cell was saturated with
H2 at pH = 14 (under which conditions the hydrogen oxida-
tion reaction has a redox potential of –0.83 V). Hence the total
theoretical voltage output of such a fuel cell is in excess of 2 V,
whereas a conventional fuel cell maintains the same pH for
both chambers and therefore is limited to a total theoretical
voltage output of only 1.23 V. In practice, Goodwin and Walsh
were able to obtain voltage outputs >1.8 V, thus significantly
exceeding the theoretical maximum performance of a conven-
tional fuel cell under analogous conditions.
The foregoing examples almost all use somewhat extreme
Figure 10. The closed bipolar electrode cell system used by Goodwin pH conditions (highly acidic and/or highly alkaline), in part
and Walsh to spatially decouple O2 and H2 production from water because these are the conditions under which conventional
electrolysis.[55] water electrolysis has been studied in most detail. However,
electrolysis under less extreme pH conditions may have ben-
A Nafion membrane separated the two compartments in each efits for materials compatibility and durability. Motivated by a
cell, thus separating the compartment containing the closed desire to develop decoupling strategies that would be effective
bipolar electrode from the other, which housed a Pt electrode at more neutral pH values, Li et al. studied the ability of ferro-
in 0.1 m KOH. The operation of the device involved water oxida- cene derivatives to decouple the OER from the HER.[56] In their
tion at a platinum electrode coupled with reduction of Fe(CN)63– experimental design, (ferrocenylmethyl)trimethylammonium
at the closed bipolar electrode in one cell, while in the other, chloride (FcNCl) acted as the decoupling agent, undergoing
oxidation of Fe(CN)64– occurred at the other end of the closed oxidation and reduction in tandem with the half-reactions of
bipolar electrode with concomitant hydrogen evolution at the water splitting. This decoupled process was performed using a
second Pt electrode. Since the HER and OER were performed two-compartment H-cell, where in one compartment, a carbon
in entirely separate cells in this arrangement, the issue of gas counter electrode was immersed in a 50 × 10−3 m solution of
mixing was eliminated. However, the rates of production of FcNCl in 0.5 m Na2SO4 (pH = 6.5). In the other chamber, two
these gases remained intrinsically linked, via the closed bipolar other electrodes were placed: Ni2P on Ni foam to perform the
electrode. By periodically switching the direction of the current, HER and a Ni foam electrode to perform the OER. These elec-
each redox species could be regenerated, thereby allowing con- trodes were connected electrically to the electrode in the decou-
tinuous operation. pling agent solution in turn, to allow temporally separated HER
Since the electrolytes in the two cells in this system are and OER to proceed (Figure 11).
entirely separated, two electrolytes at vastly different pH values FcNCl was well-suited its role as a decoupling agent on
can be used in the two electrochemical cells (cf. the use of account of its high solubility in water, the position of its redox
bipolar membranes by Ho et al.[53]). Taking advantage of this, couple between the onset potentials of the OER and HER, and
Goodwin and Walsh used their system to demonstrate a very its stability under successive redox cycling events. When used
elegant example of decoupled fuel cell operation. Hence, one as a decoupling agent for electrolytic water splitting, FcNCl
Figure 11. Experimental setup used by Li et al. with a (ferrocenylmethyl)trimethylammonium chloride decoupling agent (“DA”).[56] The OER and HER
were performed in consecutive steps, coupled with the reduction and reoxidation (respectively) of the decoupling agent.
was able to mediate (in turn) the OER (without simultaneous production (the amount of O2 production that was observed
hydrogen evolution) and the HER (without simultaneous during the HER step in the decoupled system amounted to less
oxygen evolution) both at full Faradaic efficiency. The system than 2% of the amount of oxygen that would be expected in
proved robust to multiple successive redox cycles, despite the conventional (coupled) water electrolysis). Similarly, the decou-
fact that it did not prevent the pH from varying during these pled system was found to produce oxygen with a Faradaic effi-
cycles (the pH value of the electrolyte rose to pH 9 during ciency of 91 ± 5%; production of hydrogen during this step was
the HER as protons were consumed, before decreasing back to not detected. Decoupling of the OER and HER was thus dem-
pH 6.5 by the end of the OER process as these protons were onstrated. The pH change measured during the HER was rela-
replaced). Indeed, after 20 cycles, no change was found in the tively small when using this decoupling agent, suggesting that
redox chemistry of the mediator, indicating its high stability to the quinone derivative was reversibly accepting both electrons
redox cycling within this pH range. Furthermore, the authors and protons and acting as an effective Electron-Coupled-Proton
also demonstrated that sunlight-driven hydrogen production Buffer. However, the stability of the buffer was greatly inferior
was possible with this system, by employing a photovoltaic to that of phosphomolybdic acid. Indeed, over 20 oxidation/
module under solar irradiation to drive currents for the HER reduction cycles, the charge storage capacity of this hydroqui-
of around 20 mA cm–2 (with concomitant reoxidation of the none sulfonate Electron-Coupled-Proton Buffer was found to
decoupling agent). Under otherwise analogous conditions, but reduce by 1% per cycle, which was attributed to oligomerization
in the absence of decoupling agent, hydrogen production was of the oxidized form of the quinone derivative. Similarly, the
minimal. quinone displayed rather a high rate of crossover through the
Nafion membrane employed to stop the buffer from accessing
the OER/HER compartment (≈2.7 × 10−6 mol h−1). The authors
4. Soluble Organic Redox Mediators proposed that both of these issues might be overcome through
the use of a larger, more sterically hindered quinone derivative
Early on in the development of the concept of decoupled elec- that would cross the membrane more slowly and be less prone
trolysis, it was noted that spatial and temporal separation of to oligomerization.
oxygen evolution and hydrogen (or hydrogen-equivalent) pro- To this end, some of the same authors later examined the
duction through the use of recyclable redox mediators had use of anthroquinone-2,7-disulfonic acid (AQDS) as an alter-
strong parallels with the mitochondrial electron transport native quinone-based Electron-Coupled-Proton Buffer,[62] a
chain. Many of the proton and electron carriers involved in choice inspired in part by the successful utilization of this
such transport chains are based on quinones.[57–60] It is perhaps molecule as a stable 2-electron redox couple in an all-organic
natural therefore to wonder whether Electron-Coupled-Proton redox flow battery.[63] Cyclic voltammetry of AQDS revealed
Buffers based on quinones could be effective decoupling that the compound had a reversible redox couple centered
agents for water splitting. Such considerations motivated around +0.21 V versus SHE, and prolonged electrochemical
Rausch et al. in 2013 to investigate the simple quinone potas- cycling (100 cycles of consecutive oxidation and reduction) of
sium hydroquinone sulfonate (derived from 1,4-hydroquinone) this couple in a two-compartment cell in 1 m H2SO4 revealed
as a decoupling agent.[61] The addition of the sulfonate group a decay in total capacity after these cycles of only 5.75%, rep-
confers water solubility on the mediator in both its oxidized resenting a marked improvement over the hydroquinone sul-
and reduced forms, rendering this decoupling agent possibly fonate system. Analysis of the gaseous products of this redox
the simplest water-soluble quinone-based system that could be cycling indicated that oxygen and hydrogen were produced in
devised. In comparison to phosphomolybdic acid that was (up their respective steps with excellent decoupling, both at 100%
to that point in time) the only other recognized example of an Faradaic efficiency. These results taken together illustrated
Electron-Coupled-Proton Buffer, potassium hydroquinone sul- the suitability of AQDS for use as an Electron-Coupled-Proton
fonate also exhibited a significantly reduced molecular weight Buffer in decoupled water splitting. The authors then assem-
(≈1900 vs 228 Da) and hence the prospect of a significantly bled a dual flow cell system, consisting of two back-to-back elec-
improved ratio of molecular weight to electrons stored. trolyzers. In this system, water oxidation was carried out in one
Analysis of potassium hydroquinone sulfonate by cyclic cell with accompanying Electron-Coupled-Proton Buffer reduc-
voltammetry in phosphoric acid at pH 0 indicated the pres- tion. The reduced AQDS was then routed to the second cell,
ence of a reversible, 2-electron redox couple at +0.65 V versus where hydrogen was produced in tandem with reoxidation of
SHE; this couple therefore being suitably positioned with the AQDS. To reach current densities of 1 A cm−2, the decou-
regard to the onset potentials of the OER and HER at this pH. pled OER and HER steps required 2.01 and 0.96 V, respectively.
Thus encouraged, decoupled electrolytic water splitting was Using the higher and lower heating values of hydrogen, energy
attempted using a 0.5 m solution of the quinone derivative as efficiencies of 63% and 52% respectively were calculated for
the decoupling agent at a carbon electrode, and using a Pt elec- the ratio of electrochemical energy required to produce the
trode to perform the OER and then the HER in turn. Compared hydrogen versus the energy that could be obtained from the
to a cell performing the direct electrolysis of water using this combustion of that amount of hydrogen. However, after contin-
setup (OER on the Pt electrode and HER on the carbon elec- uous operation for over 24 h at a current density of 0.25 A cm−2,
trode), an energy efficiency of around 80% was estimated for the potentials required to maintain this current density on the
the decoupled system. The decoupled system was able to gen- OER and HER cells rose by 33 and 103 mV, respectively, sug-
erate hydrogen with a Faradaic efficiency of 98%, with almost gesting that buffer degradation remains only a partially solved
complete decoupling of this hydrogen production from oxygen problem in this system.
5. Solid State Redox Mediators the NiOOH/Ni(OH)2 electrode had completely decoupled the
two half-reactions of water splitting. The gaseous products were
5.1. NiOOH/Ni(OH)2 Electrodes quantified, and Faradaic efficiencies for both the HER and OER
were >90%. The authors then demonstrated how the reduc-
In all the examples of decoupled electrolysis listed thus far, the tion of the NiOOH electrode used in the oxygen evolution step
decoupled reactions have been mediated by species dissolved in (Equation (10)) could be coupled with the oxidation of Zn(0) to
the electrolyte. However, there is no strict requirement for the Zn2+ (rather than the oxidation of water/hydroxide), forming a
decoupling agent to be a soluble molecular species, and indeed NiOOH-Zn battery. When tested at a current of 200 mA, this
solid-state decoupling agents bring unique capabilities to battery was found to have a discharge voltage of ≈1.6 V with a
decoupled systems on account of their heterogeneous nature. total discharge time of ≈10 min. NiOOH could then be regener-
The first acknowledged example of a solid-state decoupled ated by carrying out the hydrogen evolution step (Equation (9)),
electrolysis system was reported by the groups of Wang and essentially recharging the battery. Hence this study again high-
Xia in early 2016,[64] using NiOOH/Ni(OH)2 as the decoupling lights the opportunities for new approaches to flexible energy
agent (a choice inspired by the charge/discharge reactions of storage and conversion that are afforded by the use of electro-
NiOOH/Ni(OH)2 when used as the cathode in commercial alka- chemical decoupling strategies.
line batteries).[65] The authors supported their nickel hydroxide Independently to Wang and Xia, the groups of Grader and
on carbon nanotubes to create a solid-state mediator/electrode Rothschild reported the use of the same NiOOH/Ni(OH)2
system, which was used to decouple the OER and HER of water mediator in a closed bipolar electrode-type system for decou-
splitting at high pH. The equations operating in this system pled water electrolysis under alkaline conditions.[66] Accord-
are shown in Equations (9) and (10), and further illustrated ingly, simultaneous hydrogen and oxygen generation was
in Figure 12. Hence, in the HER step, oxidation of Ni(OH)2 to achieved in two spatially separated, two-compartment cells
NiOOH (in which the Ni2+ center is oxidized to Ni3+) is coupled from 1 m NaOH electrolytes. Both of the cells employed a
to the production of hydrogen (Equation (9)). The decoupling NiOOH/Ni(OH)2 electrode, linked by copper wire, and a Ni foil
agent is then rereduced to Ni(OH)2 with concomitant oxygen electrode at which the gaseous products were generated. Over
production in the OER step. the course of 20 h, at an applied current density of 5 mA cm–2,
the system was able to generate both H2 and O2 continuously.
1 Once the cell voltage reached a certain threshold (indicating
Ni (OH)2 → NiOOH + H2 (9)
2 that the nickel hydroxide electrodes had been fully charged/
discharged), the current polarity was reversed, driving the reac-
1 tions performed in each cell in the opposite direction. Over the
2NiOOH + H2 O → 2Ni (OH)2 + O2 (10)
2 20 h, the total charge/discharge time for each cycle was found
to decrease in duration by an average of 0.3% per cycle; this
Using cyclic voltammetry, the researchers confirmed that the was attributed to incomplete charging of the NiOOH/Ni(OH)2
NiOOH/Ni(OH)2 redox couple fell between the onset potentials electrode in the HER cell. Following this, the researchers per-
of the HER and OER. The system was then tested by performing formed longer cycles (>6 h) where the electrodes were charged
100 redox cycles, with voltage readings suggesting stable opera- to 448 mAh (≈34% of their rated capacity), with the overall
tion under these consecutive H2 and O2 generation steps. In experiment lasting 125 h. Analysis of the product gases revealed
situ differential electrochemical mass spectrometry was used that H2 and O2 were produced at ≈100% Faradaic efficiency. The
to analyze the purity of the gaseous products formed. In the NiOOH/Ni(OH)2 closed bipolar electrode cell arrangement was
hydrogen evolution step, no O2 above the background level was also integrated with an Si photovoltaic module to form a solar-
detected. Similarly, analysis of the gases produced in the oxygen powered water splitting system, and a solar-to-hydrogen conver-
evolution step revealed that no H2 was generated, and thus that sion efficiency of 7.5% was achieved. This result was compa-
rable to those obtained with the state-of-the-art solar-powered
water splitting systems at time of writing.[67–71]
Some of the same authors subsequently demonstrated that
the oxygen evolution/mediator reduction step of NiOOH/
Ni(OH)2 could be rendered spontaneous, thus removing one
set of electrochemical losses from the system.[72,73] Using a
cobalt-doped nickel hydroxide electrode (Ni0.9Co0.1(OH)2), the
hydrogen evolution step was first performed electrochemically
at 25 °C (in an analogous fashion to Equation (9)), to generate
the oxidized form of the cobalt-doped nickel hydroxide electrode
(Ni0.9Co0.1OOH). This “charged” electrode was then removed
from the electrolysis cell and placed in 5 m KOH which had
been heated to 95 °C, at which temperature the decomposi-
tion reaction of Ni0.9Co0.1OOH to regenerate Ni0.9Co0.1(OH)2
Figure 12. Schematic illustrating the mode of action of NiOOH/Ni(OH)2
as a solid decoupling agent electrode. OER is coupled to NiOOH reduc- (releasing O2 in the process) is both exothermic and sponta-
tion (red arrows) and HER is coupled to Ni(OH)2 oxidation (green neous. This system was tested using consecutive 100-second
arrows). cycles of hydrogen and oxygen production, at a fixed current
density of 50 mA cm–2, evincing a voltage efficiency of 98.7% hydrogen and oxygen at an average current of 55 mA and a
(voltage efficiency = Vth/Vcell, where Vth is the thermoneutral solar-to-hydrogen efficiency of ≈0.7%.
voltage of water splitting). As the oxygen evolution step in
this system was spontaneous at 95 °C and as the energy for
this thermal step could be provided by waste heat, the overall 5.2. Other Solid Metal Oxides
efficiency of this process has the potential to be considerably
higher than for systems where both oxidation and reduction of Soon after the publication of NiOOH/Ni(OH)2 as a decoupling
the NiOOH/Ni(OH)2 couple are performed electrochemically. agent, Xiao and co-workers reported the use of FeOx as a solid
Recently, the Grader and Rothschild groups have demon- state mediator electrode.[75] Their system employed three elec-
strated decoupled hydrogen and oxygen production using trodes: an Ni-Fe anode, a Pt/C cathode, and the FeOx solid state
NiOOH/Ni(OH)2 electrodes driven purely by solar irradiation, mediator electrode (supported on Ni foam). During charging,
whereby the O2 and H2 are produced in entirely different cells oxygen was evolved at the Ni-Fe anode as the FeOx (in the
which are connected only electrically.[74] A schematic of the same compartment of the electrochemical cell) underwent a
concept behind this setup is shown in Figure 13, which used two-electron reduction. Then, during discharge, hydrogen was
a closed-bipolar-type NiOOH/Ni(OH)2 electrode. The oxygen- produced at the Pt/C cathode (in a separate compartment,
evolving cell contained a hematite (α-Fe2O3) photoanode, which separated from the first compartment by an anion exchange
was interfaced with a monocrystalline silicon photovoltaic membrane) alongside reoxidation of FeOx decoupling agent.
module to provide additional potential bias. Indeed, this photo- The performance of the device was assessed by carrying out
anode/photovoltaic ensemble provided sufficient energy to 50 consecutive charge/discharge cycles, showing that the
drive all of the electrochemical reactions that ensued. O2 was capacity retention and Faradaic efficiency were 97% and >90%,
evolved in this cell with simultaneous reduction of the NiOOH respectively. The authors were also able to demonstrate solar-
electrode also present in the cell. Meanwhile, in the separate powered decoupled electrolysis, by substituting the Ni-Fe anode
hydrogen evolution cell, the H2 was evolved at a Pt-coated Ti for a TiO2/Co-Pi photoanode and exposing this to sunlight. The
mesh cathode as Ni(OH)2 was oxidized. Compared to solar- solar-to-hydrogen conversion efficiency of this configuration
driven decoupled electrolysis protocols that use soluble redox was found to be 3.3%.
mediators, this approach has the advantage that there is no In 2017, Choi et al. employed a manganese dioxide mediator
need to pump any decoupling agent solutions between cells, electrode to decouple the half-reactions of water splitting.[76]
and therefore no need for membrane separators. However, This mediator electrode was used in a three-electrode setup
the main disadvantage is that the solid-state decoupling agent alongside an Ni(OH)2 positive electrode and a lanthanum-
electrodes have a finite capacity, and that they must be replaced nickel metal hydride negative electrode. Both hydrogen and
(or swapped round) once they reach this capacity limit in order oxygen were produced in separate steps as a function of which
for electrolysis to continue. Using a system whereby multiple electrodes were connected; in the first step, the oxygen evolu-
NiOOH/Ni(OH)2 electrodes were present in each cell and used tion reaction was accompanied by the reduction of the mediator
in succession, the authors were able to carry out ten water electrode (Equation (11)), whilst in the second step the oxidation
splitting cycles of over eight hours’ duration each, producing of MnOOH (Equation (12)) occurred with simultaneous reduc-
tion of water to form hydrogen.
1
2MnO2 + H2 O → 2MnOOH + O2
2 (11)
2MnOOH → 2MnO 2 + H 2 (12)
In this cell, a current of 5 mA was maintained over 10 h
for both steps, at 25, 40, and 60 °C. Although the oxygen and
hydrogen generation steps could be effectively decoupled, the
authors noted that the energy conversion efficiency of their
system was low in comparison to conventional (i.e., coupled)
devices, which they attributed to the high overpotentials associ-
ated with the use of the MnO2 electrodes.
5.3. Solar-Thermal Decoupled Electrolysis
When heated to high temperatures in air, certain transition

metal oxides can be reduced to lower oxides with the release
of oxygen. For example, at temperatures above 1370 °C, the
Figure 13. The system employed by Landman et al.[74] whereby oxygen
process
is produced in a photoelectrochemical-photovoltaic tandem cell and
hydrogen is produced separately in a conventional electrochemical cell,
using separated NiOOH and Ni(OH)2 electrodes to decouple the OER 1
3Fe 2 O3 → 2Fe3 O4 + O2(13)
and HER. 2
yellow powder was observed to form in the slurry as the pri-

mary product of electrochemical oxidation; unreacted mag-
netite was separated from this product through the use of
magnets. Powder X-ray diffraction then revealed that the yellow
product was FeOOH. The authors then completed the thermal-
electrochemical cycle by heating this FeOOH to 1400 °C at a
rate of 10 °C min–1, whereupon simultaneous thermogravi-
metric and differential scanning calorimetry analyses indicated
that the FeOOH was first thermally dehydrated to Fe2O3, before
Figure 14. The solar thermal decoupled process proposed by Palumbo this Fe2O3 underwent thermal reduction to produce Fe3O4 with
et al.[77] using the example of iron oxides. release of O2 (Equation (13)). Some of the same authors sub-
sequently showed that a similar thermal-electrochemical cycle
occurs, and similar thermal decomposition reactions are known for decoupled oxygen and hydrogen production from water was
for Co and Mn oxides. Palumbo et al. used this as their starting also possible with cobalt oxides.[78] This approach is somewhat
point for assessing the prospects for a combined thermal- remarkable in that the decoupling agent is neither a monolithic
electrochemical cycle for decoupled water splitting, for these electrode, nor a soluble molecular species. Instead, the decou-
three metal oxides, according to the general scheme shown in pling agent is a suspension of otherwise insoluble particles.
Figure 14.[77] Whether or not such a system could be implemented on a large
According to this scheme, thermally generated magnetite scale for continuous operation remains to be seen, but the con-
(Fe3O4) can be reoxidized electrochemically to give Fe2O3, with cept certainly seems to merit further study.
simultaneous hydrogen generation occurring at the cathode.
The oxygen and hydrogen generation steps are thus com-
pletely decoupled via the use of this metal oxide mediator. 5.4. Solid Organic Decoupling Agents
Palumbo et al. demonstrated the feasibility of the electro-
chemical aspects of this work using a cell design such as that Decoupling of the HER and OER has also been described using
shown in Figure 15. Fe3O4 was suspended in either H2SO4 reversible n-type doping of the solid-state battery material,
or KOH, forming a slurry of magnetite particles in the elec- polytriphenylamine (PTPAn).[79] The organic polymer PTPAn
trolyte. Due to gravity, the magnetite particles tend to sink has a structure consisting of conductive polyparaphenylene
toward the bottom of the cell, leaving the upper part of the cell chains on which electroactive polyaniline units are attached
free of particles (and hence just electrolyte solution to a first (see Figure 16a), giving the material excellent reported redox
approximation). Through judicious choice of stirring rates, the cycling stability, and making it well-suited for use as a redox
authors were able to maintain two regions (one with particles, mediator.[80–82] In acidic electrolyte (0.5 m H2SO4), cyclic vol-
and one without) in their cell throughout the electrolysis. Into tammetry performed by Wang and co-workers indicated that
the slurry region of the cell was placed a Pt foil electrode to PTPAn has two redox couples which reside between the onset
act as the anode. Meanwhile, a Pt-coated Mo wire was inserted voltages of the HER and OER. For the decoupled water electrol-
into the top half of the cell to act as the cathode. Electrolysis ysis experiments, hydrogen was evolved at a Pt-coated Ti mesh
was then initiated in order to oxidize the magnetite particles, electrode while RuO2/IrO2-coated Ti mesh was used as the
whilst simultaneously generating hydrogen at the cathode. Gas oxygen evolving electrode; these reactions followed Equations
chromatography analysis of the headspace of the cell revealed (1) and (2), respectively. Galvanostatic electrolysis at a current of
that hydrogen was produced in this experiment with a Faradaic 100 mA was found to produce hydrogen and oxygen with Fara-
efficiency of ≈100%. Moreover, no oxygen was detected during daic efficiencies approaching 100%. Decoupled electrolysis was
electrochemical hydrogen generation, suggesting complete then driven using an Si photovoltaic module to demonstrate
decoupling of the HER from oxygen production. Instead, a that the system could convert solar energy and water directly
to H2 and O2. A solar-to-hydrogen conversion efficiency of 5.4%
was achieved using this photovoltaic system, when exposed to
sunlight.
In 2019, some of the same authors reported the use of
pyrene-4,5,9,10-tetraone (PTO) as a solid-state mediator to
successfully decouple hydrogen and oxygen production from
water.[83] In this study, the HER and OER were separately cou-
pled to the reversible enolization reaction of PTO (Figure 16b).
In contrast to PTPAn, this PTO-based mediator undergoes
reversible protonation and deprotonation during redox cycling
and so has the potential to buffer the solution pH during opera-
tion. Cyclic voltammograms taken of the compound revealed
two reversible redox couples which both fell between the
onset potentials of the HER and OER when using a Pt-coated
Figure 15. The layered electrochemical cell employed by Palumbo et al.[77] Ti mesh cathode and RuO2/IrO2-coated Ti mesh anode. This
using the example of iron oxides. analysis also revealed that the redox processes of PTO were not
Figure 16. a) The polytriphenylamine (PTPAn) redox couple employed by Wang and co-workers.[79] b) The pyrene-4,5,9,10-tetraone (PTO) redox couple.
iffusion limited, suggesting that the buffer is indeed in the

d Proton Buffers) can in theory be used as hydrogenation agents,
solid state. The mediator performed well for decoupled oxygen replacing gaseous hydrogen as a reagent. Ultimately, this could
and hydrogen evolution during electrolytic water splitting in lead to the replacement of dangerous and/or toxic chemical rea-
0.5 m H2SO4 over multiple cycles, with Faradaic efficiencies for gents by sustainable electricity and water.
both gases approaching 100%. The polyoxometalate silicotungstic acid has found utility in
Finally in this section, the conducting polymer polyaniline this regard as a sustainable hydrogenation agent for a number
has also been utilized as an electrode material to decouple the of organic transformations. In 2018, MacDonald et al.[87] used
HER and OER under acidic conditions.[84] Wang et al. carried the two-electron reduced form of this compound (H6SiW12O40,
out cyclic voltammetry on polyaniline film electrodes, after which they generated electrochemically with concomitant
pressing a powder of the polymer onto Ti mesh. They discov- oxidation of water) as a source of protons and electrons for the
ered two redox couples, which they attributed to two different reduction of a range of nitroarene compounds to their aniline
doping states of polyaniline; both of these couples had redox analogues in (on the whole) good to excellent yields (Figure 17a).
potentials between the onset potentials of the HER and OER. The silicotungstic acid could then be recycled, rereduced, and
Decoupling experiments were performed in 0.5 m H2SO4, in reused without any appreciable drop in catalytic performance.
a three-electrode configuration, with a Pt HER electrode and a Intriguingly in this example, it was found that H6SiW12O40 was
RuO2/IrO2 electrode for the OER. When assessing the charge effective for these hydrogenation reactions without the need
storage capabilities of polyaniline, the authors found that it for any cocatalyst, thus providing distinct advantages over tra-
far exceeded several other redox mediators, such as phospho- ditional chemical approaches to nitroarene reduction (e.g., the
molybdic acid and PTPAn. Using a charge–discharge rate of use of H2 gas with a Pt/C catalyst or the use of sacrificial sol-
0.2 A g–1, the reversible discharge capacity of polyaniline was uble hydrogenation agents with various cocatalysts).
found to be 125 mAh g–1. At this same charge–discharge rate, Wu et al. have used the same compound (H6SiW12O40, also
the stability of polyaniline under consecutive cycling was also prepared through decoupled electrolysis with simultaneous
investigated. It was found that over 40 cycles, the Coulombic water oxidation) to perform the hydrogenation of phenylacety-
efficiency of the cycling remained at ≈100%; capacity reten- lene and acetophenone (Figure 17b).[85] In this case, a Pt/C or
tion after this cycling was also high (92%). To investigate the Pd/C catalyst was found to be essential for reductive activity.
suitability of this system for solar applications, the researchers Ethanol/water mixtures were used as the media for both the
employed an Si solar cell as a power source. With an applied hydrogenation reactions (to improve substrate solubility) and
potential of ≈1.0 V from the solar component, decoupled water for the electrochemical generation of H6SiW12O40. The maximal
splitting was achieved when using the polyaniline mediator conversions of phenylacetylene and acetophenone were 100%
electrode, although no solar-to-hydrogen conversion efficiency and 80% respectively, and some selectivity over the products’
is quoted. depth of reduction could be obtained by alteration of the reac-
tion conditions. Taken together, these two studies suggest that
reduced soluble decoupling agents have considerable potential
6. Decoupled Electrolysis for Chemical Synthesis as sustainable and easy-to-handle hydrogenation agents for
organic synthesis.
The ability to store electrons for extended periods of time on Decoupled electrolysis has also been employed in reactions
reduced decoupling agents raises the prospect of using these where organic substrates are oxidized. Li et al. used the decou-
species as reducing equivalents for chemical processes other pling agent Na4[Fe(CN)6] (which they also showed to be effec-
than hydrogen generation. This approach has two especially tive for decoupled water electrolysis) to decouple the HER from
attractive features. First, if these reduced decoupling agents are the oxidation of 5-hydroxymethylfurfural to 2,5-furandicar-
produced using electrons (and protons) derived from water, then boxylic acid.[56] 5-Hydroxymethylfurfural is a readily available
they constitute sustainable reducing equivalents. Second, those product of dehydration of certain sugars and thus constitutes
decoupling agents that also store protons (Electron-Coupled- a sustainable feedstock chemical; the authors proposed that
Figure 17. Organic transformations mediated by reduced silicotungstic acid prepared by decoupled water electrolysis: a) Reductions of nitroarenes as
reported by MacDonald et al.[87] b) Hydrogenation of phenylacetylene and acetophenone as reported by Wu et al.[85]
its chemical transformation to 2,5-furandicarboxylic acid rep- further purification. The authors argued that this separation of
resented a higher-value anodic counterpart for hydrogen evo- the product gases would decrease the complexity of any scaled-
lution than the oxidation of water. Accordingly, the authors up version of the process as well as allowing a portion of the
assembled a two-compartment cell separated by a cation energy spent on the anodic oxidation of pollutants (10–20%) to
exchange membrane. The HER was first performed at a CoP on be recovered in the form of hydrogen fuel.
carbon electrode, with concomitant oxidation of the decoupling The final examples of the application of decoupled elec-
agent at the carbon counter electrode. In the second step, this trolysis for performing reactions beyond water splitting that
mediator was rereduced as 5-hydroxymethylfurfural oxidation we shall consider both relate to the chlor-alkali process. In the
occurred at a Ni anode. 100% conversion of 5-hydroxymethyl- chlor-alkali process, a sodium chloride solution is electrolyzed
furfural (giving an 83% yield of 2,5-furandicarboxylic acid) was to generate Cl2, H2, and NaOH as the products. Together, these
reported, using mild electrochemical conditions. This approach products are themselves used in over 50% of all industrial pro-
could offer an effective and environmentally friendly approach cesses, underlining the fundamental importance of the chlor-
for combining the electrolytic production of hydrogen with the alkali process to the chemical industry at large. Historically,
generation of useful chemicals in situations where sustainably Cl2, H2, and NaOH were produced in mercury-containing cells
sourced organic feedstocks are available. according to the Castner–Kellner process (itself an electro-
This Fe(CN)63–/Fe(CN)64– decoupling agent has also been chemical decoupling strategy, whereby Cl2 and H2 evolution
employed by You and co-workers to decouple hydrogen produc- are decoupled using a mercury amalgam electrode as the
tion from the oxidation of organic pollutants during electro- decoupling agent).[88] In recent years, however, mercury cells
chemical decontamination of wastewater.[86] In a conventional have fallen out of favor due to concerns over mercury’s tox-
electrochemical cell for oxidation of organic pollutants, the cor- icity. Hence, most chlor-alkali cells now use either asbestos
responding cathode reaction is the generation of hydrogen. The diaphragms or fluorine-containing ion-exchange membranes
authors suggested that this presents a hazard under some con- to separate the chlorine and hydrogen that are produced. How-
ditions and is also wasteful, as the H2 is rarely harvested. They ever, Hou et al. argued that the high cost of these separators
therefore proposed decoupling as a route by which hydrogen and their short lifetimes during operation made the need for
generation could take place outside the pollutant oxidation cell, improvements vital. Therefore, these authors proposed a mem-
for safety and ease of hydrogen collection. In a system similar brane-free process whereby the Cl2 evolution and H2/NaOH
to that used by Goodwin and Walsh,[55] two separate two-com- production steps were decoupled by employing the reversible
partment cells were bridged by a closed bipolar electrode. This Na-ion intercalation/deintercalation reaction of an Na0.44MnO2-
allowed the generation of hydrogen via water splitting at a Pt/C based electrode.[89]
cathode, with concomitant oxidation of Fe(CN)64– to Fe(CN)63– An illustration of this decoupled process and the reactions
at the anode, to occur in one cell. In the other cell, oxidation involved is provided in Figure 18. Hence water reduction to
of the organic pollutant phenol was achieved on a TiSO anode, generate H2 and hydroxide is accompanied by sodium deinterca-
with accompanying Fe(CN)63– reduction to Fe(CN)64– at the lation from the decoupling agent electrode. Subsequently, chlo-
cathode. At current densities of 16 mA cm–2, the phenol removal ride ions are oxidized to Cl2 with the simultaneous reduction of
efficiency at the TiSO anode over 2 h was found to exceed 96%, the decoupling electrode, which occurs together with reinterca-
whilst the Faradaic yield for hydrogen production at the Pt/C lation of sodium ions to restore the original Na0.44MnO2 stoi-
cathode in the other cell was quantitative. This hydrogen was chiometry. The Na0.44MnO2-based electrode has previously been
generated in a separate cell to the organic oxidation reaction employed in sodium ion batteries and so displays the required
(which generates O2 as a side product) and so required no sodium ion intercalation/deintercalation properties; its redox
Figure 18. The two-step decoupled chlor-alkali process reported by Hou et al.[89]
waves are also almost exactly midway between the onset poten- Hence, in the first cell, oxygen reduction (to hydroxide) is
tials of hydrogen and chlorine evolution. paired with oxidation (and desodiation) of a Na0.44MnO2-based
In the first step, hydrogen evolution on a Pt-coated Ti-mesh electrode to generate NaOH. The desodiated Na0.44–xMnO2 elec-
electrode was found to proceed at a Faradaic efficiency of 100%, trode is then placed in a chloride-containing electrolyte and
whilst in the second step, chlorine evolution on a RuO2/IrO2- used as the cathode in a second electrolysis cell, alongside a
coated Ti mesh displayed a Faradaic efficiency of 90%, which silver anode. Operating this cell rereduces (and resodiates) the
the authors attributed to the hydrolysis of Cl2 to give soluble Na0.44MnO2 electrode, whilst at the anode insoluble AgCl forms.
species such as HClO. The authors also noted that the current In the final step, the AgCl electrode is used as the cathode in a
density that the system can reach is limited by the kinetics of third electrolytic cell alongside a graphite anode. As the AgCl is
sodium ion intercalation/deintercalation into and out of the reduced (regenerating Ag(0)), chloride ions are released which
Na0.44MnO2-based electrode. Technologically relevant current migrate to the anode where they are discharged as Cl2. The
densities for the HER and chlorine evolution reactions of up overall reaction thus produces no hydrogen and is
to 0.5 A cm–2 were achieved, but only if very large Na0.44MnO2
4Na + + 4Cl − + O2 + 2H2 O → 4NaOH + 2Cl 2 (14)
electrodes were employed. Attempting to improve the kinetics
of this intercalation/deintercalation process would therefore be The authors suggested that such an approach decouples
one area in which further investigation could prove beneficial, NaOH and chlorine production and so prevents the produc-
and which might bring about the realization of some of the tion of caustic chlorates which could otherwise damage the
benefits of decoupling for this reaction (including avoiding Na0.44MnO2 electrode. Using oxygen as the reductive couple in
the need for a membrane separator and preventing mixing of the first cell was also held to reduce the overall voltage require-
the H2 and Cl2 product gases). ment for Cl2 and NaOH production. Excellent stability to mul-
Zhao et al. have taken this work a step further, by proposing tiple redox cycles was demonstrated for each of the three pro-
a system for decoupling Cl2 and NaOH production that uses two cesses, with high Coulombic efficiencies. Moreover, the authors
decoupling agents and three different electrochemical cell config- were also able to show that this concept can be expanded to
urations.[90] An illustration of this concept is provided in Figure 19. other salts, e.g., to the continuous production of NaOH and
Figure 19. The three-step decoupled chlor-alkali process reported by Zhao et al.[90]
HNO3 from a solution of NaNO3. This route therefore offers the near term due to the obvious benefits this has for solar-to-
considerable promise, although it may prove nontrivial to hydrogen devices. Likewise, solar-driven electrochemical pro-
design large-scale systems where multiple electrodes are easily cesses of all sorts can benefit from the decoupling of the rates
switched between cells. of the relevant half-reactions that this process allows: slow, solar
intensity-limited processes can be used to trickle-charge decou-
pling agents, which can then be used in more rapid reactions
7. Conclusions and Outlook that are not limited by the instantaneous solar flux. Again, the
benefits for the collection of hydrogen from solar-driven water
In this review, we have examined the current state-of-the-art splitting are obvious and have been highlighted by a number
in decoupled electrolysis for water splitting, following the of the studies discussed in this review. In the longer term,
development of the field from its conceptualization in 2013 we anticipate that the ability to use electrochemical decou-
through to the numerous elaborations of decoupled elec- pling as a means to obtain sustainable reduction equivalents
trolysis that have since been developed. Key milestones along (e.g., hydrogen equivalents from water) will have considerable
this journey have included the demonstration of solar-driven impact on chemical synthesis in general. Approaches of this
hydrogen production using decoupling strategies, the discovery nature may include further elaboration on the organic hydro-
of decoupling agents that can be induced to perform one of the genation reactions that are discussed above, but perhaps more
half-reactions of water splitting spontaneously (e.g., by manip- excitingly could also include new concepts and device designs
ulation of the temperature or by suitable choice of electrodes for critical underpinning processes such as CO2 and N2 reduc-
and/or catalysts), the development of robust solid-state decou- tion. Given the rapid progress and immense creativity that has
pling agents, the conjunction of decoupling strategies with already been in evidence in the field, it seems that the future of
bipolar electrolysis, and the application of decoupling strategies decoupled electrolysis is bright.
to reactions beyond water splitting (e.g., coupling H2 produc-
tion with organic upgrading oxidation reactions or performing
organic hydrogenation reactions using protons and electrons Acknowledgements
derived from water). Furthermore, it will be apparent that
M.D.S. thanks the Royal Society for a University Research Fellowship
decoupling can be applied both for electrolytic processes (i.e., (UF150104) and acknowledges the Engineering and Physical Sciences
those requiring a net energy input such as water splitting) and Research Council for supporting his work in this area (EP/K023004/1
galvanic processes (where spontaneous chemical reactions are and EP/R020914/1). P.J.M. and A.D.S. both thank the Royal Society for
harnessed to produce electrical power as in fuel cells). Ph.D. scholarships. The authors note that a similar review has recently
A number of key challenges remain in the development of been published on the pre-print arXiv website.[91] This review and their
own were developed in parallel by different groups of authors at different
decoupled electrolysis. The majority of these can be distilled
institutions and are thus completely independent of each other.
into just two main brackets: device complexity and overall
system stability. In terms of the latter, materials compatibility
between the decoupling agents and other cell components
Conflict of Interest
(e.g., membrane separators) and the stability of the agents
themselves to repeated redox cycling often remains unproven, M.S. holds two patents on the use of decoupling agents for water
largely due to a lack of data on the long-term performance of splitting.
decoupled systems (as indicated, for example, by the “Number
of Cycles Tested” column in Table 1). Robust data on long-term
system stability must be obtained before commercial applica- Keywords
tions become a reality. Meanwhile, decoupled electrolysis sys- decoupled electrolysis, electron-coupled-proton buffers, hydrogen
tems often give rise to increased requirements for additional evolution reaction, oxygen evolution reaction, redox mediators, solar-to-
balance of plant (and hence involve greater complexity) com- hydrogen, water splitting
pared to simpler, coupled approaches. For decoupling agents in
Received: July 30, 2020
solution, this manifests as a requirement for additional pumps
Revised: September 29, 2020
and flow systems, and often the decoupling agent solutions are
Published online: October 13, 2020
more viscous than water or other commonly encountered sol-
vents. For solid-state decoupling agents, developing workable
protocols for continuous operation of the resulting systems will
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Patrick James McHugh graduated with an M.Sc. in Chemistry from the University of Glasgow in
2018. During his degree, he spent a year on placement at Humboldt-Universität zu Berlin working
for Prof. Thomas Braun. Since graduating, Patrick has been pursuing a Ph.D. in Electrochemistry
under the supervision of Dr. Mark Symes. In 2019, he was accepted by the European Space
Agency as part of a student team to participate in their FlyYourThesis! Programme.
Athanasios D. Stergiou graduated with a B.Sc. in Chemistry from the University of Ioannina in
2016. After obtaining an M.Sc. degree in Green and Sustainable Chemistry from the University of
Nottingham (2017), he joined the Symes group at the University of Glasgow to pursue a Ph.D. in
electrochemistry. His research interests include indirect electrosynthesis, continuous flow electro-
chemistry and electrocatalysis.
Mark D. Symes obtained his M.Sc. degree from the University of Cambridge (2005) and a Ph.D.
from the University of Edinburgh (2009), before undertaking postdoctoral appointments at the
Massachusetts Institute of Technology and the University of Glasgow. He was elevated to the fac-
ulty at Glasgow in 2013 and is now a Royal Society University Research Fellow and Senior Lecturer
in electrochemistry, electrocatalysis, and electrochemical technology at Glasgow.

Advanced Energy Materials - 2020 - McHugh - Decoupled Electrochemical Water Splitting From Fundamentals To Applications

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Decoupled Electrochemical Water Splitting: From

rely on fossil fuels is of great importance.

DOI: 10.1002/aenm.202002453 4OH− → O2 + 2H2 O + 4e − OER ( pH14, E = 0.40V ) (4)

[ECPB( two −electron reduced)][H+ ]2 → H2 + ECPB (6)

a separate hydrogen-evolving cell where it could be reoxidized

ecoupling agent. On a carbon electrode, both of these reduc-

electrochemical cell was saturated with O2 at pH = 0 (under

5.3. Solar-Thermal Decoupled Electrolysis

When heated to high temperatures in air, certain transition

yellow powder was observed to form in the slurry as the pri-

iffusion limited, suggesting that the buffer is indeed in the

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Advanced Energy Materials - 2020 - McHugh - Decoupled Electrochemical Water Splitting From Fundamentals To Applications

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Advanced Energy Materials - 2020 - McHugh - Decoupled Electrochemical Water Splitting From Fundamentals To Applications

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Copyright

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Share this document

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Advanced Energy Materials - 2020 - McHugh - Decoupled Electrochemical Water Splitting From Fundamentals To Applications

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Copyright:

Available Formats

Review

Decoupled Electrochemical Water Splitting: From

rely on fossil fuels is of great importance.

DOI: 10.1002/aenm.202002453 4OH− → O2 + 2H2 O + 4e − OER ( pH14, E = 0.40V ) (4)

[ECPB( two −electron reduced)][H+ ]2 → H2 + ECPB (6)

a separate hydrogen-evolving cell where it could be reoxidized

­ ecoupling agent. On a carbon electrode, both of these reduc-

electrochemical cell was saturated with O2 at pH = 0 (under

5.3. Solar-Thermal Decoupled Electrolysis

When heated to high temperatures in air, certain transition

yellow powder was observed to form in the slurry as the pri-

­ iffusion limited, suggesting that the buffer is indeed in the

You might also like

ecoupling agent. On a carbon electrode, both of these reduc-

iffusion limited, suggesting that the buffer is indeed in the