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Fuel Processing Technology 236 (2022) 107437

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Fuel Processing Technology


journal homepage: www.elsevier.com/locate/fuproc

Research article

Preparation of renewable porous carbons for CO2 capture – A review


Yafei Shen a, b, *
a
Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Collaborative Innovation Center of Atmospheric Environment and
Equipment Technology, School of Environmental Science and Engineering, Nanjing University of Information Science and Technology (NUIST), Nanjing 210044, China
b
Residues and Resource Reclamation Centre, Nanyang Environment and Water Research Institute, Nanyang Technological University, Singapore 637141, Singapore

A R T I C L E I N F O A B S T R A C T

Keywords: A diversity of renewable wastes such as biomass and plastic can be employed for the synthesis of porous carbons,
Waste plastic which have emerged as promising materials for CO2 capture under a wide range of conditions owing to their
Biomass unique properties. Because of limited review articles in this field, this paper provided the recent progress and
Porous carbons
significant challenges in the synthesis of renewable porous carbons for CO2 capture with the objective of guiding
CO2 capture
future works on the CO2 abatement technologies towards a sustainable direction. Among the post-consumer
N functional groups
plastics, PET has been widely used for the synthesis of porous carbons for effective CO2 capture because of its
high carbon and oxygen content. In general, porous carbons derived from waste biomass and plastic are quite
attractive for CO2 capture due to their tunable textural properties, simple synthesis methods and high CO2
adsorption capacities, which are closely associated with the structures and properties of porous carbons (e.g.,
microporous structure, heteroatoms doping). Particularly, the doped N species (e.g., pyridinic-N, pyrrolic-N) can
transform the electronic state of the H atoms in the –CH and –NH groups on porous carbons to form hydrogen
bonds between H and the O atom of CO2 molecule, thus for enhancing the CO2 adsorption.

1. Introduction the capture and comprehensive utilization of CO2 has a great practical
significance. Here the whole process of CCUS mainly includes CO2
The uninterruptedly utilization of fossil fuels has brought huge CO2 capture, utilization, and storage [5]. In common, the CO2 capture
emissions to the Earth [1]. It was reported that the concentration of methods include adsorption (solid phase), absorption (liquid phase) and
atmospheric CO2 increased from 277 ppm in 1750 to 410 ppm in 2019 integrated process [6]. Furthermore, the captured CO2 can be stored in
[2], thus resulting in the increase of global temperature to 2 ◦ C above the the soil or reused. In the utilization approach, the captured CO2 can be
pre-Industrial Revolution levels [3]. More importantly, the concentra­ converted into C1-C2 compounds (e.g., CO, CH4, CH3OH, and C2H4) for
tion of CO2 was predicated reaching up to 950 ppm by the end of this use as fuels or chemicals [7–9]. In addition, the captured CO2 can be
century, which would lead to drastic changes in the atmospheric compressed, and then transported for diverse applications such as
chemistry [4]. Based on this issue, great research and development have carbon-based fertilizers to achieve soil sequestration [10]. Carbon cap­
been triggered in the field of CO2 capture. In recent years, various ture and sequestration (CCS) is a promising technology for minimizing
strategies have been developed increasingly to mitigate anthropogenic CO2 emissions from the point sources such as coal-fired power plants
climate change because of CO2 emission [5]. China has taken active [11], involving the capture and transportation of CO2 to storage site
measures to curb CO2 emissions. On September 22, 2020, President Xi [12]. The significant challenge in the entire process is the high operation
Jinping announced at the United Nations General Assembly that China cost of CO2 capture. The current situation of CCS has been reviewed in
would take more powerful measures, strive to reach the peak of CO2 terms of the technology readiness levels of CCS technologies on a global
emissions by 2030, and strive to achieve carbon neutrality by 2060. scale. It is noteworthy that United States is ahead of other countries in
Carbon capture, utilization, and storage (CCUS) technology plays an capturing the largest amounts of CO2 (7–8.4 MtCO2 per year) using CCS,
important role in cutting down carbon emissions. As illustrated in Fig. 1, followed by China (0.4–2 MtCO2 per year) and Europe (0.7–1 MtCO2 per

* Corresponding author at: Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), Collaborative Innovation Center of
Atmospheric Environment and Equipment Technology, School of Environmental Science and Engineering, Nanjing University of Information Science and Technology
(NUIST), Nanjing 210044, China.
E-mail address: [email protected].

https://doi.org/10.1016/j.fuproc.2022.107437
Received 17 May 2022; Received in revised form 9 July 2022; Accepted 23 July 2022
Available online 2 August 2022
0378-3820/© 2022 Elsevier B.V. All rights reserved.
Y. Shen Fuel Processing Technology 236 (2022) 107437

year) [13]. synergistic optimization. Recently, this technology has attracted much
In common, the processes of CO2 capture are classified into three attention since a diversity of functional materials can be used for CO2
types (Fig. 2) [14]. In general, the pre-combustion capture technology separation and capture [28]. Among these technologies, the post-
is used for capturing CO2 prior to the combustion process [15]. Inte­ combustion capture technology is the most extensively used in in­
grated gasification combined cycle (IGCC) power plants mostly use this dustry. For example, SaskPower (Canada) and TMC Mongstad (Norway)
technology to capture CO2. These IGCC power plant systems initially can capture 1,000,000 t and 300,000 t of CO2 per year, respectively
convert fuels (e.g., biomass, fossil fuels) into syngas (a mixture of CO and [29]. Removal of impurities from the captured CO2 is the main hurdle at
H2) through partial oxidation or gasification process [16]. Particulate ambient conditions due to low concentration of CO2 in flue gas (4 vol%
matter can be firstly removed from syngas, which is converted CO and in natural gas-fired system and 13–15 vol% in coal-fired system) [30].
H2O into CO2 and H2 in a water gas shift (WGS) reformer. Sorbents can This technology is quite appropriate for existing power plants with less
be used for CO2 capture at later stage. Here H2 can be applied in various modification in infrastructure [13].
fossil fuel-fired power plants with less CO2 emission [15,17]. The con­
centration of CO2 ranging of 15–60% makes it easy to capture, but the 2. Porous materials for CO2 capture
process of gasification and WGS reaction is expensive [18]. The oxy-fuel
combustion technology for CO2 capture has attracted attention in Since it is difficult to cleavage the C–
– O bond with a high bond en­
recent years because of its lower cost compared with other technologies ergy (750 kJ/mol) in the CO2 molecule, the adsorption by porous ma­
[19,20]. It was reported by the International Energy Agency (IEA) in terials is a promising method for CO2 capture. The absorption by
2020 that the oxy-fuel combustion technology could be commercialized aggressive amine solvents not only requires high-energy regeneration of
in coal-fired power plants [21]. Pure O2 taking place of air is used to absorbents, but also releases hazardous products [31]. Nano-porous
burn fuel, thus resulting in a significant reduction of N2 in flue gas. Here materials can play a crucial role in CCS because they exhibit a high
CO2 and H2O are further purified from particulates by the drying and adsorption capacity and good selectivity. More importantly, the prop­
liquefaction process. Finally, the liquefied carbon enriched product is erties of these porous materials can be manipulated easily to fit the
transported to storage site [22]. To acquire a moderate temperature of prospect of optimal adsorption energy for CO2 molecules. Recently,
furnace, the optimal flame temperature can be managed by recycling O2 significant development has been made in the area of micro- and meso-
(27–35%) from flue gas. Additionally, the optimal level of O2 for the porous materials for CO2 capture, mainly including metal-organic
combustion process is calculated at boiler inlet, depending on boiler frameworks (MOF) [32], zeolites [33], zeolitic imidazole frameworks
design and fuel properties [16]. The efficiency losses of oxy-fuel com­ (ZIF) [34], biomass-derived porous carbons [35], porous organic poly­
bustion systems in coal-fired power plants can be reduced 7–11% by mers (POPs) [36], porous polymer foams [37], and mesoporous carbon
upgrading process [23]. The drawback of this technology is separation nitrides [38]. In usual, the adsorption of CO2 by porous materials can be
of O2 from air that requires additional energy [24,25]. affected by several factors including specific surface area (SSA), pore
The post-combustion capture technology aims to separate and cap­ volume and size, and surface functional groups. Among these factors,
ture CO2 from flue gas after burning fossil fuels, including adsorption, pore size is a key factor. Particularly, porous materials rich in micro­
absorption, membrane separation, and cryogenic fractionation [5]. It is pores are suitable for capturing CO2 at low-pressures, which are very
the most mature technology because of flexible operation and lowest useful for the post-combustion capture [39]. Besides, porous materials
requirements for existing power plants transformation [26,27]. In rich in mesopores or meso-micropores are appropriate for capturing CO2
practice, these CO2 capture technologies can be integrated to realize at relatively high pressures [40].

Fig. 1. Principle of the CCUS technology [5].

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 2. CO2 capture configurations including pre-combustion, oxy-fuel combustion and post-combustion capture in fossil fuel-fired power plants [11].

Several aspects on designing appropriate CO2 capture materials ac­ [42]. For example, MOF- and POP-based catalysts are considered as
cording to the CO2 properties was displayed in Fig. 3. In recent years, good candidates for CO2 capture and conversion due to large SSA,
significant progress have been made in the development of various microporous crystalline structures, metal active sites, tunable bandgaps,
porous materials regarding to structural engineering, surface function­ and controllable surface functional groups [43,44]. Bare zeolites and
alization, and on par adsorption capacities with the traditional amine- porous carbons without efficient metal active sites have lower activity in
based solvents for CO2 capture, but their success in the aspect of tech­ CO2 conversion [41].
nology readiness levels has not achieved the industrial scale [41]. The adsorption of CO2 onto porous materials generally occurring
Consequently, more knowledge in this research area would be urgently through physical and/or chemical pathways is mostly associated with
required to prove the potential of porous materials in the large-scale CO2 their textural properties and surface functional groups. Accordingly, the
capture. In the other hand, the captured CO2 can be converted into design of porous materials with highly porous features (e.g., surface
useful products (e.g., fuels, chemicals) via cost-effective and environ­ area, pore volume) offers precise control to enhance CO2 adsorption at
mentally benign pathways including photo-catalysis and electro- low or high pressures. For instance, MOFs, zeolites, and POPs with high
catalysis. Here the conversion of CO2 to different species (e.g., CO, microporosity show excellent CO2 adsorption performance at low
HCOO− , and CH3OH) usually needs a catalyst that can offer a platform pressures. Porous carbons possessing tunable pore features to micro- or
rich in active sites and high porosity for efficiently charge transfer and mesoporous structures are suitable for CO2 adsorption at both low and
CO2 conversion. Using a porous material as both absorbent and catalyst, high pressures. Otherwise, mesoporous carbon materials are suitable for
the capture and conversion of CO2 can be achieved in a single system CO2 capture at high pressures [41]. In addition to the pore filling, the

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 3. CO2 molecule properties, CO2 capture process requirements, and material attributes for CO2 capture using porous materials.

doping with basic functional groups and metal centers can offer space of-life processes for any CCS material. Fig. 4 illustrates the trade-offs
for a series of interactions like acid-base, electrostatic, and hydrogen in key sorbent selection criteria for various sorbent classes. Regarding
bonding [45], which further improve the CO2 adsorption capacity. to resource allocation in deploying emissions mitigation technologies,
Porous materials usually possessing inherent metal active sites can be key questions are proposed by examining the strength and weakness of
functionalized [46–48]. In particular, the doping of porous carbon with these CO2 capture sorbents [50]. Should researchers optimize capture
basic species enhances the CO2 adsorption due to the acid-base in­ processes towards a limited set of sorbents, or rather optimize individual
teractions. Nevertheless, the presence of doped N atoms is favorable to sorbent for each process, or even each plant? Higher process efficiency is
generate hydrogen bonds between the carbon surface and CO2 mole­ possible with sorbents purpose-built for specific CCS. Unfortunately, the
cules for enhancing the CO2 adsorption [49]. Here the doped N atoms high cost to de-risk the production, utilization, and disposal as well as
can transform the electronic state of the H atoms in the –CH and –NH recycle of new sorbents has simulated a minimal number of low-cost and
groups on porous carbons to form hydrogen bonds between H and the O well-understood sorbents. Practically, viable solutions will need a de­
atom of CO2 molecule. In general, an ideal porous carbon material for gree of versatility in both sorbent and process design. In general, acti­
CO2 capture should have high adsorption capacity and selectivity, low vated carbons are attractive candidates from an adsorbent lifecycle
heat adsorption, high recyclability, good thermal stability, fast adsorp­ perspective, since they can be prepared from low-cost, environmentally
tion kinetics, and low cost [41]. benign feedstocks (e.g., biomass waste). Furthermore, given their
The selection and stability of sorbent can greatly affect both capital generally non-polar, hydrophobic surfaces, activated carbons can cap­
and operating costs in a CCS process. For example, sorbents with high ture CO2 in the presence of moisture and minimize regeneration energy
sorption enthalpies require additional investment on the capture costs associated with adsorption-desorption cycling of water. However,
equipment for effectively controlling thermal excursions. Nonetheless, the non-polar adsorbent surface also limits the equilibrium CO2/N2
given the sorbent quantities to achieve impactful emissions mitigation, selectivity and CO2 capacity of typical carbons at conditions relevant to
much effort must be made to minimize the cost, deployment timeline, CO2 capture from flue gases (≤15% CO2). Therefore, cost savings ach­
and environmental footprint of large-scale synthesis, shaping and end- ieved with inexpensive, low-enthalpy carbon adsorbents must be

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 4. Radar charts for key sorbent selection criteria and qualitative assessment of key metrics for sorbents selection in CCS applications [50].

balanced with the potential requirements of increased adsorbent bed synthesis of porous carbon materials as shown in Fig. 5. A number of
size and/or shorter cycle times. The detailed advantage and disadvan­ excellent papers have reviewed the synthesis methods of various porous
tages of these porous materials were well summarized by Siegelman carbon materials. Recently, Chen et al. [52] reviewed the synthesis of
et al. [50]. biomass-derived porous carbon materials for energy storage/conversion
and environmental remediation. Zhang et al. [53] highlighted the
3. Porous carbons derived from sustainable resources development of carbon nanomaterials from biomass and discussed the
merits and limitations of various synthesis methods. The roles of
Among these adsorbent materials applied for CO2 capture, porous biomass resources, conversion methods and additives with desired
carbons (e.g., activated carbon) are the most prevalent and industrially characteristics were concluded. Insights into the conversion mecha­
mature materials that possess inherent superior textural properties or nisms of biomass to carbon materials were provided for different
have been suitably functionalized to develop high adsorption capacities biomass types. Matsagar et al. [54] reviewed the progress of biomass-
[51]. In general, a diversity of sustainable carbon resources including derived N-doped porous carbons (NPCs) including various synthesis
abundant biomass and plastic wastes can be used as precursors for methods, the effect of which on the properties of NPCs could provide a

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 5. Synthesis methods of various porous carbon materials from sustainable carbon resources and activation methods to produce biomass-derived hierarchical
porous carbons (HPCs).

direction for designing NPCs in diverse applications. In addition, the ordered porosity, because ordered and uniform interconnected porosity
traditional synthesis methods such as carbonization (e.g., hydrothermal in carbons can improve mass transfer of various species like molecules in
carbonization -HTC, pyrolysis) of biomass with or without activation of porous networks, which is favorable for adsorption, catalysis, and en­
biochar are thoroughly reviewed in some papers [55–57]. For instance, ergy storage/conversion applications. Szczęśniak et al. [72] reviewed
hierarchical porous carbon (HPC) can be commonly synthesized from the progress in the development and applications of biomass-derived
biomass derivatives by the template-free method including carboniza­ carbons with uniform porosity. For readers, the detailed information
tion and/or activation (e.g., one- [58,59] and two-step pyrolysis [60], in the synthesis of porous carbons from biomass can be easily found from
pyrolysis-HTC [61], pyrolysis-activation [62,63], HTC-activation [64], these papers.
one-step chemical [65–68] and/or physical [69,70] activation). As Generally, the physical and chemical activation methods for pro­
shown in Fig. 5, activation of biochar can be conducted by physical, duction of activated carbons from char have been widely discussed in
chemical or combined process with different activation agents and re­ several review articles focusing on preparation of activated carbons. In
action parameters (e.g., temperature: 350–1000 ◦ C, time: 0.5–10 h). common, the physical activation using steam or CO2 as an activating
Depending on the activation method, the pore formation and distribu­ agent is conducted at a high temperature (i.e., >1000 ◦ C), while the
tion are varied [57]. Furthermore, the engineered HPCs (EHPCs) chemical activation using various alkali (e.g., KOH, NaOH), acid (e.g.,
including heteroatom doping (e.g., N, O, S, and P) on the surface can be H3PO4) or salt (e.g., ZnCl2, K2CO3, KHCO3) introduced by the
synthesized from biomass/biochar and HPCs through some technical impregnation-drying or mixing process is conducted at a relatively low
strategies (e.g., template methods) to enhance the stability of materials temperature (normally 600–900 ◦ C). Recently, some green organic salts
performance, which is more suitable for the commercial application. It is (e.g., potassium oxalate) have attracted much concern instead of widely-
noted that direct carbonization of biomass usually leads to carbon ma­ used KOH with strong corrosive. The comparison of physical and
terials with low and inhomogeneous porosity [71]. It has attracted more chemical activation of biochar using different activating agents was
attention in the controlled synthesis of porous carbons possessing shown in Table 1. Furthermore, the physical activation using activating

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Table 1 without catalysis, atmospheric or high pressure), which involves a two-


Comparison of physical and chemical biochar activation using different acti­ step process of pyrolysis and carbonization accompanied by the release
vating agents. of hydrocarbon gases and carbon materials [83]. The products of carbon
Activating Advantages Disadvantages materials include amorphous carbons (e.g., carbon fibers, carbon
agent spheres) and graphitic carbon nanomaterials (e.g., carbon nanotubes,
Physical activation graphene).
Steam Green, highly microporous Long activating time, high The direct carbonization of waste plastics normally leads to carbon
structure activating temperature, materials with very low porosities [83]. In order to synthesize carbon
CO2 Green, highly microporous Long activating time, high
materials with high porosities, the activation process is required to
structure activating temperature
Air Green, low cost, lower energy Difficult to control, pore develop more pores. Zhang et al. [84] used low-density PE (LDPE) to
consumption heterogeneity synthesize HPCs via autogenic pressure carbonization followed by the
KOH activation (a most commonly used activation method). The non-
Chemical activation catalytic carbonization in a closed system resulted in 45% char. The
Acid (e.g., More mesoporous structure, high Strong corrosive, need to dry further KOH activation of char developed hierarchical porous structures
H3PO4) activity even at lower (only for impregnation in the carbon materials (Fig. 6a). Lian et al. [85] proved the conversion
temperature method)
of LDPE into porous carbons via a ball-milling process and subsequent
ZnCl2 High activity, more mesoporous Higher cost, smaller specific
structure surface area
carbonization with a flame retard agent [4MgCO3⋅Mg(OH)2⋅5H2O],
KOH Widely-used, High activity, Strong corrosive, which provided an in-situ hard template (MgO) and stabilized PE during
catalytic effect of K, large specific agglomeration (suitable for carbonization. Through the NH3 activation, the porous carbon exhibited
surface area, low cost impregnation method) dominant mesopores, a low ratio of O/N, and high graphitization degree.
K2CO3 Higher activity, lower cost, Weak corrosive, unstable
Besides, the addition of metals such as iron, nickel or cobalt catalyzed
catalytic effect of K, large specific (easily reacting with H2O
surface area, suitable for both and CO2 in air) the formation of carbon nanofibers, which resulted in a very positive
impregnation and milling impact on the electrochemical performance [86].
methods In recent years, the conversion of waste PET into porous carbon
KHCO3 Green, higher activity, lower Relatively high cost
materials has been widely developed. Particularly, the PET-derived
cost, catalytic effect of K, large
specific surface area, suitable for
microporous carbons have attracted considerable attention in adsorp­
both impregnation and milling tion. Liu et al. [87] synthesized the waste PET-derived HPCs possessing
methods large SSA (2238 m2/g) and meso− /macropores volume (0.51 cm3/g).
Organic salts High activity, catalytic effect of High cost, only for both The formation of hierarchical porous structure was attributed to the co-
(e.g., K, large specific surface area milling method
etching effect of sp2/sp3 hybridized carbon to develop micropores and
K2C2O4)
meso− /macropores (Fig. 6b). Furthermore, Zhang et al. [88] upcycled
waste PET into CH4-rich gas and porous carbon material through auto­
gas molecules (e.g., CO2, H2O) is usually controlled by the heteroge­ genic pressure pyrolysis and post-activation. Compared with the ZnCl2-
neous reactions through gas-solid interactions. In contrast, the chemical activated carbon, the KOH-activated carbon had a hierarchical porous
activation using chemical activators adsorbed on the char is usually structure, a large SSA (2683 m2/g) and abundant surface functional
controlled by the homogeneous reactions through solid-solid groups. Ma et al. [89] proposed a facile method to carbonize waste PS
interactions. into HPCs using Fe2O3 particles as both catalyst and template. Then the
Currently, a huge amount of waste plastics produced has led to KOH activation was used to develop micro- and meso-pores on the wall
serious ecological and environmental problems [73]. The commercial of macropores. In addition, porous carbon flakes (PCFs) were synthe­
plastics such as polypropylene (PP), polyethylene (PE), polystyrene (PS), sized by direct pyrolysis of waste PS through a template method. Man­
polyvinyl chloride (PVC) and polyethylene terephthalate (PET) are ganese dioxide (MnO2) nanosheets were selectively deposited on the
becoming indispensable in modern society [74]. However, these syn­ surface of PCFs to form hybrid (PCF-MnO2) [90]. These PS-derived
thetic polymers are non-biodegradable in nature and traditional disposal carbon materials exhibited a high specific capacitance.
way (e.g., landfills, incineration) could cause various environmental As one of the most commonly used plastics, recycling waste PVC is
hazards [75]. Therefore, it is imperative to develop economical and still challenging due to its non-biodegradability, low thermal stability,
environmentally friendly ways for recycling waste plastics. Since plas­ low product value, and especially high Cl content. Recently, Zhou et al.
tics possess uniform macromolecular structures and abundant carbon [91] developed a one-pot method to upcycle PVC into valuable carbon
elements, the conversion of waste plastics into useful carbon materials is materials, syngas and chlorides. The whole process included dechlori­
an alternative way [76]. Up to date, a few researchers have devoted on nation by Cl-fixation (ZnO or KOH), carbonization of dechlorinated
the synthesis of various carbon materials from waste plastics through polyenes, and modification of carbon materials (Fig. 6c). It is suggested
thermochemical processing such as chemical activation and chemical that specific chemical agents such as ZnO and KOH can play the roles of
vapor deposition (CVD) of pyrolysis char and hydrocarbon gases, both activating agents and fixing agents for the synthesis of porous
respectively [77–80]. Unlike biomass-derived porous carbons, there are carbons from halogen-containing polymers such as PVC. It was also re­
very limited review literatures on the synthesis of plastic-derived porous ported that chemical pretreatments using alkalis, acids and alkali-earth-
carbons for CO2 capture. In the following parts, some typical works on metal salts on pyrolysis of waste plastics with high content of organic Br,
the synthesis of porous carbon materials from waste plastics and biomass which can be converted into HBr by pyrolysis at relatively high tem­
will be comparatively discussed. perature. In particular, the alkali pretreatment was more beneficial for
the Br fixation in char [92,93].
3.1. Waste plastic-derived porous carbons The physiochemical and textural properties of porous carbons are
associated with the types of plastics. Moreover, the complexity of
Recently, the conversion of plastics into high value-added products different plastics greatly hampers the utilization of ever-used methods. It
such as fuels and carbon materials through thermochemical processing is necessary to develop general strategies for the synthesis of uniform
(e.g., pyrolysis, carbonization) has been demonstrated to be a promising porous carbons from real-world plastic waste. Recently, Wen et al. [94]
way for recycling waste plastics [81–83]. In usual, the conversion of proposed a general method for the synthesis of porous carbon nano­
plastics into carbon materials requires a thermochemical processing sheets (PCNSs) by catalytic carbonization of mixed waste plastics on
under different conditions (e.g., oxidative or inert atmosphere, with or organically-modified montmorillonite (OMMT) and the subsequent

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 6. (a) Synthesis of HPC from LDPE via autogenic pressure carbonization and KOH activation [84], (b) synthesis of HPC from PET via carbonization and KOH
activation [87], (c) Synthesis of carbon materials and syngas from PVC via one-pot pyrolysis in a closed reactor [91], and (d) synthesis of PCNS from mixed
plastics [94].

KOH activation (Fig. 6d). OMMT can promote the degradation of mixed Fe3O4 nanoparticles, which are supported on MgO acting as both cata­
plastics and then work as a template for in-situ growth of CNSs from the lyst and template for carbonization of waste plastics into HCS/PCF. Here
degradation products. Through the KOH activation, PCNSs with hier­ the porous HCS/PCF exhibited good electrochemical performance as an
archically porous structure was formed. Min et al. [95] synthesized a anode material in lithium-ion batteries (LIBs). Based on the present
hollow carbon sphere/porous carbon flake (HCS/PCF) from mixed work, the interconnected nano-SnO2 spheres/cubes with the bulk SnO2
plastic waste using a general template (MgO/Fe(acac)3) (Fig. 7a). By the flakes/blocks were further inserted to the porous HCS/PCF [96]. These
carbonization process, the MgO/Fe(acac)3 is in situ transformed into hybrid nanocomposites with built-in SnO2 nanoparticles of various

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Fig. 7. Synthesis of (a) porous hollow carbon sphere/porous carbon flake (HCS/PCF) nanomaterials [95] and (b) SnO2/HCS/PCF hybrids from real-world plastic
wastes [96].

morphologies would serve as anodes towards the advanced LIBs micropores was formed at 550 ◦ C. Meanwhile, the residual eutectic salts
(Fig. 7b). acted as porogens to form meso- and macropores. Ultimately, HPC rich in
The municipal waste plastics mentioned above could be employed micro− /meso− /micro-pores was produced after washing. Further, N,O
for synthesis of porous carbons via carbonization and activation with/ dual-doped NCF was prepared from low-temperature (340 ◦ C) carbon­
without templates. However, most plastics will completely decompose ization of waste PET using melamine and eutectic salts, which had a
or transform into highly graphitic carbons during the carbonation pro­ synergetic effect on the growth of NCF. The formed small-molecular
cess due to the lack of oxygen functional groups [97]. PET and poly­ gases (e.g., CO2, H2O) as foaming agents could build 3D inter­
carbonate (PC) containing plentiful ester bonds (-COO-) are suitable for connected pores (Fig. 8b). With the combined features of self-floating,
the synthesis of porous carbons with oxygen functional groups. It was lightweight, interconnected porous structure, low thermal conductiv­
proved that hard carbons could be synthesized from ester bond-rich ity, super-wetting, and super-hydrophilicity, NCF exhibited high light
plastics by a simple pyrolysis at high temperatures (>1200 ◦ C) [98]. A absorption and solar-to-heat conversion, as well as low water evapora­
number of strategies (e.g., combined catalysis, active template, fast tion enthalpy [100]. In addition, a strategy of stepwise crosslinking was
carbonization) have been developed for converting plastics into carbon developed using melamine and ZnCl2/NaCl eutectic salts for converting
materials (e.g., PCNS, graphene) for advanced applications (e.g., PET into NPC at 550 ◦ C. The relevant mechanism was shown in Fig. 8c.
supercapacitor), but these methods suffer from high carbonization The coordination of two tandem crosslinking reactions was critical to
temperature (e.g., >700 ◦ C) [94–98]. Recently, Zhang et al. [99] control the microstructure of NPC [101]. Without activation, NPC
developed the controlled carbonization of PET into porous carbon for possessed large SSA (1173 m2/g), abundant N dopants, and rich O-
solar evaporation (Fig. 8a). Firstly, ZnCl2/NaCl eutectic salts were containing groups. These combined features endured NPC with excellent
melted at 250 ◦ C for controlling the carbonization of PET. Then ZnCl2 performance in CO2 capture and solar steam generation. Therefore,
promoted the dehydration and decarboxylation of PET into vinyl- these works will advance the research on green reutilization of polyester
terminated chain fragments and aromatic rings at 280 ◦ C. After wastes to produce sustainable carbons for energy conversion and stor­
further crosslinking and cyclization, carbon material frame with highly age, environmental remediation, etc.

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 8. (a) The “controlled carbonization” of PET [99], (b) low-temperature carbonization of PET to synthesis N,O dual-doped NCF for interfacial solar evaporation
[100], and (c) mechanism of PET carbonization [101] using ZnCl2/NaCl eutectic salts.

Waste tires as industrial plastics are generated increasingly all over graphene (Fig. 9c). This 3D graphene with high conductivity could be
the world [102]. Rubber, carbon black, inert fillers (e.g., silica, used as a supercapacitor electrode with excellent capacitive and rate
alumina), steel, textile and fabric cords (e.g., nylon, kevlar), sulfur, zinc performance. Zhang et al. [113] proposed a facile synthesis of HPC from
oxide, and different antioxidants/antiozonants are the main components the waste tire pyrolysis oil (WTPO), which containing abundant aro­
of tires [103]. The improper disposal (e.g., landfill, incineration) of matic hydrocarbons and high S content. Magnesium acetate was mixed
waste tires causes serious environmental and health problems [104]. with heavy oil and tetrahydrofuran (THF) by grinding. HPC was ob­
Thermochemical processes such as pyrolysis and gasification are tained by evaporation, carbonization and MgO removal (Fig. 10a). HPC
considered as the most promising ways for recovering of various prod­ synthesized at optimum condition exhibited large SSA and micro-
ucts (e.g., fuels, materials) from scrap tires [105–108]. More impor­ mesopore structure resulting in a considerable performance on dye
tantly, it has been demonstrated that pyrolytic products such as char and contaminant removal. Furthermore, Li et al. [114] synthesized the S-
oil can be used as precursors for the synthesis of high value-added car­ doped porous carbon nanorods from WTPO (labeled as WPCNs) by the
bon materials [109–114]. In terms of waste tires to porous carbons, it is MgO template-directed method (Fig. 10b). WPCNs had the rod-like hi­
very necessary to separate the complex components in tires for acquiring erarchical microporous structure, large SSA and excellent structural
rubbers. On one hand, various porous carbons can be synthesized by the stability, which benefited for reducing the diffusion distance and resis­
traditional rubber pyrolysis combined with “char activation” processes tance of electrolyte ions. In addition, the hollow structure possessing the
mainly including chemical activation (e.g, KOH, H3PO4) (Fig. 9a) good buffer function was capable of restraining the volume change
[109,110] and physical activation (e.g., CO2) [111]. In general, the during charge and discharge processes, ensuring the extraordinary
physical activation requires a higher temperature than the chemical structural integrity of the electrode. Therefore, turning abundant
activation. It was noticed that these tunable porous carbons exhibited municipal and industrial plastic wastes into functional carbon materials
good performance in energy storage (Fig. 9b). Wang et al. [112] for advanced applications (e.g., environmental remediation, energy
developed one-step KOH-catalyzed pyrolysis of waste tire to synthesize a storage and conversion,) is a paramount achievement in the science and
monolithic 3D graphene. Under high temperature above 1000 ◦ C, the scientific community.
generated K vapor could induce the carbon atom rearrangement, which
drove the conversion of soft carbon into graphene structure. Here the 3.2. Biomass-derived porous carbons
material morphology underwent an evolution from carbon nanospheres,
monolithic carbon conglomeration and finally to vertically grown 3D Until now, a variety of carbon materials have been produced from

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Fig. 9. (a) Synthesis of porous carbon from waste tire through a traditional pyrolysis-activation method [110], (b) waste tire derived HPCs as energy storage
materials [111], and (c) synthesis of 3D graphene structure from waste tires [112].

sustainable biomass precursors such as plants [115–119], animals controllable synthesis of biomass-derived carbon materials. In partic­
[120–123], insects [124–126], and aquatic organisms [127–130] by ular, HTC has been widely developed due to easily tailoring the micro­
thermochemical processes such as hydrothermal carbonization (HTC) structures of carbon materials, but it still has some inherent limitations.
[131,132], pyrolysis [120,133], microwave irradiation [134,135], and For instance, it is conducted in a lower temperature range (i.e.,
laser processing [136]. According to their structures and morphologies, 150–350 ◦ C) [138], and the obtained carbon materials are rich in O-
biomass-derived carbon materials can be generally categorized into 0D functional groups. Additionally, the multifarious hydrolysis products
carbon spheres/dots, 1D carbon fibers/tubes, 2D carbon sheets, and 3D from the HTC process of biomass have a negative effect on keeping the
carbon aerogel/hierarchical carbon materials [137]. The diverse mi­ pristine structure [139]. Chemical activation is another commonly used
crostructures and surface properties enable carbon materials application approach for controlling the structures of biomass-derived carbons to
in many areas. For instance, 0D carbon dots are suitable for fluorescent produce highly porous carbons, but additional neutralization and
bioimaging, while 3D carbon aerogels have considerable performances washing steps are required. General synthesis strategies of biomass-
in energy storage and pollutant removal. High-strength carbon fibers derived porous carbon materials with desired structures and proper­
with few defects are often used as reinforced materials, while porous ties are preferred [137]. Fig. 11a illustrates some considerable aspects
carbon nanofibers with abundant atomically defect sites have high po­ for the conversion of biomass into carbon materials. Since biomass re­
tential to be used as electrochemical materials for energy storage, oxy­ sources composed of complicated components have specific pyrolysis
gen reduction reaction (ORR), and hydrogen evolution reaction (HER). mechanisms [140], the selection of appropriate biomass is the key step
Therefore, the structural control of biomass-derived carbon materials is for the synthesis of carbon materials with desired structures and mor­
important in promoting their industrial applications. phologies. During the carbonization of biomass, a series of correlative
In recent years, researchers have taken much effort to realize the reactions (e.g., dehydration, decarboxylation, depolymerization,

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Fig. 10. Synthesis of (a) HPC [113] and (b) WPCNs from WTPO [114].

isomerization, aromatization, and charring) occur. The decomposition often used to improve the SSA and porosity of carbon materials [137].
of most biomass occurs at 200–400 ◦ C to produce char. In this stage, a Until now, the synthesis of biomass-derived carbon materials for
variety of functional groups (e.g., carboxyl, carbonyl, phenol, quinone, wide application (e.g., energy conversion and storage, pollutants
and lactone) will be formed, endowing the carbon materials with unique removal) is still an emerging subject. A number of excellent review
properties. When the temperature increases, the carbon materials will papers have been published in this field [52–54,72,142]. Hence, the
lose these functional groups and release gaseous products, which further relevant subjects will not be discussed further. Returning to the subject
change the carbon structures [137]. of this review, biomass-derived porous carbons have been considered as
The carbonization strategies are classified into “structure inheritance one kind of flexible and sustainable carbon materials for CO2 capture.
carbonization” and “restructuring carbonization”. The pristine struc­ Recently, Shao et al. [143] prepared microporous carbons from poplar
tures of biomass are mostly kept in the former process, while destroyed wood sawdust (PWS) by three synthetic routes (Fig. 12). Particularly,
in the later process (Fig. 11b). Biomass-derived carbon materials with the residual PWS after the bioethanol process were used for synthesis of
various structures and properties can be synthesized by selecting porous carbons by KOH and ZnCl2 activation. By regulating the syn­
appropriate carbonization strategies. As a typical restructuring carbon­ thetic routes and the activation conditions, these porous carbons
ization method, the HTC of low-molecular-weight biomass is easy to exhibited diversified morphology (i.e., sponge, nanosheets, honeycomb
control for the synthesis of carbon materials at low temperatures. structure), tunable porosity (SSA: 511–2153 m2/g), and narrow micro­
Particularly, a programmable heating process at a wide temperature pore distribution (0.55–1.2 nm). These carbons had a high CO2 uptake
range can be used for the “structure inheritance carbonization”. Laser or (217 mg/g at 273 K, 1 bar), and had moderate isosteric heat of CO2
Joule heating assisted carbonization can heat the biomass up to adsorption (21.1–43.2 kJ/mol), good cyclic ability, and high CO2/N2
>2000 ◦ C within a second, which is used to synthesize highly graphitic selectivity. The CO2 capture of porous carbon was mostly dependent on
carbon materials in a short time. In addition, the reaction atmosphere the micropore volume (d < 1 nm).
and thermal stability of the carbonization process influence the struc­ Chemical activation using activating agents (e.g., KOH, NaOH,
tures of carbon materials [141], which can be controlled by several ZnCl2, and H3PO4) has been widely developed [144], but these agents
additional processing methods. For example, the pre-HTC of biomass is are highly corrosive, toxic and with latent risks (e.g., flame and explo­
used to remove impurities and introduce desired chemicals. Chemical sion) [145,146]. To resolve these issues, potassium salts such as KHCO3
activation with alkaline salts (e.g., K2CO3) is widely used to improve the and K2C2O4 with weak corrosiveness have attracted more concern due to
SSA and porosity of carbon materials. Introducing transition metals can their good pore tailoring performance [145,147]. The potassium salts
greatly promote the graphitization of amorphous carbon. Besides, can affect both the pyrolysis process (carbonization) of biomass and the
physical activation such as controlled gasification with H2O or CO2 is properties of porous carbon [148–150]. When different potassium

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Fig. 11. (a) Main factors of compositions, carbonization processes, and additional processing strategies for conversion of biomass into carbon materials with diverse
structures and wide applications and (b) Comparison of the characteristics in the “restructuring carbonization” and “structure inheritance carbonization” process of
biomass to carbon materials [137].

Fig. 12. Three synthetic routes of PWS-derived porous carbons with multiple requirements [143].

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oxysalts are adopted, the porous carbons derived from glucose are quite the organic salts have shown excellent performance on the synthesis of
different regarding to porosity and morphology [150]. Deng et al. porous carbons from biomass and char for specific application, but the
[147,148] developed a facile leavening method using KHCO3 to produce pore-forming mechanism of organic salt is still insufficient. Hence, it is
HPCs from various biomass precursors. Here H2O and CO2 from the important to reveal the specific interactions between organic salts and
pyrolysis of biomass with KHCO3 resulted in forming abundant macro­ biomass, which is helpful for understanding the effect of organic salts on
pores for cellulose and hemicellulose-derived carbons. KHCO3 is effec­ the microstructures of biomass-derived porous carbons.
tive for most biomass precursors, but the pore tailoring is impeded for The development of green, highly efficient and universal pore
lignin-rich precursors caused by the limited interaction in the inter­ tailoring approaches has become the popular subject on the synthesis of
face of char and porogen [147,151,152]. Sevilla et al. [145] found that biomass-derived porous carbons [166]. Recently, Xia et al. [167] studied
the porosity of biomass-derived carbons could be greatly improved using the mechanism of porous carbons synthesized from different bio­
K2C2O4 and melamine (porogen). The formed KCNO with a low melting polymers (i.e., cellulose, hemicellulose, and lignin) by pyrolysis-
point (315 ◦ C) compared to KOH (380 ◦ C) exhibited a better perfor­ activation process using organic salt porogen (potassium acetate -
mance due to the highly etching of char by melting salt [153]. KAc). The mixture of KAc and biopolymer was firstly pyrolyzed for
Furthermore, carbonization of potassium/calcium-rich biomass pre­ carbonization. KAc was dispersed on the surface of char by the hydrogen
cursors can also produce highly developed porous carbons [154,155]. bonds between hydroxyl (–OH) in char and carboxyl (O–C=O) of KAc
Since the dispersity of salt is affected by the melting behavior, the rather than melting (Fig. 13a). The decomposition of KAc took place to
dispersion of porogen might be associated with the pore tailoring per­ form K2CO3 and gases (e.g., CH4, CO2). Meanwhile, KAc catalyzed the
formance for different precursors. In usual, organic potassium-based pyrolysis of biopolymers with different mechanisms. When the tem­
salts such as oxalate [145,156], citrate [157], acetate [158], and perature increased above 600 ◦ C, KAc was fully converted into deposited
formate [159] as green porogens possessing relatively low melting point carbon layer on the surface of char and K species (e.g., K2O, K2CO3),
(<400 ◦ C) can perform better dispersity in the char intermediate. Be­ which could further contribute to carbon etching for developing abun­
sides, it has been reported that various alkali metal-based organic salts dant micropores (Fig. 13b). So far, potassium-based compounds (e.g.,
(e.g., acetate [160,161], citrate [162,163], lignosulfonate [164] and K2CO3, KHCO3, organic salts) have been widely used as greener acti­
others [165]) can be directly converted into porous carbons. Generally, vating agents. It is noted that the actual activating agent of K2CO3 is also

Fig. 13. Pore tailoring and surface reconstruction effect of KAc in morphology/porosity evolution (a) and carbon structure evolution (b) of biochars derived from
different biopolymers [167].

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the main intermediate product during KOH activation. Compared with porous carbons can be normally produced from biomass through one-
KOH, these activating agents can achieve lower pore development, but (direct activation) and two-step (carbonization-activation) processes,
allow higher carbon yields and preserve the precursor morphology. while the porous carbons are only produced from plastic waste through
Confinement of the reactants in an inert medium (e.g., KCl) forms a two-step processes. Due to the heterogeneity of components and existing
eutectic mixture with K2CO3 below the given temperature (at which the minerals in biomass, the microstructures of biomass-derived porous
redox reaction with carbon taking place), enhancing the reactivity between carbons are hard to regulate, thus leading to the non-uniform porous
the carbonaceous matter and K2CO3. Compared to traditional physical structures compared with plastic-derived porous carbons. However,
and chemical activation, an important advantage of this confined acti­ some specific biomass such as rice husk are rich in nano-silica, which can
vation is the increase of the carbon yield. Therefore, more efforts should be acted as a natural template for developing porous structure. Addi­
be made in developing green activation processes to enhance the carbon tionally, some N-containing biomass could prepare the N-doped porous
yield. It is noteworthy that doping heteroatoms especially nitrogen may carbons, while plastic waste needs to prepare the N-doped porous car­
also have significant effects on the development of porosity, no matter bon using the extra N precursors. In general, the plastic-derived porous
whether they come from carbon precursor or foreign additive (e.g., carbon with uniform porosity has a high potential to be used for
melamine, urea) [167]. Usually, the obtained porous carbons with ultra- emerging applications such as electrochemical conversion.
large SSA (>3000 m2/g) and pore volumes (>2 cm3/g) exhibit a micro-
mesoporous structure with a large proportion of mesopores, in com­ 4. Porous carbons for CO2 capture
parison to the K2CO3 or KOH-activated porous carbon with a predomi­
nant microporous structure. Novel methods should be sought for tuning Porous carbons have emerged as promising materials for CO2 capture
the pore size distribution of porous carbons that are very suitable in under a wide range of conditions owing to their unique properties [45].
specific applications (e.g., supercapacitor, gas uptake). To avoid the use Particularly, porous carbons derived from sustainable carbon precursors
of activating agents, the self-activation methods have attracted such as biomass and plastic wastes have attracted increasing concern.
increasing attention. Moreover, the synthesis of porous carbon can be The following sections will conclude the recent progress in targeted
realized by one-step carbonization process. The self-activation involves synthesis of plastic and biomass-derived porous carbons, with specific
three pore-forming mechanisms: i) chemical activation (carbon oxida­ emphasis on revealing the correlation of structure and performance in
tion by carbonates or oxides), ii) physical activation (carbon gasification CO2 capture. Additionally, the underlying mechanism of CO2 adsorption
by CO2), and iii) endo-template process (after removal of inorganic onto porous carbons with a defined pore structure and surface chemistry
matters embedded in the carbon matrix). Accordingly, the carbon pre­ is discussed. Furthermore, the challenges in the development of porous
cursors such as organic/polymeric salts or biomass need to contain the carbons for practical CO2 capture are proposed.
elements as follows: alkali metals (e.g., K, Na), alkaline earth metals (e.
g., Ca, Mg) or others (e.g., Fe, Zn). The easy, sustainable, low-cost pro­
4.1. Waste plastic-derived porous carbons for CO2 capture
duction of highly porous carbons will be achieved by selecting biomass
rich in alkali and alkaline earth elements through the pyrolysis under
A few literatures have reported on the use of waste plastic-derived
restricted flow conditions.
porous carbon in the application of CO2 capture (Table 2). Among
Compared with the porous carbons produced from various biomass
those common-used plastics, PET has been mostly employed for the
and plastic waste, several differences could be pointed out. Firstly, the
synthesis of porous carbons that can effectively capture CO2 because of

Table 2
Reported works on waste plastic-derived porous carbons for CO2 capture.
Plastic type Synthesis condition Porous carbon texture CO2 adsorption Adsorption Ref.
capacity condition

PET Two-step carbonization (700 ◦ C) and activation Microporous carbon (SSA: 1690 2.31 mmol/g at 30 ◦ C under 1 bar [168]
(700 ◦ C, KOH/carbon mass ratio of 3) m2/g, micropore volume: 0.78 with 100% CO2
cm3/g)
PET Two-step carbonization (700 ◦ C) and activation Microporous carbon (SSA: 1690 1.31 mmol/g at 30 ◦ C under 1 bar [169]
(700 ◦ C, KOH/carbon mass ratio of 3) m2/g, micropore volume: 0.78 with 12.5% CO2
cm3/g)
PET Two-step carbonization (600 ◦ C) and activation Microporous carbon (SSA: 1812 4.42 mmol/g at 25 ◦ C under 1 bar [170]
(700 ◦ C, KOH/carbon mass ratio of 2) m2/g, micropore volume: 0.71
cm3/g)
PET Two-step carbonization (600 ◦ C) and activation N-doped microporous carbon (SSA: 4.58 mmol/g at 25 ◦ C under 1 [171]
(700 ◦ C using KOH and urea) 1165 m2/g, micropore volume: atm
0.460 cm3/g)
PET One-step carbonization (550 ◦ C) using N-doped microporous carbon (SSA: 4.67 mmol/g at 25 ◦ C under 1 bar [101]
melamine and ZnCl2/NaCl eutectic salts 1173 m2/g)
PVC Three steps including spheroidization, Microporous carbon sphere (SSA: 5.47 mmol/g, CO2/ at 25 ◦ C with 100% [172]
oxidation cross-linking, and 1738 m2/g) N2 selectivity: 6.9 CO2
activation‑carbonization
PVC Two-step Pre-oxidation: 260 ◦ C and activation Porous carbon (SSA: 2507 m2/g, 3.9 mmol/g at 25 ◦ C under 100 [173]
(700 ◦ C, KOH/PVC mass ratio of 3) pore volume: 1.11 cm3/g) kPa
Polyimide One-step carbonization (600 ◦ C) using triblock N-doped HPCs (SSA: 579 m2/g, 5.56 mmol/g, CO2/ at 25 ◦ C under 1 bar [174]
copolymer P123 as mesoporous template pore volume: 0.34 cm3/g) N2 selectivity: 17
Resorcinol–formaldehyde resin One-step carbonization (700 ◦ C) with KOH/ Microporous carbon (SSA: 1235 4.83 mmol/g, CO2/ at 25 ◦ C under 1 bar [175]
resin mass ratio of 1 m2/g, micropore volume: 0.57 N2 selectivity: 17–45
cm3/g)
Mixed plastics (PP, PE, PS, PET, Two-step catalytic carbonization: 700 ◦ C and Porous carbon nanosheet (SSA: 6.75 mmol/g at 40 ◦ C under 10 [176]
and PVC) activation (850 ◦ C, KOH/carbon mass ratio of 1734 m2/g, pore volume: 2.441 bar
6) cm3/g)
Mixed plastics (HDPE, LDPE, One-step carbonization (600 ◦ C) using Microporous carbon (SSA: 1055 3.81 mmol/g at 25 ◦ C under 1 bar [177]
and PP) potassium acetate (KOAc/HDPE mass ratio of m2/g)
4)

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its high carbon and oxygen content. Recently, Kaur et al. [168,169] sustainable and economically viable production of CO2 capture material
synthesized the PET-derived porous carbons with highly microporous from waste PET. The CO2 uptakes were 2.68 mmol/g for PET6-CO2–9,
structures by a carbonization (700 ◦ C) and KOH activation (700 ◦ C) 3.03 mmol/g for PET6-K7, and 3.28 mmol/g for PET6-KU7 at 25 ◦ C (1
process. The adsorption uptakes were 1.31 mmol/g (12.5% CO2) and bar). Based on the life-cycle assessment (LCA), the KOH/urea chemical
2.31 mmol/g (100% CO2) at 30 ◦ C (1 bar). The adsorption kinetics activation process had higher environmental impacts than the CO2
followed the fractional-order kinetic model, and the isotherm data were physical activation process (~200%) and the KOH chemical activation
well fitted to the Freundlich isotherm model. The negative values of process (− 1.74% to 125%). Among the impact categories, the global
enthalpy and Gibbs free energy suggested the adsorption process was warming potential (GWP) was undoubtedly the most important. The
exothermic, thus confirming the feasibility of the adsorption process in CO2 physical activation process had the lowest GWP (Fig. 14a and b).
the spontaneous nature [169]. Yuan et al. [170,171] also converted The techno-economic assessment (TEA) revealed various viable sce­
waste PET into porous carbons by the carbonization (600 ◦ C) and acti­ narios for the industrial-scale production of porous carbons. All three
vation (700 ◦ C) using NaOH or KOH. Moreover, the modification of processes can produce porous carbons with 20% energy loss and the sale
surface properties such as N-doping can be realized by adding a nitrogen of products at the lowest market price (€200 per ton). The net present
precursor (e.g., urea) before the activation process [171]. The PET- value (NPV) was evaluated for producing each of PET-derived porous
derived porous carbon prepared by the KOH activation at 700 ◦ C carbon in different scenarios by varying the heat-to-power conversion
exhibited a high CO2 uptake of 4.42 mmol/g at 25 ◦ C (1 bar). Generally, losses and the selling prices of porous carbons. Generally, the production
the adsorption of CO2 onto the PET-derived porous carbons was mainly of porous carbon by the CO2 physical activation (i.e., PET6-CO2–9) was
related to the pore size below 0.8 nm in diameter [170]. It was noticed considered as the most feasible process because of its lower environ­
that the PET-derived N-doped microporous carbon by activation using mental impact and higher economic benefit. Based on the GWP reduc­
KOH and urea at 700 ◦ C exhibited the highest CO2 uptake of 4.58 mmol/ tion across China, the CO2 physical activation process had a high
g (at 25 ◦ C and 1 bar) and CO2/N2 selectivity, suggesting that it is potential to reduce the GWP from 42.32 to 429.56 kg CO2 eq. per FU
feasible to treat flue gas (10% CO2 and 90% N2). More importantly, the (Fig. 14c), which favored to attaining carbon neutrality by 2060 in
adsorption of CO2 on porous carbons was affected by micro-pores and China.
nitrogen/oxygen functional groups [171]. Up to date, research works on the synthesis of porous carbons for CO2
Waste plastic-derived porous carbons for CO2 capture can provide capture have focused on modifying their textural properties (e.g., large
promising solutions to both climate change and plastic pollution. Yuan SSA, high microporosity, and abundant N-doped groups) to enhance the
et al. [178] further synthesized the PET-derived porous carbons (i.e., CO2 adsorption performance. In particular, the physical and chemical
PET6-CO2–9, PET6-K7, and PET6-KU7) by the CO2 physical activation activation processes can significantly improve the textural properties of
(900 ◦ C) and KOH/urea chemical activation (700 ◦ C) processes, which porous carbons, but they normally require high-energy consumption
were comparatively evaluated to select an appropriate process for the and activating agents. Compared with the KOH/urea chemical

Fig. 14. (a) Environmental impact and economic benefit of waste PET-derived porous carbons, (b) Comparison of the released/mitigated GWP for the activation
methods, and (c) potential GWP reduction across China (including 23 provinces, 5 autonomous regions, and 4 municipalities) using the CO2 physical activation and
KOH/urea chemical activation processes. The production units for waste PET-derived porous carbons favor China especially for the provinces with higher GWP for
electricity generation [178].

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activation, the porous carbon from the CO2 physical activation process the most feasible for converting waste plastics into porous carbons with
often requiring a high reaction temperature (900 ◦ C) shows a lower CO2 a maximum SSA of 1055 m2/g and a high CO2 uptake (Fig. 16b) along
uptake, but it has lower environmental impact and higher economic with a good cyclability/stability (Fig. 17e). However, KOH with stronger
benefit [178]. Therefore, the LCA and TEA analysis should be conducted corrosive was not effective to produce porous carbons due to the full
to select feasible processes for the industrial-scale production of CO2 decomposition of waste plastics. The CO2 uptake isotherms were well
capture materials. In addition to waste PET, other waste plastics such as fitted with the Langmuir model (normally type I isotherms) reaching
PVC, PP, and PE widely present in the municipal solid waste have been saturation at ~10 bar (Fig. 16a). The CO2 uptake increased with an
used to produce porous carbons for CO2 capture. For instance, Wang increase in the ratio of KOAc/HDPE up to a maximum of 18 wt% (4.1
et al. [172] synthesized the porous carbon spheres from pure PVC mmol/g). Moreover, a larger micropore surface area (the blue dots in
powders through three steps including spheroidization, oxidation cross- Fig. 16b) can contribute to a higher CO2 uptake. Although the increase
linking and carbonization-activation. The carbon spheres with micro­ of synthesis temperature increased the surface area of porous carbon,
porous structure (SSA: 1738 m2/g) exhibited excellent performance in the CO2 uptake at 1 bar was not significantly enhanced as the activation
CO2 adsorption capacity (5.47 mmol/g, 24.1 wt% at 25 ◦ C). Further­ temperature was above 600 ◦ C (Fig. 16c). In addition to the HDPE, the
more, Liu et al. [173] synthesize microporous carbons from waste PVC properties of porous carbon were not affected by using the high-
pipe by a facile chemical KOH activation method. To achieve high solid molecular-weight polymer (e.g., PP). The same synthesis conditions
yield and chlorine removal from PVC, the air pre-oxidation (260 ◦ C) was can be used for treating mixed postconsumer plastic (PCP) such as PP,
employed. The KOH activation (700 ◦ C) followed by acid washing LDPE, and HDPE with a mass ratio of 1:1:1 (Fig. 16d). So far, PET (a
process was an effective way to recover all calcium- and 92% of high-fixed‑carbon-content polymer) has been widely developed for the
titanium-based compounds (the main metal additives in the PVC pipe) in synthesis of porous carbons. Hence, this approach would make up the
the form of soluble salt. Those metal additives could act as a hard carbonization of low-fixed‑carbon-content waste plastics at mild acti­
template to develop microporosity for CO2 adsorption. The optimal vation conditions.
porous carbon with a high SSA (2507 m2/g) and pore volume (1.11 cm3/ In recent decades, the pyrolysis process has been extensively devel­
g) exhibited high CO2 adsorption capacity (6.90 mmol/g) and CO2/N2 oped for converting waste plastics into valuable products such as liquid
selectivity. oil and solid char. Nevertheless, it is necessary to resolve a number of
Unfortunately, most of current studies on converting waste plastic challenges or limitations on waste plastics pyrolysis. For instance, the
into porous carbon materials are limited to single component plastic, direct pyrolysis of waste PVC can produce a considerable amount of
which requires a sorting treatment. Moreover, few studies on mixed benzoic acid and hydrochloric acid, thus causing corrosion problems to
plastics in the real world have been reported to date. Gong et al. [176] the equipment. The pyrolysis process of common-used plastics can
synthesized the carbon nanosheets (CNS) by catalytic carbonization of produce high aromatic contents of oil, but some toxic aromatic hydro­
mixed plastics mainly consisting of PP, PE, PS, PET, and PVC on the carbons (e.g., tar) have a negative impact on the environment, human
organically modified montmorillonite (OMMT). Through the KOH health and facilities. Liquid fuel produced from plastic pyrolysis may not
activation, the production of porous CNS (PCNS) with a hierarchical be suitable for commercial application due to high sulfur content. In
meso-microporous structure were achieved through the in-situ growth. addition, the pyrolysis process can produce a solid char, but an optimal
PCNS exhibited large SSA (1734 m2/g) and pore volume (2.441 cm3/g), activation temperature is required to acquire a high yield of char used
leading to its high performance in CO2 uptake (Fig. 15). Recently, for porous carbon production. Compared with municipal plastic wastes
Algozeeb et al. [177] developed an alternative approach for pyrolysis of (especially for PET), few works have been conducted for developing
waste plastics (LDPE, HDPE and PP) with low-fixed‑carbon-content industrial plastic wastes (e.g., tyre)-derived porous carbons in CO2
using a potassium activator such as KOH, potassium oxalate (K2C2O4), or capture. Although many waste plastic-derived porous carbons exhibit
potassium acetate (KOAc) to produce ultra-microporous carbons via a excellent CO2 adsorption capacity in the small-scale experiments, the
single-step carbonization at 600 ◦ C. Among potassium salts, KOAc was LCA and TEA analysis is urgently required for driving these potential

Fig. 15. Synthesis of PCNS from mixed plastics for CO2 uptake and H2 storage [176].

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Fig. 16. (a) CO2 sorption isotherm of 4,1-HDPE-600, (b) CO2 uptake of HDPE-derived porous carbons with different ratio of KOAc/HDPE, (c) CO2 uptake of HDPE-
derived porous carbons synthesized at different temperatures (KOAc/HDPE ratio: 4), (d) CO2 uptake of porous carbons synthesized from different plastic types, and
(e) CO2 uptake throughout 100 cycles from 10− 4 to 1 bar. [177].

carbon capture materials in the large-scale application. impregnation and dry mixing, porous carbons are generally synthesized
from biomass or biochar by one- and two-step carbonization along with
activation processes. During the chemical activation process (normally
4.2. Biomass-derived porous carbons for CO2 capture
at 600–900 ◦ C), KOH is widely adopted as the activating agent for the
development of pores (especially micro-pores). Compared with KOH,
Among available porous carbon materials, biomass-derived porous
other activating agents such as potassium acetate with weaker corrosive
carbons are quite attractive for CO2 capture because of their good
property have been recently developed. Moreover, the physical activa­
textural properties, simple synthesis methods and high CO2 adsorption
tion processes (e.g., CO2 activation) reported in only a few literatures
performance. More significantly, the inexpensive and renewable
require higher temperatures (e.g., >900 ◦ C). It is noticed that synthesis
biomass resources that can reduce the overall expense of the CO2 cap­
of porous carbons with diverse morphologies such as sphere and aerogel
ture process. Similar to the synthesis of plastic-derived porous carbons,
is mostly dependent on biomass species and synthesis methods. Biomass
single- and multi-step processes in terms of carbonization (e.g., pyrol­
resources originating from agroforestry wastes can be reutilized as
ysis, HTC) and activation (e.g., physical, chemical) have been widely
promising carbon precursors because of their low-cost and abundantly
developed. Porous carbons can be synthesized from biomass or biochar.
available. Particularly, the reutilization of unexpected tar by-product
Although biochars have their own advantage of abundant surface
from biomass pyrolysis and gasification can realize the green valoriza­
functional groups, porous carbons are superior to biochars because of
tion of full components in a closed-loop biorefinery process. In general,
high SSA and developed porosity. The quantity of surface functional
the CO2 capture by biomass-derived porous carbons is significantly
groups depends on synthesis methods and biomass precursors. Up to
affected by carbon characteristics (e.g., SSA, micropore volume, and
date, a great number of works have been reported on the synthesis of
surface functional groups) and adsorption conditions (e.g., temperature,
biomass-derived porous carbons for CO2 capture and some typical works
pressure, and CO2 concentration). The CO2 uptake can reach up to 6.0
are shown in Table 3. Excluding pretreatment processes such as wet

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 17. Synthesis of waste sugarcane bagasse-derived porous carbons via physical and chemical activation for CO2 adsorption [223].

mmol/g at 25 ◦ C (1 bar) [191]. Regarding to adsorption conditions, the way to enhance the CO2 absorption onto porous carbons, since the
capacity of CO2 adsorption increases with the reduction of temperature presence of abundant basic sites on the carbon surface can act as an
and with the increase of pressure [221]. anchor for capturing weakly acidic CO2 molecules [51]. In particular,
the N atoms on the walls of micropores can promote the Lewis acid-base
4.2.1. Effect of surface area and porosity of porous carbon interactions between the carbon and CO2 molecules. Recently, two main
Regarding to characteristics of carbon materials, surface area and approaches including in situ synthesis and post-treatment method have
porosity are the two dominant factors in controlling the CO2 adsorption. been developed to prepare NPCs [226]. The in-situ synthesis is to pre­
It is concluded from the reported works that porous carbons with large pare NPCs directly from the N-containing biomass precursors and N-
SSA and high microporosity normally have high CO2 adsorption ca­ containing chemicals, which is the principal way to prepare NPCs with
pacities [222]. Guo et al. [223] synthesized porous carbons from waste high contents of structural N. The post-treatment method is to treat
sugarcane bagasse using different activating agents (air, CO2, H3PO4 and biochar with N dopant for incorporating N into carbon materials, which
NaOH). Compared to the porous carbons by physical activation (PAC-A can introduce both the chemical N and structural N [227]. Besides, some
and PAC-C), the porous carbons by chemical activation (PAC-P and PAC- pre-treatments of biomass or biochar are employed to facilitate the N
S) exhibited better textural properties. Particularly, NaOH-activated doping. Due to the significant effect of N content and N species on the
carbon (PAC-S) featured largest SSA (1149 m2/g) and pore volume acid gases (e.g., CO2, SO2) adsorption, the synthesis process is very
(1.73 cm3/g), resulting in a superior CO2 uptake of 4.28 mmol/g at 25 ◦ C important to endow the NPCs with highly efficient adsorption perfor­
and 1 bar (Fig. 17). Furthermore, the isosteric heat of adsorption (43.96 mance (Fig. 18a). The discussion of these methods and the N trans­
kJ/mol) indicated the strong binding force of the surface basic sites formation mechanisms could be found in the literature [228]. Recent
towards CO2 molecules. In addition to SSA and microporosity, hydro­ efforts have been made in the modification of porous carbons with N
phobicity, aromaticity and heteroatoms present in biochar can greatly functional groups by N-containing chemicals such as melamine and urea
influence the CO2 adsorption [224]. Li et al. [197] prepared the KOH- through a pretreatment process (e.g., impregnation) [229,230]. Pang
activated rice husk char and investigated the role of micropores in et al. [231] synthesized the NPCs using waste hazelnut shell (carbon
CO2 adsorption. It was found that narrower micropore sizes (<0.7 nm) precursor), melamine (N-doping agent), and KOH (porogen). The porous
and higher nitrogen content could benefit for improving the CO2 carbon with high N content and highly porous structure resulted in high
adsorption capacity (2.11 mmol/g) even at a low pressure (0.1 bar). CO2 adsorption capacities up to 4.23 mmol/g at 25 ◦ C and 1 bar
Similarly, Sevilla et al. [225] proved the dominant role of narrow mi­ (Fig. 18b). However, chemically fusing the porous carbons with amine
cropores (<1 nm) in CO2 capture. Compared to the severe KOH acti­ or N-containing compounds often leads to the extreme reduction of SSA
vation, the mild KOH activation resulted in forming narrow micropores and pore volume due to the pore blocking [232], which has become a
with lower SSA, thus contributing to high CO2 uptake of (4.8 mmol/g at major bottleneck in the utilization of N-containing chemicals for the
25 ◦ C and 1 bar). Besides, it was proved that microporous structure, synthesis of NPCs. In contrast, the introduction of abundant N-con­
hydroxyl groups and heteroatoms (e.g., N, O) were main factors taining biomass (e.g., microalgae) as N-doping agents are not prone to
collectively enhancing the CO2 adsorption (7.49 mmol/g at 1 bar and these issues compared to their chemical counterparts [233,234]. Balou
0 ◦ C) onto the porous carbons derived from KOH activation of gelatin et al. [235] prepared the N-enriched hydrochar through the HTC of
and starch [182]. lignocellulosic biomass (Citrus aurantium waste leaves) and N-rich
microalgae (spirulina) as the N-doping agent. Furthermore, the hydro­
4.2.2. Effect of heteroatom-doping onto porous carbons char was activated using ZnCl2/CO2 to produce NPCs with high N con­
Doping basic or electron rich heteroatom (especially for N) is another tent and ultra-microporosity, which resulted in high CO2 adsorption

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Table 3
Reported works on biomass-derived porous carbons for CO2 capture.
Carbon precursors Synthesis condition (exclude pre-treatment) Porous carbon texture CO2 adsorption capacity Adsorption Ref.
condition

Biomass resources
D-glucose One-step carbonization (800 ◦ C) using Porous carbon spheres with SSA of 1917 m2/g and 6.62 mmol/g 0 ◦ C (1 bar) [179]
potassium acetate specific pore volume of 0.85 cm3/g
D-glucose Two-step carbonization (HTC with urea at N-doped porous carbon spheres with SSA of 1734 4.26 and 6.70 mmol/g 25 and 0 ◦ C (1 [180]
180 ◦ C) and KOH activation (650 ◦ C) m2/g and micropore volume of 0.77 cm3/g bar)
Starch Two-step carbonization (HTC at 190 ◦ C) Porous carbon spheres with SSA of 3350 m2/g and 4.5 mmol/g 25 ◦ C (1 bar) [181]
and CO2 activation (1000 ◦ C) pore volume of 1.75 cm3/g
Gelatin and starch Two-step carbonization (pyrolysis at Porous carbons with SSA of 1636 m2/g 7.49 and 3.84 mmol/g 0 C and 25 C
◦ ◦
[182]
450 ◦ C) and KOH activation (700 ◦ C) (1 bar)
2
Cellulose Two-step carbonization (pyrolysis at HPC aerogel with SSA of 1364 m /g 3.42 mmol/g 25 ◦ C (1 bar) [183]
200 ◦ C) and CO2 activation (800 ◦ C)
Cellulose Two-step carbonization (HTC with N-doped porous carbon with SSA of 1703 m2/g 1.56 mmol/g 25 ◦ C (1 bar) [184]
melamine at 270 ◦ C) and KOH activation and micropore volume of 0.65
cm3/g (N content: 1.68%)
Cellulose Two-step carbonization (with urea/ Porous carbon frameworks with SSA of 1032 m2/ 193.7 mg/g 25 ◦ C (1 bar) [185]
thiourea at 600 ◦ C) and KOH activation g, micropore volume of 0.7135 cm3/g,
(800 ◦ C) abundance of narrow micropores of <0.94 nm,
and optimum pyrrolic nitrogen content (58%)
Lignin One-step carbonization and activation N-doped HPCs with SSA of 2779 m2/g and 8.6 and 5.48 mmol/g 0 ◦ C and 25 ◦ C [186]
(800 ◦ C) of KOH and NH3 micropore volume of 1.10 cm3/g (N content: (1 bar)
5.6–7.1%)
Sugarcane Two-step carbonization (pyrolysis at 900 ◦ C N-doped HPC with SSA of 1111 m2/g (N content: 3.34 mmol/g 25 ◦ C (1 bar) [187]
bagasse with zinc acetate) and activation (900 ◦ C) 3.4%)
using melamine
Orange peel One-step carbonization and activation Porous carbon with SSA of 1636 m2/g and 4.6 mmol/g 25 ◦ C (1 bar) [188]
(800 ◦ C) with KOH micropore volume of 0.74 cm3/g
Poplar wood Two-step carbonization (HTC at 160 ◦ C) Porous carbon with SSA of 2153 m2/g and 126.1 mg/g 25 ◦ C (1 bar) [143]
and activation (800 ◦ C) using KOH/ZnCl2 micropore volume of 0.85 cm3/g
Coconut shell Two-step carbonization (pyrolysis at N-doped porous carbon with SSA of 1535 m2/g 5 mmol/g 25 C (1 bar)

[189]
500 ◦ C) and activation (650 ◦ C) using urea
and KOH
Coconut shell Two-step carbonization (pyrolysis at N-doped porous carbon with SSA of 1082 m2/g 3.71 mmol/g 25 ◦ C (1 bar) [190]
500 ◦ C) and activation (600 ◦ C) using urea
and K2CO3
Vine shoots Two-step carbonization (pyrolysis at Porous carbon with SSA of 767 m2/g 4.07 mmol/g 25 ◦ C (1 bar) [191]
600 ◦ C) and CO2 activation (800 ◦ C)
2
Vine shoots Two-step carbonization (pyrolysis at Porous carbon with SSA of 1305 m /g 6.04 mmol/g 25 C (1 bar)

[191]
600 ◦ C) and KOH activation (600 ◦ C)
Arundo donax One-step carbonization and activation Microporous carbon with SSA of 1122 m2/g and 6.3 mmol/g 0 ◦ C (1 bar) [35]
(700 ◦ C) using KOH micropore volume of 0.5 cm3/g
Arundo donax One-step carbonization and activation Mesoporous carbon with SSA of 3298 m2/g and 30.2 mmol/g 0 ◦ C (30 bar) [192]
(500 ◦ C) using ZnCl2 pore volume of 1.9 cm3/g
Spent coffee grounds Two-step carbonization (400 ◦ C) and KOH Microporous carbon with SSA of 2785 m2/g and 3 mmol/g 50 C (1 bar)

[193]
activation (700 ◦ C) micropore volume of 0.793 cm3/g
Grape marc Two-step carbonization (600 ◦ C) and KOH Oxygen-rich porous carbon with SSA of 2473 m2/ 6.2 mmol/g 0 ◦ C (1 bar) [194]
activation (800 ◦ C) g, micropore volume of 0.72 cm3/g and pore
diameter of 0.74 nm
Chestnut shell Two-step carbonization (HTC at 250 ◦ C) Porous carbon with SSA of 1253.91 m2/g 1.7 mmol/g 25 ◦ C (1 bar) [195]
and KOH activation (700 ◦ C)
2
Walnut shell Two-step carbonization (HTC at 250 ◦ C) Porous carbon with SSA of 1488.89 m /g 2.1 mmol/g 25 C (1 bar)

[195]
and KOH activation (700 ◦ C)
2
Macadamia nut shell Two-step carbonization (HTC at 250 ◦ C) Porous carbon with SSA of 1150.92 m /g 1.97 mmol/g 25 ◦ C (1 bar) [195]
and KOH activation (700 ◦ C)
Hazelnut shell Two-step carbonization (pyrolysis at N-doped porous carbon with SSA of 1099 m2/g 4.32 mmol/g 25 ◦ C (1 bar) [196]
500 ◦ C) and activation (550 ◦ C) using
sodium amide (NaNH2)
Rice husk Two-step carbonization and KOH activation Porous carbon with SSA of 2695 m2/g and 6.24 mmol/g 0 ◦ C (1 bar) [197]
(780 ◦ C) micropore volume of 1.1 cm3/g
Rice husk Two-step carbonization (pyrolysis) and CO2 Hierarchical micro- and meso-porous carbon with 3.1 mmol/g 25 ◦ C (1 bar) [198]
activation (900 ◦ C) using K2CO3 SSA of 1097 m2/g, micropore volume of 0.34 cm3/
g, and mesopore volume of 0.49 cm3/g
Pine cone Two-step carbonization (pyrolysis at Porous carbon with SSA of 2110 m2/g and 20.9 wt% 25 ◦ C (1 bar) [199]
600 ◦ C) and KOH activation (700 ◦ C) micropore volume of 0.78 cm3/g
Pine cone Two-step carbonization (pyrolysis at Microporous carbon with SSA of 1787 m2/g 4.15 mmol/g 25 C (1 bar)

[200]
500 ◦ C) and KOH activation (600 ◦ C)
2
Pine cone Two-step carbonization (pyrolysis at Porous carbon with SSA of 3135 m /g 7.63 mmol/g 0 ◦ C (1 bar) [201]
500 ◦ C) and KOH activation (650 ◦ C)
Palm sheath One-step carbonization and activation Porous carbon with SSA of 840 m2/g 3.48 mmol/g 25 ◦ C (1 bar) [202]
(650 ◦ C) using KOH
Licorice residue Two-step carbonization (HTC at 270 ◦ C) Porous carbon with SSA of 1305 m2/g 3.89 mmol/g 25 ◦ C (1 bar) [203]
and KOH activation (600 ◦ C)
2
Biomass cork waste One-step carbonization and KOH activation Porous carbon nanoflakes with SSA of 2380 m /g 4.27 mmol/g 25 C (1 bar)

[204]
(700 ◦ C) and micropore volume of 0.896 m3/g
(continued on next page)

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Table 3 (continued )
Carbon precursors Synthesis condition (exclude pre-treatment) Porous carbon texture CO2 adsorption capacity Adsorption Ref.
condition

Algae Two-step carbonization (pyrolysis at N-doped porous carbon with SSA of 1018.55 m2/g 2.76 mmol/g 25 ◦ C (1 bar) [205]
500 ◦ C) and KOH activation (800 ◦ C) (N content: 5.55%)
Water chestnut shell Two-step carbonization (500 ◦ C) and N-doped porous carbon with SSA of 1416 m2/g 4.50 mmol/g 25 ◦ C (1 bar) [206]
activation (500 ◦ C) using NaNH2
2
Lotus leaf Two-step carbonization (500 ◦ C) and KOH N-doped porous carbon with SSA of 1487 m /g 3.87 mmol/g 25 C (1 bar)

[207]
activation (500 ◦ C) using melamine
Lotus stalk One-step carbonization and activation Porous carbon with SSA of 1188 m2/g 3.68 mmol/g 25 ◦ C (1 bar) [208]
(600 ◦ C) using KOH
Rotten strawberry Two-step carbonization (HTC at 180 ◦ C) N-doped porous carbon with SSA of 1117 m2/g 4.49 mmol/g 25 ◦ C (1 bar) [209]
and KOH activation (650 ◦ C) using
melamine
Water caltrop shell Two-step carbonization (pyrolysis at N-doped porous carbon with SSA of 2384 m2/g 4.22 mmol/g 25 ◦ C (1 bar) [210]
500 ◦ C) and KOH activation (600 ◦ C) using
melamine
Seaweed (sargassum One-step carbonization and activation Porous carbons with SSA of 291.8 m2/g (SCK-800- 1.05 mmol/g (SCK-800- 25 ◦ C (1 bar) [211]
and enteromorpha) (800 ◦ C) using KOH 1) and 60.2 m2/g (ECK-800-1) 1) and 0.52 mmol/g
(ECK-800-1)
Seaweed (sargassum Three-step carbonization (800 ◦ C) and urea- N-doped porous carbons with SSA of 579.2 m2/g 4.06 mmol (NSK (2)) 25 ◦ C (1 bar) [212]
and enteromorpha) doping (350 ◦ C) and KOH activation (NSK (2)) and 372.9 m2/g (NEK (2)) and 3.25 mmol/g (NEK
(600 ◦ C) (2))
Chitosan One-step carbonization (1000 ◦ C) with LiCl- N-doped HPC with SSA of 2025 m2/g and N 5.6 mmol/g 25 ◦ C (1 bar) [213]
ZnCl2 molten salt content of 5.1 wt%
Chitosan One-step carbonization (700 ◦ C) with 2,4,6- N-doped micro-porous carbon with SSA of 1684.8 4.74 mmol/g 0 ◦ C (1 bar) [214]
triaminopyrimidine m2/g
Shrimp shells Two-step carbonization (600 ◦ C) and Ternary (N, S, O)-doped HPC with SSA of 2095 236.80 mg/g and CO2/ 0 C (1 bar)

[215]
activation (900 ◦ C) using KOH, melamine m2/g, micropore volume of 1.2647 cm3/g, and N2 gas selectivity (84.3)
and sodium thiosulfate high N 4.1%, S 4.6%, and O 13.4%
Crab shells One-step carbonization (600 ◦ C) using KOH N-doped porous carbon with SSA of 1004 m2/g 4.26 mmol/g 25 ◦ C (1 bar) [216]
activation (N content: 6.2%)
Crab shells Two-step carbonization (450 ◦ C) and KOH N-doped porous carbon with SSA of 2404 m2/g (N 3.82 mmol/g 25 ◦ C (1 bar) [217]
activation (650 ◦ C) content: 4.9%)
Biomass by-products
Furfuryl alcohol One-step carbonization and activation N-doped porous carbon with SSA of 1943 m2/g 3.2 mmol/g 0 ◦ C (1 bar) [218]
(1000 ◦ C) using CO2 and urea
Biomass tar One-step KOH activation (700 ◦ C) N-doped microporous carbon with SSA of 1076 4.11 mmol/g 25 ◦ C (1 bar) [219]
m2/g and N content (3.03%)
Bio-tar One-step KOH activation (800 ◦ C) Porous carbon with SSA of 2595 m2/g 5.35 mmol/g 0 ◦ C (1 bar) [220]

capacity (8.43 mmol/g at 0 ◦ C and 1 bar) (Fig. 18c). Wang et al. [205] heteroatom. Furthermore, the CO2 capture by porous carbon is mainly
further prepared the N-doped porous carbon by in-situ pyrolysis of N- controlled by the physisorption. Pyridine is the most efficient N-func­
abundant Taihu blue algae for CO2 capture. The porous carbon prepared tional group of porous carbon for CO2 capture (Fig. 19). Up to date, most
by carbonization and KOH activation at 800 ◦ C (N-C-800) exhibited high of works on the heteroatom-doping into biomass-derived porous carbons
CO2 uptake capacity of 2.76 mmol/g (1 bar and 25 ◦ C) with the CO2/N2 for CO2 adsorption have focused on the N-doped porous carbon. Limited
selectivity of 39.3. Apart from micropore volume, the porous carbon rich literature can be found in the S or P-doped porous carbon for CO2
in graphitic N sites can also greatly contribute to enhance the CO2 adsorption. In the future work, co-doping N with other heteroatoms
adsorption (Fig. 18d). Combined with the density functional theory should be increasingly developed to enhance the CO2 adsorption
(DFT) calculations [236], higher adsorption energy of N-C-800 (− 13.6 performance.
kJ/mol) compared with N-free carbon framework (− 6.9 kJ/mol) would
render the efficient adsorption of CO2 molecules onto the graphitic N 4.2.3. Effect of metal oxides doping onto porous carbon
sites [237]. Besides, a number of works have been conducted by blending with
Co-doping of N and other heteroatom (e.g., O, S) is also beneficial to alkaline-earth-metal oxides (e.g., CaO, MgO) to synthesize porous car­
the adsorption of CO2, since it can increase the surface polarities of bon/metal oxide composites for enhancing CO2 capture [241–244].
adsorbents [238–240]. For instance, Liu et al. [238] prepared N- and O- Especially, MgO has attracted much attention in the field of CO2 capture,
rich porous carbons from palm sheath by one-step NaNH2 activation. owing to its ability for CO2 physiochemical sorption over a broad tem­
The porous carbons had large SSA (2181 m2/g), narrow micropore sizes perature range, while requiring only moderate energy for CO2 regen­
and high polar groups (O and N). The ultra-micropores (< 0.9 nm) eration [245]. Moreover, MgO can be integrated with porous carbon to
dominated the CO2 adsorption at high pressure, while both ultra- facilitate high dispersion, thus for enhancing CO2 adsorption [246]. Liu
micropores and heteroatoms (O and N) affected the CO2 adsorption at et al. [242] proposed a sustainable approach to synthesize mesoporous
low pressure. Besides, the porous carbon had good selectivities of CO2/ carbon stabilized MgO nanoparticles (NPs) by fast pyrolysis of the
N2, CO2/CH4 and CH4/N2 along with high CO2 uptake (5.78 mmol/g at MgCl2-loaded biomass, which can be prepared by biomass adsorption of
0 ◦ C and 1 bar). Wu et al. [239] synthesized the porous carbon from MgCl2 from seawater. MgCl2 is transformed into MgO NPs, while the
potato starch by the HTC (180 ◦ C) and CO2 activation (1000 ◦ C) process. biomass is carbonized to form mesoporous carbon stabilized MgO NPs
Then heteroatoms (N and O) were incorporated to porous carbon by the (mPC-MgO), showing good performance in the CO2 capture (the
non-thermal plasma modification in air. More importantly, the plasma maximum capacity: 5.45 mol/kg). Another product of bio-oil can be
treatment can rapidly realize the doping of heteroatom without chang­ used as fuels or chemicals (Fig. 20a). Recently, Ekanayake et al. [244]
ing the textural properties of porous carbon. Combined the experiments proposed an effective power-to-decarbonization approach based on the
with DFT calculations, it was found that co-doping N and O onto porous atmospheric pressure plasma (APP) assisted synthesis of carbon-MgO
carbon was more effective in CO2 adsorption compared to single doping nanohybrids for CO2 capture. MgO NPs were originated from

21
Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 18. Synthesis of (a) waste biomass-


derived NPCs for acid gases removal [228],
(b) the NPCs from hazelnut shell for CO2
capture [231], (c) the NPCs from citrus aur­
antium waste leaves (CAWL) and microalgae
(spirulina) for CO2 capture [235], and (d)
the NPCs by in-situ pyrolysis of N-abundant
Taihu blue algae for CO2 capture [205]. (For
interpretation of the references to colour in
this figure legend, the reader is referred to
the web version of this article.) (For inter­
pretation of the references to colour in this
figure legend, the reader is referred to the
web version of this article.)

inexhaustible plasma-electrified seawater, and biomass was used as the agroforestry residues are often limited in performance because of their
carbon source. The APP treatment introduced N species on the carbon poor morphology control, uneven, low-active sites, and weak mechan­
surface to enhance the CO2 capture. In usual, porous carbons with ical strength. In comparison, liquid or liquefiable biomass (e.g., carbo­
micropore sizes (>1 nm) benefit to adsorb and store CO2. Ultra­ hydrate, microalgae, and bio-oil) is an emerging class of carbon
micropore (<1 nm) exhibits better uptake and selectivity of CO2. Gan precursors. Their inherent performances such as fluidity, miscibility and
et al. [247] synthesized the porous carbon-zeolite composite from silica- formability have been widely developed, contributing to liquefiable
rich waste biomass (rice husk) for CO2 capture. The porous carbon- biomass-derived porous carbons with controllable sizes (evenly
zeolite composite possessed a hierarchically porous structure of distributed active sites and adjustable porosity). More recently, He et al.
micro− /meso-pores (carbon) and ultramicroporous pores (Na-X [248] provided a comprehensive review on the multi-scale design and
zeolite), which exhibited high CO2 uptake (Fig. 20b). Porous biochar has functional synthesis methods, mainly including sol-gel, reverse emul­
a good foundation for CO2 adsorption due to the co-existence of micro- sion, HTC and spray drying. Liquefiable biomass-derived porous carbons
and meso-pores. Meanwhile, the Na-X zeolite with ultra-micropores were further discussed in CO2 capture and conversion, highlighting the
(0.7–0.9 nm) are most responsible for the high uptake of CO2 (dy­ methods for improving the CO2 capture performance and catalytic
namic diameter: 0.33 nm) rather than those with larger micropores (>1 conversion efficiency by regulating carbon properties. In recent decades,
nm). most reported works have provided similar methods for (i) the synthesis
Porous carbons produced from solid biomass wastes such as of biomass-derived porous carbons under different carbonization/

22
Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 19. (a) Adsorption energies and optimized structures of CO2 on different N- and O-doped carbon surfaces and (b) adsorption energies of CO2 on different N/O-
codoped carbon surfaces (Gray ball: C, white ball: H, red ball: O, and blue ball: N atoms). [239]. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.) (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

activation conditions and (ii) the adsorption of CO2 under different 5. Integrated Process for CO2 Capture and Conversion
adsorption parameters. However, the optimization of synthesis route by
means of integrating carbonization and activation with a reasonable Biomass-derived porous carbons have been considered as alternative
guideline is still unclear. Apart from the adsorption parameters, the materials for CO2 separation and capture in some specific industries.
carbon properties such as textural properties and surface functional However, the significant challenge is still to produce sophisticated
groups have been extensively considered as dominant factors for CO2 porous carbons with tunable properties and high CO2 capture perfor­
capture. Consequently, prioritization techniques are urgently required mance. If the adsorbed CO2 molecules are converted into fuels (e.g., CO)
for guiding the synthesis of biomass-derived porous carbons for CO2 [252,253] and chemicals [254–258], the overall scheme will provide a
capture. For instance, several mathematical prediction models such as sustainable and high value-added process of recycling the emitted CO2.
machine learning [249,250] and artificial neural networks [251] have Until now, most studies have been restricted on the capture and sepa­
been adopted to thoroughly reveal the underlying dependent relation­ ration of CO2, but the utilization of sustainable porous carbon materials
ships of CO2 adsorption capacity on material properties and adsorption as catalysts or supports for the conversion of CO2 into value-added fuels
conditions, thereby reducing the experiments consumption. Yuan et al. and chemicals have gained less attention. Among these materials, NPCs
[249] used three tree-based machine learning models (i.e., gradient have been widely studied due to their tunable structure and properties,
boosting decision trees, light gradient boosting machines, and extreme high stability, and good conductivity. Notably, N-species present in
gradient boost) for predicting CO2 adsorption onto biomass-derived carbon skeleton (e.g., pyridinic N, pyrrolic N) can work as the Lewis
porous carbons. Among three models, the gradient boosting decision basic sites to activate the contacted molecules, thus promoting their
trees showed the best predictive performance (Fig. 21). The CO2 catalytic conversion. Furthermore, the pore structure (especially hier­
adsorption models will be more generalized and accurate if additional archical porous structure) is beneficial for mass transfer, which allows
influential factors along with the sufficient amount of available data are the reactants and products to transfer smoothly over the catalysts. Be­
provided. In the future, more interface software needs to be explored for sides, the porous structure can enrich the gas molecules in favor of the
facilitating the direct selection of appropriate porous carbons that are catalytic reaction [54,257].
applied in different CO2 adsorption requirements [250]. Shao et al. [256] synthesized NPCs through the KOH activation of
walnut shells with melamine using two routes (Fig. 22a). The NPCs
possessed the narrow micropores (0.6–1.5 nm), high SSA (949–2847
m2/g) and high N content, which resulted in their high CO2 uptakes

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Fig. 20. (a) Mesoporous carbon stabilized MgO nanoparticles synthesized by pyrolysis of MgCl2 preloaded waste biomass for CO2 capture [242], and (b) hierarchical
porous carbon-zeolite composite synthesized from typical silicon-rich rice husk biomass for CO2 capture [247].

(2.7–4.0 mmol/g) at 25 ◦ C and 1 bar (Fig. 22b). A high selectivity (19) 100 kPa). On the other hand, the NPCs could work as a metal-free
was achieved for the CO2 capture even in a mixture of CO2/N2. catalyst for selective N-formylation of various amines with CO2 and
Furthermore, the Ag0 NPs incorporated to NPCs could work as a catalyst PhSiH3 to produce formamides.
for converting propargylic alcohols with CO2 into carbonates via a Electrochemical reduction using renewable energy is another
cycloaddition reaction under mild conditions (Fig. 22c and Fig. 22d). promising method for converting CO2 into high value-added chemicals
Tang et al. [257] synthesized NPCs through the pyrolysis of tannic acid and fuels because of its mild reaction condition (room temperature and
with urea for methylation of amines with CO2. As a metal-free catalyst, atmospheric pressure). This method can reduce the emission of CO2 and
the pyridinic N and pyrrolic N anchored in NPCs working as the Lewis alleviate the shortage of fossil fuels [252]. Since the CO2 molecule is
basic sites could attack CO2 to weaken the C– – O bonds and lower the highly stable, the cleavage of the C– – O bond requires high energy.
molecule conversion barrier, thus facilitating the methylation of N-H Additionally, the complex proton and electron transfer processes of CO2
into N,N-dimethylamine. Besides, the porous structure could enrich CO2 reduction reaction are usually accompanied by competitive hydrogen
and accelerate mass transfer, thus synergistically enhancing the CO2 evolution reaction (HER). The reduction of CO2 to CO is considered as
conversion. Here the N-formylation reaction involves a hydrosilation of one of the economically viable routes due to its relatively high product
CO2 to generate silyl formate intermediate and a successive nucleophilic selectivity and low energy consumption. Electrocatalysts can play the
substitution of amine and silyl formate to generate formamide [257]. key role to overcome the inherent energy barrier of electrochemical CO2
The CO2 adsorbed in NPCs could be activated on the alkaline pyridinic-N reduction and realize the fast reaction kinetics [253]. Recently, a variety
and pyrrolic-N sites. In addition, Yang et al. [258] developed a solvent- of N-doped carbon catalysts such as N-doped carbon nanotubes, C3N4,
free method to prepare NPCs by carbonization of chitosan (precursor) and MOF-derived NPCs [259–262] have attracted much attention for
and NaNH2 (activator) (Fig. 23). On the one hand, the prepared NPCs electrochemical CO2 reduction because of their large surface area,
exhibited efficient CO2 adsorption capacity (6.33 mmol/g at 0 ◦ C and tunable electrochemical activity, and a high suppressing effect for HER

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 21. Machine learning for predicting CO2 adsorption onto waste biomass-derived porous carbons [249].

[263–265]. Here doping N heteroatoms to the carbon frameworks can based CO2 absorption process, the addition of biochar can accelerate
redistribute the charge/spin density of adjacent carbon atoms for tuning the mass transfer of the gas-liquid contact surface and increase the gas-
the electronic environment and forming fresh catalytic/charged sites, liquid contact area, enhancing the reaction rate and improving the CO2
which further enhance the CO2 adsorption and stabilize the in­ capture efficiency. Biochar can also offer the nuclei of NH4HCO3 crys­
termediates [266–269]. Particularly, co-doping pyridinic N and tals, thus greatly promoting the nucleation generation and achieving
graphitic N exhibits a synergistic effect on the electrochemical CO2 synergistic effects.
reduction. CO can be easily desorbed from the N-doped carbon catalysts,
which is mostly attributed to the weak interaction between CO and N- 6. Conclusions and outlook
doped carbon. In addition, high SSA and rich micro− /meso-porous
structures are other important factors in creating more active sites and Porous carbons such as activated carbons are considered as the most
speeding up the diffusion of electrolyte/reactants for the electro­ prevalent and industrially mature materials, which possess inherent
chemical CO2 reduction [270–274]. However, the electrochemical CO2 superior textural properties or have been suitably functionalized to
reduction with lower operating overpotential and high product selec­ achieve high adsorption capacities. Biomass and plastic wastes abun­
tivity under mild reaction conditions is challenging. Until now, a few dantly available can be used as sustainable precursors for the synthesis
works have been reported on biomass-derived carbon catalysts for the of porous carbon materials. The conversion of plastics into carbon ma­
electrochemical CO2 reduction, focusing on NPCs for the reduction of terials usually requires a thermochemical processing under different
CO2 into CO [252,253,275,276]. conditions (e.g., oxidative or inert atmosphere, with or without catal­
To improve the CO2 uptake of biochar, the modification process is ysis, low or high pressure), which involves a two-step process of pyrol­
necessary to create abundant porous structures and functional groups, ysis and carbonization accompanied by the release of various
which can be achieved by a strong acid or base activation process. hydrocarbon gases and carbon materials. Biomass-derived porous car­
Moreover, the severe activation process leads to a low yield of carbon. bons with diverse structures and properties can be synthesized by using
Therefore, it has caused significant challenges to the cost control and appropriate carbonization/activation strategies. The HTC of low-
utilization environment of highly active biochar, restricting its wider molecular-weight biomass easy to be controlled can synthesize
application. To date, the post-combustion CO2 capture technologies nano‑carbon materials at low temperatures. Particularly, a program­
have been widely developed focusing on using liquid ammonia/mono­ mable heating process in a wide temperature range can be employed for
ethanolamine and solid carbon materials. However, the former (liquid the “structure inheritance carbonization”. The reaction atmosphere and
phase) has limited capture efficiency due to strong volatility and thermal thermal stability of the carbonization process influence the structures of
degradation, and the latter (solid phase) has limited CO2/N2 selectivity. carbon materials, which can be controlled by several additional pro­
Recently, Feng and his colleagues [5] put forward an integrated biochar- cesses. Usually, the pre-HTC of biomass is used to remove impurities and
ammonia strategy for CO2 capture (Fig. 24). Based on the ammonia- introduce desired chemicals. In addition, chemical activation with

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 22. (a) Synthesis of N-doped microporous carbons from walnut shells using two routes, (b) CO2 uptake by the N-doped porous carbons, (c) production of cyclic
carbonates using different catalysts, (d) production of various cyclic carbonates from propargyl alcohols reacting with CO2 using Ag/WSNC-3 as a catalyst [256].

Fig. 23. Synthesis of NPCs from chitosan and NaNH2 for CO2 capture and conversion into formamides [258].

activating agents (e.g., KOH, K2CO3, ZnCl2) and physical activation (e. carbon materials are suitable for CO2 capture at high pressures. In
g., controlled gasification with H2O or CO2) are widely used to improve addition to the pore filling, the doping with basic functional groups and
the surface area and porosity of carbon materials. The presence of metal centers can offer space for a series of interactions such as acid-
transition metals can also significantly promote the graphitization of base, electrostatic, and hydrogen bonding, which further enhance the
amorphous carbon. CO2 adsorption. In particular, the doped N atoms can transform the
The adsorption of CO2 onto porous materials generally occurring electronic state of the H atoms in the –CH and –NH groups on porous
through physical and/or chemical pathways is mostly associated with carbons to form hydrogen bonds between H and the O atom of CO2
their textural properties and surface functional groups. Accordingly, the molecule, thus enhancing the CO2 adsorption. An ideal porous carbon
design of porous materials with highly porous features (e.g., surface material for CO2 capture should have high adsorption capacity and
area, pore volume) offers precise control to enhance CO2 adsorption at selectivity, fast adsorption kinetics, low adsorption heat, high recycla­
low or high pressures. In particular, porous carbons possessing tunable bility, good thermal stability, and low cost.
pore features to micro- or mesoporous structures are suitable for CO2 Porous carbons derived from sustainable biomass and plastic wastes
adsorption at both low and high pressures. Otherwise, mesoporous have considered as promising materials for CO2 capture under a wide

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Y. Shen Fuel Processing Technology 236 (2022) 107437

Fig. 24. Integrated biochar (solid) - ammonia (liquid) system for CO2 capture [5].

range of conditions. Single- and multi-step processes in terms of carbons with hierarchical structures are more beneficial for enhancing
carbonization (e.g., pyrolysis, HTC) and activation (e.g., physical, the channel transmission and catalytic conversion (e.g., electrochemical
chemical) have been widely developed for the synthesis of porous car­ conversion) of CO2 molecules. In addition to the catalytic conversion of
bons from biomass or biochar. Although biochar has its own advantage captured CO2 into high value-added chemicals and fuels, the porous
of abundant surface functional groups, porous carbons are superior to carbons rich in CO2 can be made into carbon-based fertilizers for algal
biochar because of high surface area and developed porosity. Similar to culture and agricultural production. Finally, more advanced computa­
the synthesis of porous carbons from biomass, PET among those tional simulations such as machine learning with various algorithms (e.
common-used plastics has been widely used for the synthesis of porous g., random forest, decision tree) should be developed for optimizing the
carbons that can effectively capture CO2 due to its high carbon and preparation conditions of porous carbons and their CO2 adsorption pa­
oxygen content. However, a number of challenges need to be addressed rameters combined with economic efficiency and environmental
in the future, focusing on feedstock selection, porous carbons prepara­ benefit. Not limited to pursuing high adsorption performance, the LCA
tion/modification, and porous carbons for CO2 capture/conversion and TEA analysis should be also performed to fully evaluate developed
through the whole process. processes for producing porous carbon materials, which will be adopted
Firstly, the feedstock such as biomass wastes with low bulk density for CO2 capture and conversion in the industrial-scale applications.
should be selected according to the principle of adaptation to local
conditions, which can greatly reduce the expense of transportation. CRediT authorship contribution statement
Particularly, plastic wastes (especially for PET) can be easily recycled
and have a high potential to be used as alternative carbon precursors. Yafei Shen: Writing – original draft, Writing – review & editing,
Secondly, more net zero-pollution processes should be developed for the Methodology, Project administration, Supervision.
synthesis of microporous carbons for efficient CO2 capture. For instance,
the gaseous pollutants (e.g., tar) should be avoided or in-situ eliminated Declaration of Competing Interest
during the thermochemical process. Thirdly, it is necessary to develop
advanced processes such as microwave or plasma-assisted process for The authors declare that they have no known competing financial
activation/modification of char in mild and energy-saving manners. interests or personal relationships that could have appeared to influence
Fourthly, it is necessary to develop the pyrolysis/gasification poly- the work reported in this paper.
generation processes for valorization of multi-source organic wastes
(e.g., biomass - plastic, nonnitrogenous biomass - nitrogenous biomass) References
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32
Y. Shen Fuel Processing Technology 236 (2022) 107437

Yafei Shen received his PhD degree from Tokyo Institute of


Technology in 2015. Currently, he is a professor at the School of
Environmental Science and Engineering, Nanjing University of
Information Science and Technology. His main research in­
terests include thermochemical conversion of biomass, syn­
thesis and application of functional carbon materials, organic
solid wastes valorization, etc.

33

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