1-s2.0-S221298202300104X-main

Journal of CO2 Utilization 72 (2023) 102493
Contents lists available at ScienceDirect
Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou
Review article
Sustainable CO2 management through integrated CO2 capture

and conversion
Kexin Zhang a, b, *, Dongfang Guo a, b, Xiaolong Wang a, b, Ye Qin a, Lin Hu a, Yujia Zhang a,
Ruqiang Zou c, Shiwang Gao a, b
a
China Huaneng Clean Energy Research Institute, Beijing 102209, PR China
b
National Key Laboratory of High-Efficiency Flexible Coal Power Generation and Carbon Capture Utilization and Storage, Beijing 102209, PR China
c
Beijing Key Laboratory for Theory and Technology of Advanced Battery Materials, School of Materials Science and Engineering, Peking University, Beijing 100871, PR
China
A R T I C L E I N F O A B S T R A C T
Keywords: The excessive emission of CO2 causes severe environmental problems. Sustainable CO2 management based on
Integrated CO2 capture and conversion carbon capture and utilization plays important role in addressing emission-control issue. Among various routes,
Electrochemical conversion synergistic coupling between CO2 capture and conversion brings prospects for energy conservation by simul
Thermochemical conversion
taneously avoiding the energy-intensive regeneration, compression and transportation steps in conventional
Dual-functional materials (DFMs)
Interactions between adsorbents and catalysts
sequential pathway. Herein, this review summarizes the state-of-the-art progress in promising materials for in
tegrated capture and conversion of CO2 in terms of electrochemical CO2 reduction and thermochemical CO2
hydrogenation. The integrated electrochemical process eliminates the critical issues faced by CO2 gas-fed elec
trolysers, and integrated thermochemical process performing in a single reactor under isothermal conditions
benefits from lower energy consumption and less capital investment. Rational design and precise manipulation of
key adsorbents/absorbents and catalysts and the influence of interactions between them are discussed. Several
considerations are put forward from industrial application perspectives and potential development directions of
materials and systems that boost the high selectivity towards valuable products. This review highlights the major
challenges and emerging opportunities in integrated CO2 capture and utilization systems, which provides
guidance for future investigations.
1. Introduction [4]. The storage process requires large capital investment [5], and the
safety issues still remain [6]. Therefore, as a promising alternative to
The exploitation of fossil fuels has been increasing to meet the storage, the utilization of captured CO2 as feedstock to produce
industrialization advances, which results in significant CO2 emissions. high-value-added chemicals can reduce carbon emissions as well as
The atmospheric concentration of CO2 has increased from less than 300 create economic benefits [7]. Renewable resources can be supplied to
ppm [1] in pre-industrial era to 417.91 ppm (data on October 31, 2022) conversion process, enabling the storage of intermittent renewable en
today [2]. The ever-increasing CO2 in atmosphere causes severe climate ergy in chemical bonds for easy transportation [8]. Thus, CO2 capture
change and related environmental and energy issues. The Paris Agree and utilization (CCU) is considered as a more sustainable process for
ment specifies the goal of keeping the global average temperature rise circular carbon-neutral economy.
below 2 ℃ above pre-industrial level by the end of this century, thus the Most capture processes feed CO2-rich gas to adsorbents or absorbents
total CO2 emissions should be controlled to less than 20 GtCO2 per year that selectively capture CO2, followed by the regeneration of adsor
by 2050 [3]. CO2 capture and storage (CCS) is a kind of technology that bents/absorbents by pressure or temperature swing and the release of
can capture CO2 from concentrated emission sources such as high concentration CO2 for further utilization [9]. The regeneration and
coal-derived flue gas or cement kilns and diffuse sources like ambient compression steps are the most energy-intensive parts of capture, ac
air, then compress and transport the captured CO2 and permanently counting for up to 90% of the total energy consumption of the capture
storage them by mineralizing or injecting into the ground or deep ocean process (taking amine-media as example) [10]. Reactive separation of
* Corresponding author at: China Huaneng Clean Energy Research Institute, Beijing 102209, PR China.
E-mail address: [email protected] (K. Zhang).
https://doi.org/10.1016/j.jcou.2023.102493
Received 6 March 2023; Received in revised form 25 April 2023; Accepted 1 May 2023
Available online 5 May 2023
2212-9820/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
K. Zhang et al. Journal of CO2 Utilization 72 (2023) 102493
CO2 through conversion in the captured state without desorption is a capture and conversion processes is shown in Fig. 2 [21], indicating the
reasonable way to reduce the cost and energy requirements of capture integration makes the overall process more energy efficient.
[11]. On the other hand, because CO2 is a thermodynamically and In addition to electrochemical conversion process, integrating CO2
kinetically stable molecule, the activation energy for most reactions of capture and in situ utilization through thermochemical conversion pro
CO2 is high, which leads to the reduction of CO2 in its native state at high cess is also an effective route for reactive capture. This integrated system
temperature or overpotential to achieve a considerable rate. On the operates with the assistance of dual-functional materials (DFMs) which
contrary, if CO2 is chemically captured, the molecular geometry will be can efficiently concentrate dilute CO2 stream and achieve the catalytic
sterically and electronically more favorable for reaction, indicating conversion reactions [6]. Compared with the sequential pathway
integration can also enhance the CO2’s reactivity for conversion [12]. (Fig. 1c), the process is simplified and the energy consumption is
Electrochemical CO2 reduction is a promising CCU technology for reduced. DFMs always consist of adsorbents and catalytic active com
chemical upgrading. An end-to-end electrochemical CO2 reduction route ponents. Generally, when carbon capture process is completed, the feed
usually contains three essential steps: CO2 capture, CO2 conversion, and gas is switched to a reducing agent for the chemical conversion of
product purification. Absorption process using solvent-based media is captured CO2, accomplishing with the adsorbent regeneration (Fig. 1d)
the most mature capture technology [13]. There are various choices of [24]. Oxides are typically employed as adsorbents, while metal species
absorbents, including aqueous ammonia [14], alkanolamines [15], serve as the catalytic centers. Methane [25], methanol [26], syngas [27],
alkaline solvents [16], as well as ionic liquids [17]. After CO2 is captured and alkanes [28] are some of crucial chemicals that can be generated by
by these absorbents, subsequently desorbed and compressed high-purity this process. Although high-temperature is usually needed which may
CO2 is transported and fed to electrolyte where conversion takes place to bring additional energy consumption, the integrated process can be
produce valuable products (Fig. 1a). By virtue of the low solubility of operated continuously and isothermally by swinging the inlet gas,
CO2 in aqueous solution [18], massive amounts of CO2 are supplied into significantly simplifying the overall process [24]. The interactions be
electrolyte in current electrochemical CO2 reduction process, but only tween adsorbent and catalyst in DFM play important role in including
< 1% is dissolved and converted. In addition, excessive CO2 supply assisting catalyst dispersion, offering effective catalytic sites, providing
makes the majority simply flow through the electrolyte and then mix close contact with catalyst and CO2, and promoting the stability of DFM
with the gaseous products, rendering the heavy burden of subsequent [24]. Thus, rational design of DFMs is conducive to improve the whole
CO2 separation for product purification [19,20]. Instead, direct elec conversion efficiency.
troreduction of captured CO2 in amine-based solvents, aqueous alkaline Integrated CO2 capture and conversion is a converging field from
media, and ionic liquids can potentially replace the energy-intensive both adsorption/absorption and catalysis, which can proceed through
regeneration step in capture (Fig. 1b). This coupled process was electrochemical or thermochemical approaches. Although some reviews
recently defined as Type-III fully integrated process by Sullivan et al. with similar topics have been published in the recent years, they have
[21]. This approach bypasses the traditional release of CO2 from the been published in either of the limited aspects of the whole process. And
capture agent, and it overcomes the inherent drawback of current the most important part of this process is the electrocatalysts for direct
electrochemical CO2 reduction technology, which relies on purified electrolysis of chemisorbed CO2 and DFMs for high-temperature ther
gaseous CO2 as feedstock. The absorbed CO2 becomes the primary CO2 mochemical conversion, which lacks systematic summary. Here we
source for subsequent conversion process. More specifically, taking present this review from a catalyst material point of view to discuss
amine-based absorbent as an example, amine (RNH2) plays the inter recent progress in understanding integrated CO2 capture and conversion
mediate role to capture CO2 first and then provides the chemisorbed CO2 with related experimental evidences and summarize the established
(RNHCOO-) as feedstock for direct electrolysis into products, meanwhile guidelines for catalyst design, which serves as an effective solution to
regenerating the amine absorbent for successive cycles [15,22]. Because both carbon-emission-control and energy-supply challenges. The
RNHCOO- is aqueous species and naturally separates from gas products, coupling between capture and conversion processes is explored, in
thus the energy-intensive separation step for product purification can be which CO2 transport and storage or sorbent regeneration and CO2-
eliminated. Besides, the RNHCOO- concentration in amine is about release steps can be minimized or eliminated. This review highlights
2–5 mol L− 1, which circumvents CO2 solubility limit in aqueous solution rational design and precise manipulation of key adsorbents/absorbents
(~0.033 mol L− 1) to support high electrolysis activity [23]. This new and catalysts and the influence of interactions between them. Several
route synergistically integrates CO2 absorption and electrolysis, and considerations are also put forward from potential development di
enables a short process chain of carbon capture and utilization. The rections and industrial application perspectives, which can benefit
energetics comparison between independent and coupled carbon readers from a wide scientific community.
Fig. 1. Schematic illustration of (a) sequential CO2 capture and electrolysis based on conventional gas-fed electrolyser, (b) a reactive separation route based on
integrated electrolyser, (c) sequential and (d) integrated CO2 capture and conversion processes via high-temperature thermochemical method.
2
Fig. 2. The energetics of integrated and sequential CO2 capture and electrochemical conversion processes.
Adapted from ref. [21] with permission. Copyright 2021 Springer Nature Publishing Group.
2. Integrated capture and conversion via electrochemical vicinity of the electrode surface. Similarly, 1-cyclohexylpiperidine
approaches (CHP) was used for capture and electrochemical reduction of CO2
[32]. Under acidic environment, the captured CO2 would be released for
The integration of upstream CO2 capture and downstream electro reduction in situ near the electrode surface. During the production of
chemical conversion by direct electrolysis of capture sorbent offers a syngas from captured CO2 at 104 mA cm− 2, 40 psig, and 25 ℃, the yield
feasible solution to cost- and energy-efficient utilization of CO2. The could reach as high as 71.7% with H2:CO ratio as low as 2.4. Although
sorbent functions simultaneously as capture solution, electrolyte, and the improved catalytic performance was achieved in above studies, the
reactive medium, and this electrochemically reactive capture is found minor desorbed free CO2 in the solution rather than the major captured
capable of yielding a variety of products depending on the electrolyte CO2 was identified as the active species in the catalytic process. This
and electrocatalyst, such as CO, formate, and syngas. implied that most of CO2 remained unused in electrolyte, and the con
version efficiency for this ex situ CO2 electrochemical reduction after
capture was low. Therefore, electrocatalysts that could reduce ami
2.1. Amine-based media for capture and conversion
ne-CO2 directly to overcome the mass-transport limitation associated
with CO2 reduction should be explored and adopted to further improve
The most mature and widely used capture medium is amine-based
the performance.
absorption solvent [29]. The first report on direct electrochemical con
Amine solution captures CO2 to form RNHCOO-, and several factors
version of CO2 from CO2-saturated amine solution was published by
will affect the direct utilization of RNHCOO- via electrochemical
Chen et al. [30]. The electrolysis was conducted in a 30% (w/w) mon
reduction. First, the concentration of RNHCOO- will affect mass trans
oethanolamine (MEA) aqueous solution with the aid of metal electrode
port, a low concentration of amine will lead to competing HER. Second,
such as In, Pb, Ag, Cu. The non-conducting MEA solution was trans
different electrodes will produce different catalytic efficiencies and
formed into a conducting one upon the dissolution of CO2. Increasing the
product distributions. Therefore, the choice of appropriate amine and
electrode surface porosity and adding the surfactant cetyl
electrode is essential to the electrocatalytic reaction. Many researchers
trimethylammonium (CTAB) could suppress the competing hydrogen
have found that Cu can effectively reduce CO2 to hydrocarbons and CO
evolution reaction (HER), and CTAB had a more significant impact. As a
[33,34]. Kraatz et al. evaluated several primary amines including MEA,
result, CO2 was reduced to CO and formate, whose yield distributions
ethylenediamine (EDA), and decylamine (DCA) using glassy carbon
highly depended on the electrode. At the potential of − 0.8 V (vs the
electrode (GCE) and Cu electrode for comparison [35]. Compared with
reversible hydrogen electrode, RHE), the coralline-like In electrode
GCE, the electrolysis in all amines exhibited higher current density and
reduced CO2 to CO and HCOO- with the faradaic efficiencies (FEs) of
catalytic efficiency on Cu electrode. EDA outperformed MEA and DCA
22.8% and 54.5%, respectively. Further mechanistic considerations
with both electrodes, and was the most effective in terms of CO2 to CO
indicated that the addition of CTAB inhibited HER passway but did not
conversion achieved in the presence of Cu electrode. The FE was
affect CO2 reduction, and the increased surface porosity hindered the
increased to 58% with a current density of − 18.4 mA cm− 2 at − 0.78 V
proton mass transport within the porous network. A recent study by
vs RHE, much better than those of GCE (2.3%, − 0.63 mA cm− 2). The
P é rez-Gallent et al. showed when a mixture of 1 M 2-amino-2-me
two active -NH+ 3 sites as two viable capture sites in EDA made it possible
thyl-1-propanol (AMP) in propylene carbonate (PC) was used as cap
to achieve this improved catalytic performance. Another important
ture solution and electrolyte, CO2 was converted into formate with a FE
factor for direct RNHCOO- reduction is the distance between RNHCOO-
of ca. 45% and a reaction rate of 0.56 mmol m− 2 s− 1 at 75 ℃ [31]. The
and electrode that should be precisely controlled [36]. The electrostatic
reaction rate was significantly improved when increasing the tempera
repulsion between negatively charged RNHCOO- and negative potential
ture from 15 ℃ to 75 ℃ due to the much larger liberation of CO2 in the
3
on electrode impedes RNHCOO- to approach electrode. By tailoring the ~0.6 V higher potential of zero charge (PZC) than that of cAg. This
electrochemical double layer (EDL) using alkali cations, Lee et al. veri positive-shifted PZC created an increased surface cation charge density,
fied the promoted direct electrolysis of RNHCOO- due to the facilitated in turn affecting the reduction activity by stabilizing the CO-2 interme
heterogeneous electron transfer [37]. The electrolyte MEA was first diate. As the PZC of electrode increased, the jCO(Cs+)/jCO(Li+) decreased
purged with CO2 to form MEA-CO2, and then N2 was purged to remove (Fig. 4i). Namely, the catalysts possessing relatively negative PZC (cPd,
the dissolved CO2. After that, MEA turned into ethanolammonium ion AuAg, cAg and cAu) displayed higher cation sensitivity. Therefore, weak
and carbamate. When using a Ag electrocatalyst as cathode in MEA-CO2, cation sensitivity or positive-shifted PZC of electrode could be regarded
the FE values of CO were below 5% in all potentials. The low FE was as the indicator of activity for CO2 electroreduction.
attributed to the inefficiency of electron transfer between electrode and To avoid the competitive HER, RNHCOO- reduction can be per
carbamate. Ethanolammonium was the only cation to form the primary formed in nonaqueous electrolyte. Prof. Gallant et al. studied the elec
EDL under negative bias. Although the orientation or conformation of trochemical behavior of CO2 chemisorbed by 2-ethoxyethylamine (EEA)
EDL may vary under different negative biases, electron transfer must in dimethyl sulfoxide (DMSO) [40]. In DMSO, the CO2 captured by EEA
first go through ethanolammonium before reaching carbamate (Fig. 3a). preferred to form carbamic acid. Addition of 0.3 M LiClO4 then induced
Tuning the composition of EDL could regulate the electron transfer dy the conversion of carbamic acid to lithium carbamate, which was
namics. The introduction of properly sized electrolyte ions could provide intrinsically electroactive. Upon electron transfer, carbamate underwent
an added degree of freedom to disrupt the undesired charge-blocking selective N-C bond cleavage to facilitate the conversion of CO2 to
layer. This facilitated electron transfer to carbamate for CO2 conver Li2CO3, and amine could be regenerated for subsequent cycling (Fig. 4j).
sion to CO while suppressing its transfer onto protonated amine, miti Afterwards, the same group investigated the electrolyte salt constituents
gating unwanted H2 evolution (Fig. 3b). Different alkali cations (Li+, across multiple cations and anions in DMSO to get more insights into the
Na+, K+, Rb+, and Cs+) with the concentration of 2 M were added to role of ions [41]. They found that anion had little effect on the con
MEA electrolyte, respectively. The CO FE values of Li+ and Na+ were version of carbamic acid to carbamate, however cation strongly modu
similar to that of 2 M MEA electrolyte, while Cs+ performed best lated the formation of carbamate through electrostatic interactions. The
(Fig. 3c). This phenomenon could be ascribed to the smaller hydrated quantity of formed carbamate varied by nearly 5-fold and decreased
ionic radius of Cs+ that the thickness of the electrochemical layer of Cs+ with the Lewis acidity of cation in the order of Li+ > Na+ > K+. This
was lower [38]. When Ag electrode and 30 wt% MEA electrolyte with trend was also verified by density functional theory (DFT) calculations.
the aid of 2 M KCl at 60 ℃ were implemented, the highest CO FE of 72% The formation of carbamate was unable to achieve spontaneously in the
at 50 mA cm− 2 and − 0.8 V vs RHE could be achieved (Fig. 3d). Ther absence of cation (free-energy change ΔG > 0) (Fig. 4k). On the con
mally assisted N-C bond cleavage and faster reactant transport resulted trary, the carbamic acid-to-carbamate conversion proceeded spontane
in performance improvement. This study demonstrated the important ously with a large negative ΔG in the presence of Li+. Na+ and K+ could
role of supporting electrolyte in delivering RNHCOO- to electrode. also induce this spontaneous process, but with smaller ΔG. Besides, N-C
In conventional amine-based capture solvent, the reaction inevitably bond weakened with larger cation size, and carbamic acid (-COOH)
occurs in the presence of bulky ammonium cations, resulting in low possessed the strongest N-C bond that was more difficult to be reduced
charge density on cathode surface and inferior reactivity. Thus, finding via cleavage of N-C bond than alkali carbamate (Fig. 4l-m). These
cation-insensitive electrode which can effectively operate in the pres findings were in good agreement with the experimental results. Upon
ence of bulky cations is important. Kim et al. reported for the first time a electrochemical reduction, however, higher reaction rate was obtained
single atom Ni catalyst embedded in N-doped carbon (Ni-N/C) (Fig. 4a- with K+. Molecular dynamics (MD) simulations revealed that this phe
b) exhibited weak cation sensitivity even in the presence of bulky cations nomenon resulted from weaker solvation strength and lower desolvation
without alkali metal assistance [39]. A notably high CO FE of Ni-N/C barrier of K+ to transfer from bulk solution to reaction site. According to
(64.9%) was achieved at − 50 mA cm− 2 in a zero-gap membrane elec the above researches, electrochemical reduction activity of RNHCOO-
trode assembly configuration, the highest performance ever reported in can be improved by tailoring cation-solvent-amine interactions, both in
MEA agent without additives. Moreover, Ni-N/C could maintain the FE aqueous and nonaqueous electrolyte.
as much as 50% even in various amine-based absorbents, whereas the Notably, salt addition in other solvents such as dimethoxyethane
CO FE of commercial Ag nanoparticles (cAg) fell to 0% with amine (DME), dimethylformamide (DMF), PC, and tetrahydrofuran (THF) re
bulkiness increasing (Fig. 4c-f). By controlling the size of alkali metal sults in severe precipitation, causing the solution unusable for electro
cations in the electrolyte, the CO2 electroreduction performance of chemical reactions [40]. In addition, the speciation of carbamate is
Ni-N/C was almost insensitive to the cation species (Fig. 4g). On the associated with temperature. In aqueous media, the free-energy barrier
contrary, cAg had a sharp increase in CO partial current density (jCO) for carbamate formation decreases with temperature increasing [42]. In
from Li+ to Cs+ (Fig. 4h). In the presence of any cation, Ni-N/C possessed nonaqueous media, elevated temperature accelerates the carbamate
Fig. 3. Interfacial electron transfer mechanism in (a) MEA-CO2 electrolyte and (b) MEA-CO2 with alkali cations electrolyte. (c) FE of CO in MEA electrolyte with
different alkali cations at applied potentials of − 0.58 V and − 0.66 V vs RHE. (d) The product distributions of CO and H2 at different current densities in 30 wt%
aqueous MEA solution with 2 M KCl at 60 ◦ C.
Adapted from ref. [37] with permission. Copyright 2020 Springer Nature Publishing Group.
4
Fig. 4. (a) Transmission electron microscopy image and (b) high-angle annular dark-field scanning transmission electron microscopy image of Ni-N/C. CO FEs of Ni-
N/C and cAg in (c) 1 M MEA, (d) 1 M 3-amino-1-propanol, (e) 1 M 2-(methylamino)ethanol, and (f) 1 M diethanolamine solutions. jCO of (g) Ni-N/C and (h) cAg in
0.05 M carbonate electrolyte with different alkali cations. (i) jCO(Cs+)/jCO(Li+) at − 1.7 V vs normal hydrogen electrode (NHE) with respect to the PZC of catalysts in
0.05 M carbonate electrolyte. (j) The reduction pathway via selective cleavage of N-C bond and amine regeneration for subsequent cycling. (k) ΔG and enthalpy
change (ΔH) of deprotonation of carbamic acid to the corresponding carbamate. (l) Structure and (m) N − C bond length in carbamic acid and alkali-metal
carbamate.
(a-i) Adapted from ref. [39] with permission. Copyright 2022 The Royal Society of Chemistry. (j) Adapted from ref. [40] with permission. Copyright 2018 Elsevier.
(k-m) Adapted from ref. [41] with permission. Copyright 2019 American Chemical Society.
generation rate [43]. Therefore, electrolyte constituents (solvent, amine, HER pathway competing with CO2 reduction on Cu electrode was water
concentration, salt) should be chosen and optimized elaborately to reduction, even in relatively acidic electrolyte [46]. The adsorbed CO
better manipulate and improve integrated capture-conversion reaction. formed during HCO-3 reduction was responsible for inhibiting water
reduction, but proton reduction was a diffusion-limited process that was
hardly influenced in this process. As previously proposed, HCO-3 always
2.2. Aqueous alkaline media with carbonate and bicarbonate for capture
acted as pH buffer [47] or proton donor [48] during electroreduction.
and conversion
Dunwell et al. revealed that HCO-3 could also act to increase the effective
CO2 concentration near the electrode surface through rapid equilibrium
When alkaline solutions, like KOH, are used as capture agents, CO2
between these two species [49]. By covering the electrode surface with
can be captured in the form of bicarbonate (HCO-3) or carbonate (CO2- 3 ).
hydrophobic layer, the proton donor ability of HCO-3 could be effectively
CO2 and hydroxide can then be recovered through energy-intensive
calcination steps. To convert the released CO2 into chemicals or fuels inhibited [50].
Because the desorbed CO2 from HCO-3 is regarded as the main elec
by electrochemical reduction pathway, it should be purified and pres
surized prior to entering the electrolyser. If this HCO-3 or CO2- troactive species, it is important to promote its release and avoid HCO-3
3 enriched
to act as proton donor to achieve high selectivity. Prof. Berlinguette and
solution is directly delivered to the electrolyser, not only the need to
recover CO2 from sorbent is bypassed but also the design of electrolyser colleagues have been working on the use of HCO-3 as feedstock to effi
ciently integrate carbon capture with CO2 electrochemical reduction.
is simplified. Besides, the direct utilization of HCO-3 or CO2-
3 as a source of
carbon is attractive as the saturated concentration (e.g., 3.3 M for The liquid-fed electrolyser employing either a monopolar membrane (i.
e. cation exchange membrane, CEM) or bipolar membrane (BPM) offers
KHCO3) is an order of magnitude higher than that of simply dissolved
CO2. an acidic environment at cathode-membrane interface (Fig. 5a). Protons
derived from water transport through the membrane and react with
The first attempt of direct HCO-3 electroreduction could date back to
1983 when Hori et al. reported the reduction of NaHCO3 to produce HCO-3 at cathode to form CO2, which is then reduced to CO at gas
diffusion electrode (GDE) [51]. The continuous production of OH- dur
formate with a small current density [44], which verified the feasibility
of direct reduction of HCO-3. However, it has to be acknowledged that ing this process regenerates the alkaline capture sorbent. By using a flow
cell containing a BPM, 3 M KHCO3 was reduced to CO with a FE of 81%
one major challenge for HCO-3 electroreduction in aqueous solution is
the loss of FE due to the competing HER [45]. HER occurs either through at 25 mA cm− 2 and 37% at 100 mA cm− 2 [23]. Because BPM delivered a
higher H+ flux from anode side to cathode side to react with HCO-3
proton reduction or water reduction. Ooka et al. found that the major
5
Fig. 5. (a) Schematic of the liquid-fed bicarbonate electrolyser architecture equipped with BPM. (b) The change of outlet CO2 concentration with time of BPM-based
electrolyser, AEM-based electrolyser, and BPM-based electrolyser without applied potential. (c) FE of CO as a function of outlet CO2 concentration of BPM- and AEM-
based electrolysers during 2 h electrolysis. (d) Summary of the reactions at membrane, catalyst surface, and in bulk solution in the cathode compartment of BPM- and
AEM-based electrolysers. The most reactive H+ donors and electrochemically active species are highlighted in orange and green. The reactions in blue are not
expected to dominate the reaction chemistry. (e) Schematic of electrolyser based on CEM and hydrogen oxidation reaction. (f) Current densities and corresponding
cell voltages of different electrolysers. (g) Experimental setup for operando pH measurements in a flow-cell electrolyser.
(a) Adapted from ref. [51] with permission. Copyright 2020 American Chemical Society. (b-d) Adapted from ref. [23] with permission. Copyright 2019 Elsevier. (e-f)
Adapted from ref. [55] with permission. Copyright 2022 American Chemical Society. (g) Adapted from ref. [62] with permission. Copyright 2020 American
Chemical Society.
6
forming a high concentration of CO2 at catalyst/electrolyte interface 100 mA cm− 2 and 400 mA cm− 2 were 64% and 27%, respectively.
(Fig. 5b-d), 20% higher FE value of CO was obtained with BPM cell Although all above researches verified the feasibility of direct HCO-3
relative to anion exchange membrane (AEM) cell at the same outlet CO2 electroreduction without CO2 feed, HCO-3 still needed to dissociate to
concentration. Besides, the use of BPM may also help to inhibit product form CO2 first that was then reduced. This approach was regarded as
crossover [52]. indirect reduction[44]. Electroreduction of HCO-3 could proceed through
Although electrolyser with BPM converts a larger fraction of CO2 direct reduction as well, where no CO2 molecule was formed prior to
feedstock than electrolyser with AEM, a significant potential is required reduction [64,65]. Direct reduction of HCO-3 to formate was first
to dissociate H2O into H+ and OH- [53] and realize current density observed by Wrighton [66] and Augustynski [64]. At Pd electrode, a
greater than 200 mA cm− 2 [54]. In order to simultaneously demonstrate large reduction peak appeared in aqueous 1 M NaHCO3 solution, which
high CO2 utilization and low voltage, the electrolyser was optimized by was absent in aqueous Na2CO3 solution with the same concentration.
replacing BPM with CEM and replacing anodic oxygen evolution with Stirring the solution could increase the peak intensity, but bubbling CO2
hydrogen oxidation (Fig. 5e) [55]. CEM lowered the Ohmic resistance would cause the peak decrease. This strongly suggested HCO-3 but not
relative to AEM by transporting highly mobile H+ instead of OH-, and dissolved CO2 was the electroactive species [64]. Later, Phani et al.
avoided the high H2O dissociation overpotential associated with BPM employed the substrate-generation/tip-collection mode of scanning
[56]. The oxidation of hydrogen instead of H2O also lowered the applied electrochemical microscopy to detect the products of HCO-3 electro
potential to drive electrolysis. Merely 2.3 V was required to reach duction on Au and Ag surface [65]. HCO-3 could undergo direct reduc
500 mA cm− 2 under this circumstance, much smaller than the potential tion on Au and Ag surface, and Au surface was more favorable than Pd in
of 12.7 V for BPM-based electrolyser (Fig. 5f). Moreover, the FE of CO producing formate from HCO-3. However, the product distribution var
could be further increased to 89% at 100 mA cm− 2 and 44% at ied with the pH of solution. In alkaline solution (pH=8.5–10), only
500 mA cm− 2 by pressurizing the feedstock to increase CO2 solubility. formate was formed as the main product; while even in slightly acidic
In addition to membrane, their researches further verified the design solution (pH=6.5) CO was obtained as the major product. This phe
of electrode, anode chemistries, pressure, and temperature of electro nomenon was also observed by Koper et al. [67]. Therefore, pursuing
lyser would affect the rate and efficiency of reaction as well. Unlike approaches for in situ process monitoring and mechanistic elucidation is
electrolyser fed with gaseous CO2, HCO-3 electrolyser does not need important during electrolysis.
hydrophobic electrode to prevent “flooding” [57,58]. By tuning the CO2 can also convert into CO2- 3 when strong base is used as capture
composition and structure of gas diffusion layer (GDL) in GDE, which solution. One way to utilize CO2- 3 is to adopt a further reaction step
was furnished with a silver catalyst layer through physical vapor converting it to HCO-3, consuming additional energy [68]. Alternatively,
deposition (PVD) and spray-coat deposition but free of hydrophobic direct CO2-3 electrolysis is more effective. A BPM electrolyser equipped
polytetrafluoroethylene (PTFE) and microporous layer (MPL) constitu with Ag electrocatalyst was used to reduce 1 M K2CO3 to syngas with a
ents, the in situ generation of CO2 from HCO-3 was enhanced. As a result, 3:1 H2:CO ratio [20]. No gaseous CO2 at reactor outlet was detected,
the FE of CO could reach as high as 82 ± 2% at 100 mA cm− 2 with CO2 confirming 100% carbon utilization of input-carbon-to-product. As a
utilization rate of ~70% [51]. However, the fabrication of this kind of result, the gas product exiting the electrolyser was pure syngas with the
composite electrode with uniform catalyst layer is still challenging, and full cell energy efficiency of 35% at 150 mA cm− 2, and this system was
the degradation under electrolysis is inevitable [59,60]. Free-standing stable under a continuous 145 h of catalytic operation.
porous metal electrode is easy to fabricate and more stable during
electrolysis, which is suitable to act as the alternative to composite 2.3. Ionic liquids and covalent organic frameworks for capture and
electrode. By adopting porous free-standing Ag foam electrode, not only conversion
the assembly of electrolyser was simplified, but also a FE of CO of 59%
could be achieved at 100 mA cm− 2 at ambient pressure [61]. Addi In addition to well-established integrated CO2 capture and conver
tionally, only 3% loss in FE arose over 80-hour consecutive operation, sion process based on amine and alkaline media, ionic liquids (ILs) and
and this porous Ag electrode was more resistant to most of impurities in covalent organic frameworks (COFs) have also been investigated as
flue gas, which formed NO-3, SO2- 2-
4 , SO3 in capture agent. When agents for CO2 capture and conversion.
increasing the inlet pressure of electrolyser to 4 atm, the FE of CO could IL, as a type of liquid sorbent, has unique physical and chemical
further increase to 95% at 100 mA cm− 2. Thus, elevated pressure properties including low vapor pressure, low volatility, good thermal
increased the amount of CO2 participating in reaction and consequently stability, more selective for CO2 than for other gases, and ionically
the rate of CO formation. Because protons play an important role in conductive [6]. By virtue of these favorable features, IL can perform as
HCO-3 electrolysis, determining the pH at electrode/membrane interface an alternative to amine-based solvent and is appropriate for the com
in GDE is critical. Operando Raman spectroscopy was used to probe the bination of CO2 capture and conversion process. Because IL is not
pH proximity to the catalyst surface [62] (Fig. 5g). It was found that pH aqueous solution, the competing hydrogen evolution can be suppressed
varied as a function of current density, temperature, and proximity to and thus the efficiency of CO2 reduction is increased [69,70]. The CO2
the catalyst surface. The pH at electrode surface was higher than that at molecule captured by IL is also advantageous for electrocatalysis due to
bulk solution, and pH gradients in flow cell were significantly smaller the bent structure [71].
than those in H-cell due to the different mass transport characteristics of In recent years, IL, especially functionalized IL, has been demon
the flow environment. The pH profile was also related to the applied strated possessing excellent capture capacity for CO2 [72,73]. And in
current density that higher current density resulted in more OH- accu parallel with rapid progress in CO2 capture technology, a series of
mulation, causing the dramatical increase of pH near the catalyst sur studies have reported increased CO2 reduction selectivity when IL was
face. In addition, pH increased from 9 to 9.6 as the temperature of used as electrolyte or additive in aqueous solution [74,75]. However,
catholyte increased from 20 ℃ to 70 ℃, with the FE of H2 dropping from the process assisted by IL which functions both as absorbent and elec
32% to 15%. The performance of GDE greatly depended on the mass trolyte has hardly ever been reported. Recently, a new concept of pho
transport of reactive species, this research mapped the pH gradients and toelectrochemical (PEC) system was proposed to capture and convert
enabled the study of mass transport process within GDE. The electrolytic CO2 into formic acid [76]. The aqueous [NH2C3MIm][Br] (0.454 M) was
formation of other high-value carbon products such as formate at high adopted within this PEC reactor, and a high FE (94.1%) and a high
current density could also be achieved in a continuous flow cell electro-to-chemical efficiency (82.6%) of formic acid at 1.7 V were
assembled with BPM and Bi cathode electrocatalyst supported on carbon achieved. In addition to the high efficiency, this PEC strategy incorpo
paper [63]. In this case, electrolysis of 3 M KHCO3 yielded formate at a rated solar energy into CO2 conversion, enabling to close the carbon
partial current density of 108 mA cm− 2, and the FE of formate at cycle and store solar energy in carbon-derived chemicals. To improve
7
the capture capability, task-specific IL (TSIL) with amine functional and COFs for integrated CO2 capture and electrochemical conversion,
groups has been developed [72,77]. The amine functional group binds both technologies are still in the conceptual phase of industrial appli
strongly to CO2 and the heat of adsorption of carbamate formation is cations. Further elaborate design and regulation will motivate their
often higher [21]. Therefore, TSIL is more suitable for capturing CO2 potential to improve the overall energy efficiency of this system.
while conventional IL is favorable for electrocatalytic conversion. Be
sides, although several groups have reported IL for CO2 electroreduction 3. Integrated capture and conversion via thermochemical
with impressive yields for CO and formate, few C-C products have been approaches
reported even for Cu electrode that is best known for producing C2+
products [21]. Hence, how to balance capture and electrocatalytic per In addition to electrochemical approaches, the coupling between
formance by structure regulation of IL is a question worth discussing. CO2 capture and conversion via thermal catalysis approaches has also
As novel crystalline porous frameworks, COFs comprise organic been studied. This integrated thermal catalysis process also needs the
components linked by strong covalent bonds [78]. COFs are well known assistance of DFMs. Generally, DFMs first capture CO2 from flue gas.
for the exceptional porosity, large surface area, low density, high When capture is finished, the feed gas is switched to reducing agent such
modularity, diverse functionality, easily adjustable pore textures, as well as H2 to convert the adsorbed CO2, accomplishing with the adsorbent
as tunable surface properties and morphology [79]. By virtue of these regeneration [24]. Various conversion routes such as CO2 methanation
unique features, COFs have been recently studied in a wide range of [84], dry reforming [85], and water-gas shift [86] are included in this
applications, ranging from adsorption materials for CO2 capture [80], process for end-use applications. High temperature is always required to
and potential catalysts for CO2 electrocatalysis [81,82]. facilitate the reaction progress. Despite the additional energy con
Using COFs for both CO2 capture and conversion provides an op sumption associated with high temperature, this integrated process can
portunity to integrate them as a single step. Liu et al. synthesized amine- be isothermally and continuously operated in the single unit by
based COF (COF-300-AR) via transforming the imine-linked frameworks switching the inlet gas. There are specific requirements for catalysts and
through reduction reaction (Fig. 6a-b) [83]. After conversion, the crys adsorbents in DFMs because the CO2 adsorption and catalytic perfor
tallinity and underlying topology of the frameworks were fully retained, mance are significantly affected by the interactions between catalysts
but the newly formed amine linkages improved the chemical and ther and adsorbents. The presence of adsorbent improves the performance of
mal stability. Surprisingly, the crystallinity was unaltered after immer catalyst through assisting catalyst dispersion and providing effective
sion in 6 M HCl and 6 M NaOH for more than 12 h. When depositing catalytic active sites, and the stability of DFM can also be promoted due
COF-300-AR on a Ag electrode to form a molecularly defined interface to their interactions. Since the specific reaction temperature limits the
for electrochemical reaction (Fig. 6c), this structure provided high selection and design of DFMs, more researches are demanded for better
selectivity of CO2 reduction against hydrogen evolution. The amine DFM design.
linkages in COF-300-AR offered chemisorption sites to selectively cap
ture CO2 by forming carbamate, while Ag surface activated carbamate
and provided sufficient electrons for reduction (Fig. 6d). This COF-Ag 3.1. CO2 conversion to CO and syngas
interface exhibited FE of CO of 53% and 80% under the potential of
− 0.7 and − 0.85 V vs RHE, respectively. The formation of carbamate Among various CO2 capture techniques, calcium looping (CaL) pro
made the simultaneous CO2 capture and electrochemical CO2 reduction cess based on high-temperature reversible carbonation/calcination re
possible. action has attracted much attention [87]. The capture cost of CaL is
Although many research advances have been made in adopting ILs competitive with that of current amine scrubbing technology owing to
the high capture capacity and abundant low-price natural CaO resources
Fig. 6. Schematic of (a) reductive reaction of benzylidene aniline conversion to benzyl aniline, (b) COF-300 reduction to COF-300-AR, and (c) interface between
COF-300-AR and Ag electrode. (d) The mechanism of CO2 reduction at COF-Ag interface.
Adapted from ref. [83] with permission. Copyright 2018 Elsevier.
8
[88,89]. Nevertheless, CaO sinters and agglomerates easily at high two major greenhouse gases, CO2 and CH4, into more valuable syngas
temperature, resulting in a rapid loss of its surface area and reactivity with a moderate ratio. The produced syngas can be further converted to
towards CO2 [90,91]. Many efforts have been made to solve sintering liquid fuels and fine chemicals via Fischer-Tropsch synthesis [104].
problem. One strategy is to incorporate high-temperature refractory Nevertheless, because the strong bond strength of C═O and C-H in CO2
oxides [92–94] and inert metals [95,96] to improve the thermal stability and CH4 and the endothermic characteristic of MDR, high temperature is
of CaO. Another one is to construct porosity within CaO [97]. always needed to achieve desirable CO2 and CH4 conversion for this
Reverse-water-gas-shift (RWGS) is one of the mature CO2 conversion thermally-driven process [105]. A feasible way is to combine MDR re
reactions [98]. Various heterogeneous transition metal-based catalysts action with CaL process where CaO is used to shift CH4 conversion
supported on metal oxides have been explored within the temperature equilibrium toward higher H2 production through in situ adsorption of
range of 200–600 ℃ [99,100]. However, the conversion efficiency is CO2 [106]. Ni has been regarded as a potential constituent for
still not high enough. Since RWGS reaction is slightly endothermic, composing DFM due to the comparable activity, low cost, and plentiful
higher temperature is more favorable [101], which opens up the pos reserve [107,108]. Tian et al. proposed a novel CaL methane reforming
sibility of matching the high temperature of CaL process. Shao et al. process, which coupled CaL and MDR via the developed CaO-Ni DFM
integrated CaL and RWGS in the same column and operated at the same [109]. Adopting CaO/Ni_9 sorbent-catalyst could generate a maximum
temperature of 650 ℃ (Fig. 7a) [102]. Through a simple one-pot sol-gel syngas yield of 10.4 mmol g− 1 and an average cyclic CO2 utilization
method, Fe3+/Fe2+ and Co3+/Co2+ redox couples were doped into hi efficiency of 65% with an average cyclic CH4 conversion efficiency of
erarchical porous CaO/MgO composite. Different FexCoyMg10CaO 86%. The in situ consumption of CO2 via MDR drove the dissociation of
composites were obtained and evaluated. Among them, the presence of CaCO3, making this energy-intensive reaction perform with superior
different valence states in oxides not only offered extra oxygen vacancies reaction kinetics than traditional CaL at lower temperature. Meanwhile,
to promote CO2 adsorption, but also lowered the potential difference of the lower temperature coupled with the strengthened metal-support
Fe3+/Fe2+ through the newly formed Fermi level in Fe5Co5Mg10CaO, interaction and the confinement effect of support improved the sinter
making electron spillover easier to improve RWGS (Fig. 7b). Besides, the ing resistance of materials [110], which commonly restricted CaL-based
sintering problem of CaO was successfully solved under the presence of CO2 capture technology. In this case, the energy consumption for CO2
high-temperature refractory MgO and highly dispersed Fe and Co ox utilization and fuel demand for syngas production were 22% and 9%
ides. A high capture capacity of 9.0–9.2 mmol g− 1, an in situ conversion lower than those of conventional MDR. It was found that CO2 sorption
efficiency near 90%, and CO selectivity close to 100% were achieved in capacity and CO productivity of CaO-Ni DFM depended on the synthetic
this integrated CaL-RWGS process. And this integrated process was methods [111]. Different from the synthetic methods of wet mixing and
much more cost-effective than the corresponding individual CaL and acidification/impregnation, propionic acid pretreatment and citric acid
RWGS process. complex were beneficial to the expansion of specific surface area and
Methane dry reforming (MDR) is also a reaction allowing the utili pore structure for accommodating and anchoring Ni species to achieve
zation of CO2 (CH4 +CO2→2CO+2 H2) [103]. This process transforms uniform dispersion. Besides, Ni could be immobilized in this process
Fig. 7. (a) Schematic of integration of CaL and RWGS in one fixed-bed column with high-temperature industrial flue gas. (b) Schematic of heterojunction-redox
mechanism of Fe5Co5Mg10CaO for adsorption enhanced in situ conversion. (c) Schematic of integration of CaL and MDR in a fluidized bed containing a mixture
of CaO and Ni supported MgO-Al2O3 to synthesize syngas. (d) Schematic of CaL-MDR process using CaO-Ni-CeO2 as DFM. (e) The CO2 concentration during
carbonation reaction within 100–900 ℃. (f) Concentration profiles of CH4, CO2, H2, and CO as a function of temperature.
(a-b) Adapted from ref. [102] with permission. Copyright 2021 The Royal Society of Chemistry. (c) Adapted from ref. [90] with permission. Copyright 2018
American Chemical Society. (d-f) Adapted from ref. [114] with permission. Copyright 2022 Elsevier.
9
which inhibited crystallite growth and agglomeration [112,113]. By a result of phase transition from Ca2Fe2O5 to more stable but less active
virtue of the good textural properties for CO2 diffusion and sorption and MgFe2O4, crystal size variation, and agglomeration.
abundant Ni active sites for reinforced catalytic activity, the desired DFMs generally consist of alkali or alkaline earth metals for CO2
Ni-CaO composite exhibited high CO2 sorption capacity capture and transition metal catalysts for CO2 conversion. Some inte
1 1
(13.28 mmol g−DFM ) and CO productivity (5.12 mmol g−DFM ) under the grated processes could operate using solely CaO in the absence of
isothermal testing temperature of 650 ℃ in integrated CO2 sorption and transition metals. Although the cost of DFM was reduced, the formation
RWGS process. This DFM could also perform stably within 17 consecu of CO was slow [120,121]. Under this circumstance, the operating
tive sorption and hydrogenation cycles. temperature ranged from 600 ℃ to 700 ℃, leading to low cyclic sta
Kim et al. used a fluidized bed containing a mixture of CaO and Ni bility. Sasayama et al. explored the potential of transition-metal-free
supported MgO-Al2O3 (Fig. 7c) to synthesize syngas with purity close to DFM Na/Al2O3 to capture CO2 and directly produce syngas via RWGS
100% and H2:CO ratio of ~1.06 [90]. The system operated efficiently [122]. The experimental results showed it could achieve CO2 conversion
over more than 10 cycles, and the concentration of unreacted CO2 in the and CO selectivity exceeding 90% and 95% at 450–500 ℃. A 50-cycle
off-gas was below 0.08%, demonstrating almost the full conversion of stability test revealed it was stable without significant deactivation.
captured CO2 in a single and integrated step. A CaO-Ni-CeO2 Furthermore, the scale-up direct syngas production from 5 vol% and
adsorbent-catalyst DFM was firstly developed (Fig. 7d), and Law et al. 400 ppm CO2 (atmospheric level) were performed using 60 g of
reported for the first time of a temperature-programmed reaction plat Na/Al2O3. When the feed concentration of CO2 was 5 vol%, the obtained
form to provide a fast and real-time analysis of the reaction kinetics of H2/CO ratio was 2.8, which was practically feasible for the
CaL-MDR based on this DFM [114]. A typical temperature-programmed Fischer-Tropsch synthesis. When using 400 ppm CO2, a high CO con
reaction profile of CaO carbonation composed of two stages within centration of 14.5 vol% with H2/CO ratio of 3.3 was obtained even
180–710 ℃ (Fig. 7e). An initial reaction occurred at low temperature though the CO2 feed concentration was two orders of magnitude lower.
(180–470 ℃), and the major carbonation occurred at relatively high This result indicated that Na/Al2O3 could directly convert and enrich
temperature (470–710 ℃). The consumption of CO2 reached a atmospheric CO2 into CO with a concentration of more than 500 times
maximum at 600 ℃. When the temperature was above 710 ℃, CaCO3 higher.
decarbonation became dominant and a complete CaO regeneration was A series of advancements have been made in integrated CO2 capture
achieved at 800 ℃. The apparent activation energy (E) of CaO carbon and conversion to CO and syngas, however, further investigations on
ation was proportional to the mass ratio of Ni, which was attributed to actual flue gas containing impurities such as H2O and O2 are also
the blockage of CO2 adsorption. The addition of CeO2 further managed important to verify the practical availability of DFMs.
to lower the E of carbonation owing to the improved overall surface area
and pore volume. Besides, CH4 was able to be activated by CeO2-mo 3.2. CO2 conversion to CH4
dified DFMs under a lower temperature with a smaller E (Fig. 7f). The H2
and CO yields were then evaluated among different DFMs, and the re CH4 is the simplest hydrocarbon with the lowest C/H ratio, which is
sults showed that they were inversely proportional to the mass ratio of widely used in heating, transportation, and power plants by virtue of
Ni. CaO-0.05Ni-0.05CeO2 possessed the highest yields, which were low cost, clean combustion products, and high calorific value
calculated as 754.4 mmolH2 gNi-1 and 456.6 mmolCO g-1 Ni based on the (55.7 kJ g− 1) [24]. The conversion between two important chemicals in
1
CO2 uptake of 10.3 mmol g−CaO . Sufficiently high cyclic stability and C1 chemistry, CO2 and CH4, has attracted great attention (CO2 + 4 H2 ═
moderate required temperature for carbonation (450 ℃) and subse CH4 + 2 H2O) [123], and integrating CO2 capture and methanation
quent dry reforming (680 ℃) were achieved. Sun et al. also incorporated shows advantages in terms of improving process and energy efficiency.
CeO2 into CaO-Ni-based DFM, and the influence of different Ce loadings Compared with RWGS, CO2 methanation can be operated in a relatively
on the performance of integrated CaL-RWGS was studied [115]. The mild condition, which reduces the system’s energy footprint.
DFM with a Ca/Ni/Ce molar ratio of 1:0.1:0.033 exhibited outstanding The first integrated CO2 capture and methanation work was pub
CO yield (7.3 mmol g− 1) over 20 cycles at 650 ℃. However, the lished in 2015 [124], and since then the number of researches has grown
unreacted CO2 was released, leading to relatively low CO2 conversion exponentially. Na2O, K2O, MgO, and CaO are the most common adsor
(51.8%). bents in this process [125,126]. Among them, CaO is widely used due to
By co-loading Ni and CeO2 nanoparticles on ZrO2-coated CaCO3, the excellent theoretical adsorption capacity and low price [24]. How
coupled CaL-MDR could perform in a single reactor by simple gas ever, sintering problem caused by volume change of CaO must be
switching [116]. The protection of ZrO2 coating stabilized Ni and CaCO3 overcome. MgO does not have the same serious sintering problem as
and prevented them from severe sintering [117]. The high mobility of CaO, and its low cost and medium adsorption temperature (~300 ℃)
lattice oxygen in CeO2 benefitted carbon gasification, resisting the make it suitable as adsorbent [24]. In addition, the carriers used to
accumulation of inactive carbon that blocked the active sites of Ni [118]. disperse the adsorbents also have an effect on the adsorption perfor
In addition, abundant oxygen vacancies derived from the redox char mance [126]. Several carrier materials including CeO2, Al2O3, and ZrO2
acteristic of CeO2 facilitated CO2 and CH4 activation, promoting syngas have been studied. Al2O3 is the most commonly used carrier, and it can
production. Markedly, this material could drive CaL-MDR process under adsorb CO2 over Al2O3-OH group at the same time [127]. Another
a thermodynamically extremely unfavorable condition, converting over important component is catalyst. Because reduction of CO2 to CH4 is a
40% of CH4 and CO2 under 5 vol% CO2 feed concentration at 720 ℃. complex eight-electron process with significant kinetic limitations
Zhao et al. found a layered double hydroxide (LDH) structure with [128], suitable catalysts for CO2 methanation to achieve acceptable
highly dispersed atoms could enhance the reactivity [119]. CaFeMg activity and selectivity are required. Ni, Ru, and Rh have been chosen as
layered double oxide (CaFeMg-LDO) bifunctional material derived from the catalytic active sites owing to the high activity. Ni possesses high
LDH was synthesized and examined in CaL-MDR process. Different activity and relatively low cost, nevertheless, it is prone to be oxidized
temperatures ranging from 700 to 1000 ℃ were conducted, among and requires much higher temperature to be reduced [129]. Noble
which 900 ℃ was determined as a suitable reforming temperature metals not only exhibit impressive catalytic performance as active sites,
because 2.5 times higher syngas concentration, higher and more stable but also can serve as promoters of Ni [124,130–132]. Unfortunately, the
H2/CO ratio were obtained. Compared with FeMg-LDO, the presence of high cost and potentially poor resistance to contaminants may hinder
Ca in CaFeMg-LDO led to a certain interaction between Ca and Fe, which their widespread applications. Notably, the interactions within adsor
improved the syngas content and H2/CO ratio. Although CaFeMg-LDO bents, catalysts, and carriers positively affect this integrated capture and
showed an enhanced syngas production due to the highly dispersed methanation process. Therefore, rational design, selection, and combi
CO2 sorption and reforming active sites, it suffered from deactivation as nation of components in DFMs are vital to achieve superior
10
performance. improved the dispersion of Ni, making Ni active sites well exposed
2D-layered Ni-MgO-Al2O3 nanosheets were developed by Zhou et al. instead of covered by the newly formed CaCO3 (Fig. 8a).
to investigate the integrated CO2 capture and isothermal methanation The addition of metal additives can also promote the catalytic per
capability [133]. The process could operate at relatively low tempera formance of DFMs. The integrated CO2 capture and reduction process
ture (≤250 ℃) with continuous and nearly 100% capture of CO2 and a was examined over Ni/Na-γ-Al2O3 in comparison to Ni/γ-Al2O3 [140].
high H2 efficiency of 60% during prolonged cycles. At isothermal con Under 5% CO2, negligible CH4 formation (10.6 μmol g−cat1) was observed
ditions, the adsorption sites could be fully regenerated upon H2 purging, for Ni/γ-Al2O3 due to its small CO2 capture capacity (12.7 μmol g−cat1). In
demonstrating the feasibility without temperature or pressure swing. contrast, one order of magnitude higher yield of CH4 was produced over
Bermejo-López et al. studied the influence of adsorbent nature and Ni/Na-γ-Al2O3 (188 μmol g−cat1), indicating Na-promotion enhanced
metallic content of xwt%Ni-ADS/Al2O3 (ADS=15% CaO or 10% CO2-catalyst interaction (Fig. 8b). Ni/Ca-γ-Al2O3 was ineffective for
Na2CO3) on the CO2 capture and methanation performance [134]. CaO capturing large amounts CO2 owing to the high stability of CaCO3. The
and Na2CO3 provided basic sites with different strength for CO2 CO2 capture capacity of Ni/K-γ-Al2O3 was larger than that of Ni/Na-
adsorption. The higher stability of calcium carbonate made CaO have a γ-Al2O3, however its CH4 selectivity was low. Thus, the hydrogenation
higher CO2 storage capacity, and the maximum capacity was observed at ability and selectivity of Ni were affected by the type of promoter
520 ℃. At this temperature, 15% Ni-15% CaO/Al2O3 exhibited (Fig. 8c). When 100 ppm CO2 was supplied at a rate of 500 mL min− 1
maximum CH4 production of 142 μmol g− 1, larger than that of 5% Ni followed by a supply of 50 mL min− 1 of H2, Ni/Na-γ-Al2O3 successfully
and 10% Ni. On the contrary, the CO2 storage capacity reached the converted CO2 into 11.5% CH4, which was 1000 times higher concen
maximum around 400 ℃ for Na2CO3, which was ascribed to the absence tration than that of the supplied CO2. The capture and conversion were
of strong basic sites penalizing the stability of carbonate. 186 μmol CH4 also investigated in the presence of O2. Although the unreacted CO2 for
g− 1 was produced for 15% Ni-10% Na2CO3/Al2O3, exceeding that of 5% 400 ppm CO2/20% O2 was higher than that of 400 ppm CO2, the CH4
Ni and 10% Ni. The above results confirmed the increase of Ni loading formation amount was comparably high and selectivity was over 90%.
facilitated close contact between adsorbent and metallic phase, pro In addition, the effect of pressure was also explored. As pressure
moting the CO2 storage and hydrogenation performance, and higher increased from ambient to 0.9 MPa under 5% CO2, the CO2 capture
CH4 yield was observed for Na2CO3 at lower temperature. CeO2 as a kind capacity increased from 209 μmol g−cat1 to 299 μmol g−cat1, while CH4 for
of carrier material has drawn intensive attention by virtue of basic na mation increased from 188 μmol g−cat1 to 266 μmol g−cat1. The CH4 selec
ture, high stability, and the ability to form oxygen vacancies [135]. The tivity increased from 93% to 96%. For 400 ppm and 100 ppm CO2, the
high affinity between metal atom and surface lattice oxygen can realize amounts of CH4 formed at 0.9 MPa increased to 159 μmol g−cat1 and 111
high metal dispersion [136], however, it is prone to generate CO rather μmol g−cat1 with CO2 conversion and CH4 selectivity exceeding 96%. The
than CH4 due to the weak CO-CeO2 bonding. Sun et al. synthesized a investigated Ni/Na-γ-Al2O3 herein efficiently captured CO2 within a
physical mixture of CaO and Ni doped CeO2 nanorods to explore CO2 wide content range and converted it into CH4 with high conversion ef
methanation based on the synergistic effect of Ni and CeO2 [137]. When ficiency and selectivity. And the results verified pressure elevation was
Ni-free CeO2-CaO was used, the CO2 capture capacity was an effective way to improve CO2 utilization efficiency.
14.9 mmol g− 1 and CO was the sole product. On the contrary, with only Supported Ru is a suitable methanation catalyst. Duyar et al. fabri
0.5% Ni addition, the CO2 conversion efficiency could reach 50.4%, and cated a series of DFMs consisting of CaO as adsorbent and Ru as
the yield and selectivity of CH4 were drastically influenced methanation catalyst, which were all supported on porous Al2O3 carrier
(1540 mmol g−Ni1 and 85.8%), shifting CH4 as the primary product. DFT [124]. A spillover to Ru sites occurred via CO2 desorption from CaO sites
calculations verified the cooperative catalytic performance of highly and chemisorption of CO2 on Ru sites, which was followed by metha
dispersed Ni and oxygen vacancies on Ni doped CeO2. CO2 was reduced nation over Ru and desorption of products. It was found that the extent
to CO over oxygen vacancies on CeO2, and CO desorbed and diffused to of CO2 spillover increased by increasing the CaO content for a given
Ni where it was hydrogenated to form CH4, the main product. amount of Ru. But the optimum composition was around 5% Ru, 10%
Additionally, the problem of volume expansion when CaO is used as CaO/Al2O3, and this DFM could perform stably over cyclic tests under
adsorbent has to be considered. After carbonation, the volume increases 8% CO2/21% H2O/air accelerated aging condition. Previous studies
dramatically from CaO (16.9 cm3 mol− 1) to CaCO3 (34.1 cm3 mol− 1) found Ca-based adsorbents could provide sites with high basicity and
[138]. This may cause the coverage of Ni active sites by CaCO3, leading were conducive to CH4 formation at high temperature, while Na-based
to the insufficient conversion of captured CO2. Therefore, regulation of adsorbents provided weak strength basic sites and favored CH4 forma
the distance between Ni and CaO is essential for the performance. tion at intermediate temperature [134,141,142]. And the addition of
Various Ni/CaO-based DFMs with different distances between active Na2CO3 into calcium adsorbents could improve the cyclic stability of
sites and adsorbents were investigated by Sun et al. [139]. Both 1% CO2 adsorption with fast kinetics [143]. Inspired by these observations,
NiCaO and 10%NiCaO synthesized by one-pot method exhibited low in the work by Bermejo-López et al., the joint presence of Na and Ca in
CO2 conversion (38% and 45%), CH4 selectivity (58% and 69%), and Ru-based DFM was studied and whether it was possible to modulate the
CH4 yield (2 mmol g− 1 and 2.5 mmol g− 1), which resulted from the basicity of DFM to enhance CH4 production in an extended temperature
expansion of adsorbent after carbonation, making Ni active sites covered range was explored [144]. A series of 4%Ru-Na2CO3-CaO/Al2O3 with
by the formed CaCO3 layer. Although 1%NiCeCaO fabricated by wet different Na2CO3/CaO ratios (a total adsorbent content of 16%) were
impregnation possessed longer distance between adsorbents and active prepared. By varying the Na2CO3/CaO ratio, the basicity of DFM was
sites than that of one-pot reduced catalyst, the CH4 yield only increased modulated which promoted the formation of basic sites with medium
to 3.3 mmol g− 1, which was attributed to the barrier effect of CeO2 strength, and their catalytic activity showed different trends with tem
mitigating the volume increase. To further avoid the negative effect of perature. The presence of Na2CO3 favored CH4 production at interme
volume change, the adsorbent CeCaO was carbonized prior to Ni diate temperature (310 ℃), while the presence of CaO favored high
impregnation. In this case, 1%Ni/CeCaCO3 had most of the Ni active temperature production (400 ℃). However, the incorporation of both
sites outside. CH4 yield and selectivity were largely increased to adsorbents improved CH4 generation over the whole temperature win
6 mmol g− 1 and 81%. However, only after one cycle, CH4 yield and dow (280–400 ℃). Besides, by determining the Ru dispersion of DFM, it
selectivity were decreased to 4.11 mmol g− 1 and 74%. CaCO3 decom was found that CaO penalized the dispersion while Na2CO3 promoted it,
posed to CaO and then carbonized at the CO2 capture stage, covering Ni and the promotion was increased by the joint presence of both adsor
active sites again. With the increase of distance by physical mixing bents. Among them, DFM composed of 8% of both Na2CO3 and CaO had
method, 1%Ni/CeO2-CaO exhibited the highest CO2 conversion (62%), the highest medium basicity and Ru dispersion, whose yield of CH4 at
CH4 selectivity (84%), and CH4 yield (8 mmol g− 1). CeO2 nanorods 370 ℃ was 364 μmol g− 1 with a high selectivity of 99%. The improved
11
Fig. 8. (a) Mechanism illustration of performance enhancement by 1%Ni/CeO2-CaO. (b) Schematic of the integrated process over Ni/(Na, K, Ca)-γ-Al2O3 using
circulating fluidized-bed reactor. (c) CO2 capture and CO/CH4 production capacities of Ni/(Na, K, Ca)-γ-Al2O3 and Ni/Al2O3 and the corresponding CO2 conversion
and CH4 selectivity. (d) CO2 capture capacities and (e) CH4 yields of (2.5, 5, 10)Ru/CeO2-MgO within 10 cycles. (f) Schematic diagram of integrated CO2 capture and
methanation process over Ru/rod-CeO2-MgO.
(a) Adapted from ref. [139] with permission. Copyright 2020 Elsevier. (b-c) Adapted from ref. [140] with permission. Copyright 2021 American Chemical Society.
(d-e) Adapted from ref. [130] with permission. Copyright 2020 Elsevier. (f) Adapted from ref. [146] with permission. Copyright 2022 Elsevier.
dispersion of Ru and promotion of contact between medium strength unlike Ni-based catalysts that will be oxidized and need relatively high
carbonates and metallic sites boosted the whole process. MgO shows temperature to be reduced to their catalytically active state [126], the
advantages in this integrated process because it has an operational unique redox properties of Ru enable it to be rapidly reduced under the
adsorption temperature of about 300 ℃, which is the ideal temperature same condition. In addition, Ru can dissociate H2 molecules into
for methanation using Ru-based catalysts [145]. A series of DFMs con stronger reductants for NiO, which lowers the reduction temperature
sisting of MgO and Ru/CeO2 with different Ru concentrations were [147,148]. Thus, small amounts of Ru will make Ni-based DFMs suitable
fabricated [130]. The oxygen vacancies in Ru/CeO2 served as important for O2-containing flue gas capture and methanation. On the other hand,
cooperative sites for CO2 conversion, and more oxygen vacancies were even at high temperature, incomplete CO2 desorption has been observed
generated with higher Ru loading. In the first cycle, 10Ru/CeO2-MgO in those metal oxide-based chemisorbents [129]. Physisorbents can
with more oxygen vacancies exhibited the highest CH4 production overcome this challenge due to the complete CO2 desorption below
(7.07 mmol g− 1) and CO2 conversion (89%). However, after 10 cycles, typical CO2 hydrogenation reaction temperature. Metal organic frame
5Ru/CeO2-MgO showed the best performance with the highest CH4 works (MOFs) are a kind of porous materials with many structural ad
production (3.36 mmol g− 1) and CO2 conversion (79%), which were vancements, possessing high surface area, large adsorption capability,
much higher than those of 2.5Ru/CeO2-MgO and 10Ru/CeO2-MgO and design flexibility [149]. Appropriate MOFs with robust thermal and
(Fig. 8d-e). This could be attributed to more oxygen vacancies remained structural stability can serve as ideal physisorbents and catalyst supports
in 5Ru/CeO2-MgO. Subsequently, it was found that Ru/CeO2-MgO with for efficient CO2 capture and methanation process [150,151]. Mg-CUK-1
different CeO2 support morphologies showed different activities [146]. is a thermally stable MOF that has been investigated as CO2 physisorbent
Ru/cube-CeO2-MgO possessed more oxygen vacancies, which enhanced [152], and its framework crystallinity or uptake is not impacted when
its CO2 adsorption capacity. However, merely oxygen vacancies could cycling in H2S and H2O vapor, demonstrating its chemical stability
not significantly boost the methanation process. Compared with [153]. Inspired by this, Zurrer et al. loaded Mg-CUK-1 with Ru and Ni
Ru/cube-CeO2-MgO (0.03 mmol g− 1 for CH4 yield and 2.7% for CO2 nanoparticles and adopted it as DFM in the combined CO2 capture and
conversion), Ru/rod-CeO2-MgO and Ru/particle-CeO2-MgO showed methanation [154]. Under simulated dry flue gas condition, Mg-CUK-1
more superior catalytic performance with 0.33 mmol g− 1 and had a CO2 uptake of 1.4 mmol g− 1. Temperature-swing CO2 capture and
0.29 mmol g− 1 for CH4 yield and 55.7% and 59.8% for CO2 conversion, conversion batch recirculation results demonstrated CO2 capture was
respectively. Different from CeO2 with cube morphology, the CeO2 with the limiting factor in the overall system performance. By minimizing
rod and particle morphology had better dispersion of Ru, higher BET catalyst loading to 3 wt%, the CO2 uptake was almost retained without
surface area, and more abundant support-metal interactions, contrib affecting subsequent methanation performance (Fig. 9a). When a 15%
uting to the enhanced activity (Fig. 8f). CO2/air stream was adopted to evaluate the effect of oxygen exposure on
When exposed to an oxidizing environment during CO2 capture, catalyst performance, 3Ru Mg-CUK-1 exhibited oxygen tolerance that
12
Fig. 9. (a) Temperature-swing CO2 capture and conversion performance under 100% and 15% CO2 stream of Mg-CUK-1 loaded with Ru or Ni nanoparticles. (b)
Influence of the type of loaded metal nanoparticle on catalyst oxygen tolerance. (c) High-resolution X-ray photoelectron spectra of Ni 2p of 0.3Ru2.7Ni Mg-CUK-1
and 3Ni Mg-CUK-1 before and after oxygen-tolerance performance test. (d) Schematic layout of integrating DFMs adjacent to the power plant and hydrogen gen
eration unit in practical implementation.
(a-c) Adapted from ref. [154] with permission. Copyright 2022 Royal Society of Chemistry. (d) Adapted from ref. [129] with permission. Copyright 2019 Elsevier.
could sustain CH4 yield of 1.4 mmol g− 1 over 10 cycles. In contrast, 3Ni interactions between metal active sites and CO2 and reaction mecha
Mg-CUK-1 was unable to retain the initial catalytic performance, nisms to specific products need to be further explored.
showing 11.4% decrease in CH4 yield after 10 cycles. Adding merely
0.3 wt% Ru into Ni Mg-CUK-1, the resulting 0.3Ru2.7Ni Mg-CUK-1 4. Conclusions and outlooks
achieved equivalent performance to 3Ru Mg-CUK-1, and meanwhile
retained performance despite oxygen exposure (Fig. 9b). The results Sustainable CO2 management is a necessary approach to carbon-
indicated proper quantity of Ru doping not only facilitated the reduction neutral society with a lower and ultimately negative carbon footprint.
of NiO to Ni (Fig. 9c), but also helped reduce the cost of DFM without This review summarizes the key and emerging developments in
compromising overall performance. In terms of practical application, advanced materials and technologies for CO2 capture, catalytic con
integrated CO2 capture and methanation can be operated near the power version, and direct utilization. Generally, five steps are integral to CO2
plant and renewable hydrogen generation unit (Fig. 9d) [129]. CO2 capture and conversion system: CO2 source, capture medium, process to
captured from flue gas can be hydrogenated by renewable H2 to produce release CO2 from capture medium, CO2 compression, and CO2 conver
CH4, which can be further recycled for re-combustion closing the carbon sion into chemicals. However, the release and compression of CO2
cycle. The heat released by methanation creates a synergistic effect that usually require a major energy input. A techno-economic feasible
drives CO2 desorption and subsequent spillover to catalytic site. approach is to integrate CO2 capture and conversion. The integrated
The intermediate temperature (~300 ℃) enables integrated CO2 process operated in a single-unit system can circumvent the regenera
capture and methanation better CH4 selectivity. And the spillover of CO2 tion of adsorbent and the compression, transportation, and storage of
from adsorbents to catalytic sites is the key step, which can be promoted captured CO2, which are the typical energy-intensive steps in conven
through the regulation of interactions between adsorbents and catalysts. tional CCU process.
Hence, a better understanding of the integration process and effective Integrated CO2 capture and conversion via low-temperature elec
adsorbent and catalyst design are needed for further promotion. trocatalysis (Table 1) and high-temperature thermal catalysis (Table 2)
In addition to CO, syngas, and CH4, other value-added chemicals have attracted fast increasing research interests in shaping new circular
such as formate [155,156] and methanol [157,158] can be synthesized carbon economy. The technical and economic viability of both inte
through integrated CO2 capture and conversion process as well. A key grated and sequential pathways further show the considerable advan
feature in the integrated process reported to date for formate and tages of the integrated pathway. For instance, if the integrated
methanol synthesis is the use of amine or alkali-metal hydroxide base as electrolysis performs similarly to the gas-fed electrolysis, approximately
capture agent, which can assist the homogeneous catalysts in the sub 44% energy consumption and 21% energy cost can be saved and a high
sequent hydrogenation step [159]. However, lots of challenges still single-pass conversion efficiency to recover CO2-lean state of amine can
remain. Their conversion reactions are still under investigation, and the be achieved [10]. When raw natural gas with 30 mol% CO2 is adsorbed
13
Table 1
Summary of progress of direct CO2 electrocatalysis from capture media.
Electrocatalyst Reaction media Applied potential Products FE (%) J (mA cm− 2) Ref.
Porous In 30% (w/w) MEA containing 0.1% (w/w) CTAB -0.8 V vs RHE CO 22.8 / [30]
HCOO- 54.5
Porous Bi 30% (w/w) MEA containing 0.1% (w/w) CTAB -0.8 V vs RHE HCOO- 36 / [30]
Porous Pb 30% (w/w) MEA containing 0.1% (w/w) CTAB -0.8 V vs RHE HCOO- 60.8 / [30]
Porous Ag 30% (w/w) MEA containing 0.1% (w/w) CTAB -0.8 V vs RHE CO 38.2 / [30]
Smooth Au foil 1 M AMP in PC -1.9 V vs Ag|AgCl CO 45 / [31]
Cu electrode EDA -0.78 V vs RHE CO 58 -18.4 [35]
Glassy carbon electrode EDA -0.78 V vs RHE CO 2.3 -0.63 [35]
Ag electrode 30 wt% MEA with 2 M KCl -0.8 V vs RHE CO 72 -50 [37]
Ni-N/C MEA / CO 64.9 -50 [39]
Ag 3 M KHCO3 -3.5 V (Full cell potential) CO 37 -100 [23]
Ag foam electrode 3 M KHCO3 2.3 V (Applied voltage) CO 89 -100 [55]
Ag foam electrode 3 M KHCO3 / CO 59 -100 [61]
Bi on carbon paper 3 M KHCO3 -4 V (Full cell potential) HCOO- 64 -100 [63]
Ag plate aqueous [NH2C3MIm][Br] (0.454 M) 1.7 V (Applied voltage) HCOOH 94.1 / [76]
COF-300-AR on Ag electrode 0.1 M KHCO3 -0.85 V vs RHE CO 80 / [83]
Table 2
Summary of DFMs, performance and reaction conditions of integrated capture and thermal catalysis system.
DFMs Adsorption and conversion CO2 capture capacity CO2 conversion Product Product yield (mmol g-1) Cycles Ref.
condition (mmol g-1) (%) selectivity (%)
CaL-RWGS
Fe5Co5Mg10CaO same temperature of 650 ℃ 9.0–9.2 ~90 ~100 / / [102]
CaL-MDR
CaO/Ni_9 600 ℃ for capture and / 86 / Max.10.4 / [109]
800 ℃ for conversion
Ni-CaO composite same temperature of 650 ℃ 13.28 38.55 ~100 5.12 17 [111]
Ni/MgO-Al2O3 same temperature of 720 ℃ 14.09 ~100 / / 10 [90]
1
CaO-0.05Ni-0.05CeO2 450 ℃ for capture and 10.3 mmol g−CaO / / 754.4 mmolH2 g-1
Ni and 10 [114]
680 ℃ for conversion 456.6 mmolCO g-1
Ni
Ca1Ni0.1Ce0.033 same temperature of 650 ℃ 14.1 51.8 ~100 7.3 20 [115]
NiCe/Ca@Zr same temperature of 720 ℃ / > 40 / / 25 [116]
Na/Al2O3 same temperature of / > 90 > 95 / 50 [122]
450–500 ℃
CO2 capture and methanation
2D-layered Ni-MgO-Al2O3 same temperature of 250 ℃ 0.32 100 100 / 10 [133]
nanosheets
15% Ni 15% CaO/Al2O3 same temperature of 520 ℃ 0.16 88 87 0.14 / [134]
15% Ni 15% Na2CO3/ same temperature of 400 ℃ 0.21 88 86 0.19 / [134]
Al2O3
0.5%Ni/CeO2-CaO same temperature of 550 ℃ / 50.4 85.8 1540 mmol g−Ni1 10 [137]
CeO2-CaO same temperature of 550 ℃ 14.9 39.5 0 0 / [137]
1%Ni/CeO2-CaO same temperature of 550 ℃ 15.3 62 84 8 20 [139]
Ni/Na-γ-Al2O3 same temperature of 450 ℃ 0.209 > 96 > 93 188 / [140]
5% Ru, 10% CaO/γ-Al2O3 same temperature of 320 ℃ 0.4 82.7 / 0.3 20 [124]
4%Ru-8%Na2CO3-8% same temperature of 370 ℃ / / 99 0.364 / [144]
CaO/γ-Al2O3
5% Ru/CeO2-MgO same temperature of 300 ℃ 4.25 79 / 3.36 10 [130]
Ru/rod-CeO2-MgO same temperature of 300 ℃ / 55.7 / 0.33 / [146]
by methanol and subsequent hydrogenated to methyl formate, the in be further promoted. Additionally, the energy efficiency of this elec
tegrated conversion process can save up to 46% of the electricity de trochemical process is still too low for industrial applications. Unlike the
mand, 8% and 7% in the cost and greenhouse emissions of the utilities electrode used in gas-fed CO2 reduction, the electrode is desired to be
compared to the process without integration [160]. Besides, more hydrophilic for integrated electrolysis to increase the electro
techno-economic assessment verifies formic acid and CO are the most chemically active surface area and minimize gas-electrode contact.
economically viable products that can be generated through current Hydrophilic porous electrodes, such as porous metallic foams, are ex
integrated capture-conversion system, with the net present values of pected for solvent to flow within the electrode structure. Therefore, the
$39.4 million and $13.5 million [161]. Syngas as valuable intermediate improved design of electrodes, electrolytes, and even cell configuration
used for production of chemicals and fuels should also be considered as is necessary for the integrated electrolyser to be economically feasible.
economically viable product that would bring advantages to improve For high-temperature thermal catalysis, it is more technologically
the market competitiveness. mature and has a higher degree of readiness for industrial-scale imple
Despite considerable progress has been made in recent years, this mentation, but requires larger energy penalty due to the high-
field is still in its infancy stage of development and several key chal temperature reaction conditions. DFM is the key component in this
lenges need to be tackled. For low-temperature electrocatalysis, the process. The sintering of adsorbents and active metal catalysts at high
overpotential and ohmic loss which lead to electrical energy consump temperature is usually the main cause of decreased catalytic activity,
tion and increase the energy penalty have not been resolved. Besides, the and the accumulation of inactive carbon during long-term reaction will
cleavage of C-N bond and the accessibility of negatively charged block the active site leading to the deactivation of catalyst. Thus,
carbamate and carbonate at the interface of electrode/electrolyte should developing low-cost DFMs that can perform at lower temperature is
14
promising, and exploring the interactions among different components [8] P. De Luna, C. Hahn, D. Higgins, S.A. Jaffer, T.F. Jaramillo, E.H. Sargent, What
would it take for renewably powered electrosynthesis to displace petrochemical
within DFM is necessary for a better understanding of the process and
processes? Science 364 (2019) 3506.
effective catalyst design to disperse active sites and prohibit the sinter [9] B. Gurkan, X. Su, A. Klemm, Y. Kim, S. Mallikarjun Sharada, A. Rodriguez-
ing. Besides, the stability issues in these systems have not been solved for Katakura, K.J. Kron, Perspective and challenges in electrochemical approaches
practical conditions when O2, H2O, and other volatiles are present. for reactive CO2 separations, iScience 24 (2021), 103422.
[10] M. Li, E. Irtem, H.P. Iglesias van Montfort, M. Abdinejad, T. Burdyny, Energy
Because many DFMs are susceptible to the attack by these impurities, comparison of sequential and integrated CO2 capture and electrochemical
constructing highly stable DFMs with selective and active affinity to conversion, Nat. Commun. 13 (2022) 5398.
ward CO2 over other gases is important. [11] A. Otto, T. Grube, S. Schiebahn, D. Stolten, Closing the loop: captured CO2 as a
feedstock in the chemical industry, Energy Environ. Sci. 8 (2015) 3283–3297.
Coupling CO2 conversion with dilute CO2 capture from air or [12] D.J. Heldebrant, J. Kothandaraman, N.M. Dowell, L. Brickett, Next steps for
seawater provides long-term opportunities for neutral or negative CO2 solvent-based CO2 capture; integration of capture, conversion, and
emission. Technologies for utilizing waste heat from industrial flue gases mineralisation, Chem. Sci. 13 (2022) 6445–6456.
[13] D.J. Heldebrant, J. Kothandaraman, Solvent-based absorption, Carbon capture
or renewable energy such as solar energy and wind energy can signifi and storage, The Royal Society of Chemistry, 2020, pp. 36–68.
cantly reduce the operation cost of the systems and make the overall [14] F. Wang, J. Zhao, H. Miao, J. Zhao, H. Zhang, J. Yuan, J. Yan, Current status and
process more environmentally sustainable. Despite many advancements challenges of the ammonia escape inhibition technologies in ammonia-based CO2
capture process, Appl. Energ. 230 (2018) 734–749.
have been achieved enabling the integrated process to feature as next- [15] S.E. Jerng, B.M. Gallant, Electrochemical reduction of CO2 in the captured state
generation carbon management technology, further researches are using aqueous or nonaqueous amines, iScience 25 (2022), 104558.
clearly required to develop inexpensive-metal-based systems that [16] E.S. Sanz-Pérez, C.R. Murdock, S.A. Didas, C.W. Jones, Direct capture of CO2 from
ambient air, Chem. Rev. 116 (2016) 11840–11876.
display high catalytic efficiency for practical application of this process
[17] S. Zeng, X. Zhang, L. Bai, X. Zhang, H. Wang, J. Wang, D. Bao, M. Li, X. Liu,
on an industrially viable larger scale. On the other hand, the local re S. Zhang, Ionic-liquid-based CO2 capture systems: structure, interaction and
action environment and product distribution under reaction conditions process, Chem. Rev. 117 (2017) 9625–9673.
can be probed by operando spectroscopy technology. Theoretical [18] F.P. García de Arquer, C.-T. Dinh, A. Ozden, J. Wicks, C. McCallum, A.R. Kirmani,
D.-H. Nam, C. Gabardo, A. Seifitokaldani, X. Wang, Y.C. Li, F. Li, J. Edwards, L.
modelling and calculations can also provide insights into the reaction J. Richter, S.J. Thorpe, D. Sinton, E.H. Sargent, CO2 electrolysis to multicarbon
mechanism and local reaction environment. Moreover, machine products at activities greater than 1 A cm− 2, Science 367 (2020) 661–666.
learning based on experiment results can accelerate and guide the design [19] C.-T. Dinh, Y.C. Li, E.H. Sargent, Boosting the single-pass conversion for
renewable chemical electrosynthesis, Joule 3 (2019) 13–15.
of CO2 capture and conversion materials [162–164]. The underlying [20] Y.C. Li, G. Lee, T. Yuan, Y. Wang, D.-H. Nam, Z. Wang, F.P. García de Arquer,
mechanism analysis, process optimization, and system management will Y. Lum, C.-T. Dinh, O. Voznyy, E.H. Sargent, CO2 electroreduction from carbonate
be facilitated as well. Overall, the feasibility and economic benefits of electrolyte, ACS Energy Lett. 4 (2019) 1427–1431.
[21] I. Sullivan, A. Goryachev, I.A. Digdaya, X. Li, H.A. Atwater, D.A. Vermaas,
integrated CO2 capture and conversion are analyzed relative to the C. Xiang, Coupling electrochemical CO2 conversion with CO2 capture, Nat. Catal.
sequential CCU pathway. Continuous strategic scheme and system 4 (2021) 952–958.
design of sustainable CO2 management will definitely promote its [22] H. Yamada, Amine-based capture of CO2 for utilization and storage, Polym. J. 53
(2021) 93–102.
development and lay a solid foundation for long-term carbon neutrality [23] T. Li, E.W. Lees, M. Goldman, D.A. Salvatore, D.M. Weekes, C.P. Berlinguette,
goal. Electrolytic conversion of bicarbonate into CO in a flow cell, Joule 3 (2019)
1487–1497.
[24] S. Sun, H. Sun, P.T. Williams, C. Wu, Recent advances in integrated CO2 capture
and utilization: a review, Sustain. Energ. Fuels 5 (2021) 4546–4559.
Declaration of Competing Interest [25] S.B. Jo, J.H. Woo, J.H. Lee, T.Y. Kim, H.I. Kang, S.C. Lee, J.C. Kim, A novel
integrated CO2 capture and direct methanation process using Ni/CaO catal-
sorbents, Sustain. Energ. Fuels 4 (2020) 4679–4687.
The authors declare that they have no known competing financial
[26] N.M. Rezayee, C.A. Huff, M.S. Sanford, Tandem amine and ruthenium-catalyzed
interests or personal relationships that could have appeared to influence hydrogenation of CO2 to methanol, J. Am. Chem. Soc. 137 (2015) 1028–1031.
the work reported in this paper. [27] S. Chen, L. Zeng, H. Tian, X. Li, J. Gong, Enhanced lattice oxygen reactivity over
Ni-modified WO3-based redox catalysts for chemical looping partial oxidation of
methane, ACS Catal. 7 (2017) 3548–3559.
Data Availability [28] K. Fujimoto, K. Omata, T. Nozaki, O. Yamazaki, Y. Han, Selective synthesis of
liquid hydrocarbons from carbon dioxide and methane, Energy Convers. Manag.
No data was used for the research described in the article. 33 (1992) 529–536.
[29] B. Dutcher, M. Fan, A.G. Russell, Amine-based CO2 capture technology
development from the beginning of 2013—a review, ACS Appl. Mater. Interfaces
Acknowledgements 7 (2015) 2137–2148.
[30] L. Chen, F. Li, Y. Zhang, C.L. Bentley, M. Horne, A.M. Bond, J. Zhang,
Electrochemical reduction of carbon dioxide in a monoethanolamine capture
This work was supported by China Huaneng Group (Grant No. medium, ChemSusChem 10 (2017) 4109–4118.
HNKJ20-H58 and HNKJ21-H18). [31] E. Pérez-Gallent, C. Vankani, C. Sánchez-Martínez, A. Anastasopol, E. Goetheer,
Integrating CO2 capture with electrochemical conversion using amine-based
capture solvents as electrolytes, Ind. Eng. Chem. Res. 60 (2021) 4269–4278.
References [32] L.A. Diaz, N. Gao, B. Adhikari, T.E. Lister, E.J. Dufek, A.D. Wilson,
Electrochemical production of syngas from CO2 captured in switchable polarity
solvents, Green. Chem. 20 (2018) 620–626.
[1] P. Tans, E. Dlugokencky, X. Lan, I. Vimont, The power of greenhouse gases,
[33] A.A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, J.K. Nørskov, How copper
NOAA Global Monitoring Laboratory, 2022. 〈https://gml.noaa.gov/ccgg/ghg
catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels, Energy
power/〉.
Environ. Sci. 3 (2010) 1311–1315.
[2] Global Monitoring Laboratory, Trends in atmospheric carbon dioxide, 〈https://
[34] K.P. Kuhl, E.R. Cave, D.N. Abram, T.F. Jaramillo, New insights into the
www.esrl.noaa.gov/gmd/ccgg/trends/gl_trend.html〉 (accessed: October 2022).
electrochemical reduction of carbon dioxide on metallic copper surfaces, Energy
[3] N. Mac Dowell, P.S. Fennell, N. Shah, G.C. Maitland, The role of CO2 capture and
Environ. Sci. 5 (2012) 7050–7059.
utilization in mitigating climate change, Nat. Clim. Change 7 (2017) 243–249.
[35] M. Abdinejad, Z. Mirza, X.-a Zhang, H.-B. Kraatz, Enhanced electrocatalytic
[4] J.W. Maina, J.M. Pringle, J.M. Razal, S. Nunes, L. Vega, F. Gallucci, L.F. Dumee,
activity of primary amines for CO2 reduction using copper electrodes in aqueous
Strategies for integrated capture and conversion of CO2 from dilute flue gases and
solution, ACS Sustain. Chem. Eng. 8 (2020) 1715–1720.
the atmosphere, ChemSusChem 14 (2021) 1805–1820.
[36] E. Santos, W. Schmickler, Electrochemical electron transfer: from marcus theory
[5] A. Sanna, M. Uibu, G. Caramanna, R. Kuusik, M.M. Maroto-Valer, A review of
to electrocatalysis, Fuel Cell Catal. (2009) 31–55.
mineral carbonation technologies to sequester CO2, Chem. Soc. Rev. 43 (2014)
[37] G. Lee, Y.C. Li, J.-Y. Kim, T. Peng, D.-H. Nam, A. Sedighian Rasouli, F. Li, M. Luo,
8049–8080.
A.H. Ip, Y.-C. Joo, E.H. Sargent, Electrochemical upgrade of CO2 from amine
[6] Z. Zhang, Y. Zheng, L. Qian, D. Luo, H. Dou, G. Wen, A. Yu, Z. Chen, Emerging
capture solution, Nat. Energy 6 (2020) 46–53.
trends in sustainable CO2-management materials, Adv. Mater. 34 (2022)
[38] S. Ringe, E.L. Clark, J. Resasco, A. Walton, B. Seger, A.T. Bell, K. Chan,
2201547.
Understanding cation effects in electrochemical CO2 reduction, Energy Environ.
[7] C. Hepburn, E. Adlen, J. Beddington, E.A. Carter, S. Fuss, N. Mac Dowell, J.
Sci. 12 (2019) 3001–3014.
C. Minx, P. Smith, C.K. Williams, The technological and economic prospects for
CO2 utilization and removal, Nature 575 (2019) 87–97.
15
[39] J.H. Kim, H. Jang, G. Bak, W. Choi, H. Yun, E. Lee, D. Kim, J. Kim, S.Y. Lee, Y. [67] R. Kortlever, K.H. Tan, Y. Kwon, M.T.M. Koper, Electrochemical carbon dioxide
J. Hwang, The insensitive cation effect on a single atom Ni catalyst allows and bicarbonate reduction on copper in weakly alkaline media, J. Solid State
selective electrochemical conversion of captured CO2 in universal media, Energy Electrochem. 17 (2013) 1843–1849.
Environ. Sci. 15 (2022) 4301–4312. [68] S. Zhang, C. Chen, K. Li, H. Yu, F. Li, Materials and system design for direct
[40] A. Khurram, M. He, B.M. Gallant, Tailoring the discharge reaction in Li- CO2 electrochemical CO2 conversion in capture media, J. Mater. Chem. A 9 (2021)
batteries through incorporation of CO2 capture chemistry, Joule 2 (2018) 18785–18792.
2649–2666. [69] J.T. Feaster, A.L. Jongerius, X. Liu, M. Urushihara, S.A. Nitopi, C. Hahn, K. Chan,
[41] A. Khurram, L. Yan, Y. Yin, L. Zhao, B.M. Gallant, Promoting amine-activated J.K. Nørskov, T.F. Jaramillo, Understanding the influence of [EMIM]Cl on the
electrochemical CO2 conversion with alkali salts, J. Phys. Chem. C. 123 (2019) suppression of the hydrogen evolution reaction on transition metal electrodes,
18222–18231. Langmuir 33 (2017) 9464–9471.
[42] B. Yoon, G.S. Hwang, Anomalous facile carbamate formation at high stripping [70] B.A. Rosen, J.L. Haan, P. Mukherjee, B. Braunschweig, W. Zhu, A. Salehi-Khojin,
temperatures from carbon dioxide reaction with 2-amino-2-methyl-1-propanol in D.D. Dlott, R.I. Masel, In situ spectroscopic examination of a low overpotential
aqueous solution, ACS Sustain. Chem. Eng. 8 (2020) 18671–18677. pathway for carbon dioxide conversion to carbon monoxide, J. Phys. Chem. C.
[43] A. Khurram, H. Gao, B.M. Gallant, Effects of temperature on amine-mediated CO2 116 (2012) 15307–15312.
capture and conversion in Li cells, J. Phys. Chem. C. 124 (2020) 18877–18885. [71] B.A. Rosen, A. Salehi-Khojin, M.R. Thorson, W. Zhu, D.T. Whipple, P.J.A. Kenis,
[44] Y. Hori, S. Suzuki, Electrolytic reduction of bicarbonate ion at a mercury R.I. Masel, Ionic liquid–mediated selective conversion of CO2 to CO at low
electrode, J. Electrochem. Soc. 130 (2019) 2387–2390. overpotentials, Science 334 (2011) 643–644.
[45] G. Marcandalli, A. Goyal, M.T.M. Koper, Electrolyte effects on the faradaic [72] E.D. Bates, R.D. Mayton, I. Ntai, J.H. Davis, CO2 capture by a task-specific ionic
efficiency of CO2 reduction to CO on a gold electrode, ACS Catal. 11 (2021) liquid, J. Am. Chem. Soc. 124 (2002) 926–927.
4936–4945. [73] G. Cui, J. Wang, S. Zhang, Active chemisorption sites in functionalized ionic
[46] H. Ooka, M.C. Figueiredo, M.T.M. Koper, Competition between hydrogen liquids for carbon capture, Chem. Soc. Rev. 45 (2016) 4307–4339.
evolution and carbon dioxide reduction on copper electrodes in mildly acidic [74] G. Iijima, T. Kitagawa, A. Katayama, T. Inomata, H. Yamaguchi, K. Suzuki,
media, Langmuir 33 (2017) 9307–9313. K. Hirata, Y. Hijikata, M. Ito, H. Masuda, CO2 reduction promoted by imidazole
[47] Y. Hori, Electrochemical co2 reduction on metal electrodes, in: C.G. Vayenas, R. supported on a phosphonium-type ionic-liquid-modified Au electrode at a low
E. White, M.E. Gamboa-Aldeco (Eds.), Modern aspects of electrochemistry, overpotential, ACS Catal. 8 (2018) 1990–2000.
Springer, New York, New York, NY, 2008, pp. 89–189. [75] X. Zhang, Y. Zhao, S. Hu, M.E. Gliege, Y. Liu, R. Liu, L. Scudiero, Y. Hu, S. Ha,
[48] Y. Chen, C.W. Li, M.W. Kanan, Aqueous CO2 reduction at very low overpotential Electrochemical reduction of carbon dioxide to formic acid in ionic liquid [EMIM]
on oxide-derived Au nanoparticles, J. Am. Chem. Soc. 134 (2012) 19969–19972. [N(CN)2]/water system, Electrochim. Acta 247 (2017) 281–287.
[49] M. Dunwell, Q. Lu, J.M. Heyes, J. Rosen, J.G. Chen, Y. Yan, F. Jiao, B. Xu, The [76] W. Lu, B. Jia, B. Cui, Y. Zhang, K. Yao, Y. Zhao, J. Wang, Efficient
central role of bicarbonate in the electrochemical reduction of carbon dioxide on photoelectrochemical reduction of carbon dioxide to formic acid: a functionalized
gold, J. Am. Chem. Soc. 139 (2017) 3774–3783. ionic liquid as an absorbent and electrolyte, Angew. Chem. Int. Ed. 56 (2017)
[50] O. Gutiérrez-Sánchez, N. Daems, M. Bulut, D. Pant, T. Breugelmans, Effects of 11851–11854.
benzyl-functionalized cationic surfactants on the inhibition of the hydrogen [77] X. Luo, Y. Guo, F. Ding, H. Zhao, G. Cui, H. Li, C. Wang, Significant improvements
evolution reaction in CO2 reduction systems, ACS Appl. Mater. Interfaces 13 in CO2 capture by pyridine-containing anion-functionalized ionic liquids through
(2021) 56205–56216. multiple-site cooperative interactions, Angew. Chem. Int. Ed. 53 (2014)
[51] E.W. Lees, M. Goldman, A.G. Fink, D.J. Dvorak, D.A. Salvatore, Z. Zhang, N.W. 7053–7057.
X. Loo, C.P. Berlinguette, Electrodes designed for converting bicarbonate into CO, [78] N. Huang, P. Wang, D. Jiang, Covalent organic frameworks: a materials platform
ACS Energy Lett. 5 (2020) 2165–2173. for structural and functional designs, Nat. Rev. Mater. 1 (2016) 16068.
[52] Y.C. Li, Z. Yan, J. Hitt, R. Wycisk, P.N. Pintauro, T.E. Mallouk, Bipolar membranes [79] R.-B. Lin, B. Chen, Reducing CO2 with stable covalent organic frameworks, Joule
inhibit product crossover in CO2 electrolysis cells, Adv. Sustain. Syst. 2 (2018) 2 (2018) 1030–1032.
1700187. [80] Y. Zeng, R. Zou, Y. Zhao, Covalent organic frameworks for CO2 capture, Adv.
[53] J. Luo, D.A. Vermaas, D. Bi, A. Hagfeldt, W.A. Smith, M. Grätzel, Bipolar Mater. 28 (2016) 2855–2873.
membrane-assisted solar water splitting in optimal pH, Adv. Energy Mater. 6 [81] C.-Y. Lin, D. Zhang, Z. Zhao, Z. Xia, Covalent organic framework electrocatalysts
(2016) 1600100. for clean energy conversion, Adv. Mater. 30 (2018) 1703646.
[54] J.A. Rabinowitz, M.W. Kanan, The future of low-temperature carbon dioxide [82] S. Lin, C.S. Diercks, Y.-B. Zhang, N. Kornienko, E.M. Nichols, Y. Zhao, A.R. Paris,
electrolysis depends on solving one basic problem, Nat. Commun. 11 (2020) D. Kim, P. Yang, O.M. Yaghi, C.J. Chang, Covalent organic frameworks
5231. comprising cobalt porphyrins for catalytic CO2 reduction in water, Science 349
[55] Z. Zhang, E.W. Lees, S. Ren, B.A.W. Mowbray, A. Huang, C.P. Berlinguette, (2015) 1208–1213.
Conversion of reactive carbon solutions into CO at low voltage and high carbon [83] H. Liu, J. Chu, Z. Yin, X. Cai, L. Zhuang, H. Deng, Covalent organic frameworks
efficiency, ACS Cent. Sci. 8 (2022) 749–755. linked by amine bonding for concerted electrochemical reduction of CO2, Chem 4
[56] E.W. Lees, B.A.W. Mowbray, F.G.L. Parlane, C.P. Berlinguette, Gas diffusion (2018) 1696–1709.
electrodes and membranes for CO2 reduction electrolysers, Nat. Rev. Mater. 7 [84] R.-P. Ye, Q. Li, W. Gong, T. Wang, J.J. Razink, L. Lin, Y.-Y. Qin, Z. Zhou,
(2022) 55–64. H. Adidharma, J. Tang, A.G. Russell, M. Fan, Y.-G. Yao, High-performance of
[57] A. Reyes, R.P. Jansonius, B.A.W. Mowbray, Y. Cao, D.G. Wheeler, J. Chau, D. nanostructured Ni/CeO2 catalyst on CO2 methanation, Appl. Catal., B 268 (2020),
J. Dvorak, C.P. Berlinguette, Managing hydration at the cathode enables efficient 118474.
CO2 electrolysis at commercially relevant current densities, ACS Energy Lett. 5 [85] J.A. Mendoza-Nieto, Y. Duan, H. Pfeiffer, Alkaline zirconates as effective
(2020) 1612–1618. materials for hydrogen production through consecutive carbon dioxide capture
[58] M.E. Leonard, L.E. Clarke, A. Forner-Cuenca, S.M. Brown, F.R. Brushett, and conversion in methane dry reforming, Appl. Catal., B 238 (2018) 576–585.
Investigating electrode flooding in a flowing electrolyte, gas-fed carbon dioxide [86] W.-H. Chen, C.-Y. Chen, Water gas shift reaction for hydrogen production and
electrolyzer, ChemSusChem 13 (2020) 400–411. carbon dioxide capture: a review, Appl. Energ. 258 (2020), 114078.
[59] E.W. Lees, B.A.W. Mowbray, D.A. Salvatore, G.L. Simpson, D.J. Dvorak, S. Ren, [87] Y.A. Criado, B. Arias, J.C. Abanades, Calcium looping CO2 capture system for
J. Chau, K.L. Milton, C.P. Berlinguette, Linking gas diffusion electrode back-up power plants, Energy Environ. Sci. 10 (2017) 1994–2004.
composition to CO2 reduction in a flow cell, J. Mater. Chem. A 8 (2020) [88] J. Luis Míguez, J. Porteiro, R. Pérez-Orozco, D. Patiño, S. Rodríguez, Evolution of
19493–19501. CO2 capture technology between 2007 and 2017 through the study of patent
[60] B.A.W. Mowbray, D.J. Dvorak, N. Taherimakhsousi, C.P. Berlinguette, How activity, Appl. Energ. 211 (2018) 1282–1296.
catalyst dispersion solvents affect CO2 electrolyzer gas diffusion electrodes, [89] J. Chen, Z. Cai, X. Chen, X. Zheng, Y. Zheng, Facile synthesis of ordered
Energ. Fuel 35 (2021) 19178–19184. mesoporous CaO-ZrO2 composite with mild conditions, Mater. Lett. 168 (2016)
[61] Z. Zhang, E.W. Lees, F. Habibzadeh, D.A. Salvatore, S. Ren, G.L. Simpson, D. 214–217.
G. Wheeler, A. Liu, C.P. Berlinguette, Porous metal electrodes enable efficient [90] S.M. Kim, P.M. Abdala, M. Broda, D. Hosseini, C. Copéret, C. Müller, Integrated
electrolysis of carbon capture solutions, Energy Environ. Sci. 15 (2022) 705–713. CO2 capture and conversion as an efficient process for fuels from greenhouse
[62] Z. Zhang, L. Melo, R.P. Jansonius, F. Habibzadeh, E.R. Grant, C.P. Berlinguette, gases, ACS Catal. 8 (2018) 2815–2823.
pH matters when reducing CO2 in an electrochemical flow cell, ACS Energy Lett. [91] H. Sun, Y. Li, X. Yan, J. Zhao, Z. Wang, Thermochemical energy storage
5 (2020) 3101–3107. performance of Al2O3/CeO2 co-doped CaO-based material under high
[63] T. Li, E.W. Lees, Z. Zhang, C.P. Berlinguette, Conversion of bicarbonate to formate carbonation pressure, Appl. Energ. 263 (2020), 114650.
in an electrochemical flow reactor, ACS Energy Lett. 5 (2020) 2624–2630. [92] A. Armutlulu, M.A. Naeem, H.-J. Liu, S.M. Kim, A. Kierzkowska, A. Fedorov, C.
[64] M. Spichiger-Ulmann, J. Augustynski, Electrochemical reduction of bicarbonate R. Müller, Multishelled CaO microspheres stabilized by atomic layer deposition of
ions at a bright palladium cathode, J. Chem. Soc., Faraday Trans. 1 (81) (1985) Al2O3 for enhanced CO2 capture performance, Adv. Mater. 29 (2017) 1702896.
713–716. [93] C. Chi, Y. Li, W. Zhang, Z. Wang, Synthesis of a hollow microtubular Ca/Al
[65] N. Sreekanth, K.L. Phani, Selective reduction of CO2 to formate through sorbent with high CO2 uptake by hard templating, Appl. Energ. 251 (2019),
bicarbonate reduction on metal electrodes: new insights gained from SG/TC mode 113382.
of SECM, Chem. Commun. 50 (2014) 11143–11146. [94] M. Broda, C.R. Müller, Sol–gel-derived, CaO-based, ZrO2-stabilized CO2 sorbents,
[66] J.F. Andre, M.S. Wrighton, Electrostatic binding of bicarbonate and formate in Fuel 127 (2014) 94–100.
viologen-based redox polymers: importance in catalytic reduction of bicarbonate [95] A. Al-Mamoori, H. Thakkar, X. Li, A.A. Rownaghi, F. Rezaei, Development of
to formate, Inorg. Chem. 24 (1985) 4288–4292. potassium- and sodium-promoted CaO adsorbents for CO2 capture at high
temperatures, Ind. Eng. Chem. Res. 56 (2017) 8292–8300.
16
[96] J. Phromprasit, J. Powell, S. Assabumrungrat, Metals (Mg, Sr and Al) modified [123] S. Rönsch, J. Schneider, S. Matthischke, M. Schlüter, M. Götz, J. Lefebvre,
CaO based sorbent for CO2 sorption/desorption stability in fixed bed reactor for P. Prabhakaran, S. Bajohr, Review on methanation–from fundamentals to current
high temperature application, Chem. Eng. J. 284 (2016) 1212–1223. projects, Fuel 166 (2016) 276–296.
[97] M.A. Naeem, A. Armutlulu, Q. Imtiaz, F. Donat, R. Schäublin, A. Kierzkowska, C. [124] M.S. Duyar, M.A.A. Treviño, R.J. Farrauto, Dual function materials for CO2
R. Müller, Optimization of the structural characteristics of CaO and its effective capture and conversion using renewable H2, Appl. Catal., B 168–169 (2015)
stabilization yield high-capacity CO2 sorbents, Nat. Commun. 9 (2018) 2408. 370–376.
[98] M.D. Porosoff, B. Yan, J.G. Chen, Catalytic reduction of CO2 by H2 for synthesis of [125] L.-P. Merkouri, T. Ramirez Reina, M.S. Duyar, Feasibility of switchable dual
CO, methanol and hydrocarbons: challenges and opportunities, Energy Environ. function materials as a flexible technology for CO2 capture and utilisation and
Sci. 9 (2016) 62–73. evidence of passive direct air capture, Nanoscale 14 (2022) 12620–12637.
[99] S. Kattel, P. Liu, J.G. Chen, Tuning selectivity of CO2 hydrogenation reactions at [126] M.A. Arellano-Treviño, Z. He, M.C. Libby, R.J. Farrauto, Catalysts and adsorbents
the metal/oxide interface, J. Am. Chem. Soc. 139 (2017) 9739–9754. for CO2 capture and conversion with dual function materials: limitations of Ni-
[100] A. Ranjbar, A. Irankhah, S.F. Aghamiri, Reverse water gas shift reaction and CO2 containing DFMs for flue gas applications, J. CO2 Util. 31 (2019) 143–151.
mitigation: nanocrystalline MgO as a support for nickel based catalysts, [127] L. Proaño, E. Tello, M.A. Arellano-Trevino, S. Wang, R.J. Farrauto, M. Cobo, In-
J. Environ. Chem. Eng. 6 (2018) 4945–4952. situ DRIFTS study of two-step CO2 capture and catalytic methanation over
[101] X. Su, X. Yang, B. Zhao, Y. Huang, Designing of highly selective and high- Ru,“Na2O”/Al2O3 dual functional material, Appl. Surf. Sci. 479 (2019) 25–30.
temperature endurable RWGS heterogeneous catalysts: recent advances and the [128] W. Wei, G. Jinlong, Methanation of carbon dioxide: an overview, Front. Chem.
future directions, J. Energy Chem. 26 (2017) 854–867. Sci. Eng. 5 (2011) 2–10.
[102] B. Shao, G. Hu, K.A.M. Alkebsi, G. Ye, X. Lin, W. Du, J. Hu, M. Wang, H. Liu, [129] M.A. Arellano-Treviño, N. Kanani, C.W. Jeong-Potter, R.J. Farrauto, Bimetallic
F. Qian, Heterojunction-redox catalysts of FexCoyMg10CaO for high-temperature catalysts for CO2 capture and hydrogenation at simulated flue gas conditions,
CO2 capture and in situ conversion in the context of green manufacturing, Energy Chem. Eng. J. 375 (2019), 121953.
Environ. Sci. 14 (2021) 2291–2301. [130] H. Sun, Y. Zhang, S. Guan, J. Huang, C. Wu, Direct and highly selective
[103] S.M. Kim, P.M. Abdala, T. Margossian, D. Hosseini, L. Foppa, A. Armutlulu, conversion of captured CO2 into methane through integrated carbon capture and
W. van Beek, A. Comas-Vives, C. Copéret, C. Müller, Cooperativity and dynamics utilization over dual functional materials, J. CO2 Util. 38 (2020) 262–272.
increase the performance of NiFe dry reforming catalysts, J. Am. Chem. Soc. 139 [131] Q. Zheng, R. Farrauto, A. Chau Nguyen, Adsorption and methanation of flue gas
(2017) 1937–1949. CO2 with dual functional catalytic materials: a parametric study, Ind. Eng. Chem.
[104] Z. Li, S. Das, P. Hongmanorom, N. Dewangan, M.H. Wai, S. Kawi, Silica-based Res. 55 (2016) 6768–6776.
micro- and mesoporous catalysts for dry reforming of methane, Catal. Sci. [132] S. Wang, R.J. Farrauto, S. Karp, J.H. Jeon, E.T. Schrunk, Parametric, cyclic aging
Technol. 8 (2018) 2763–2778. and characterization studies for CO2 capture from flue gas and catalytic
[105] Z. Li, Q. Lin, M. Li, J. Cao, F. Liu, H. Pan, Z. Wang, S. Kawi, Recent advances in conversion to synthetic natural gas using a dual functional material (DFM), J. CO2
process and catalyst for CO2 reforming of methane, Renew. Sustain. Energy Rev. Util. 27 (2018) 390–397.
134 (2020), 110312. [133] Z. Zhou, N. Sun, B. Wang, Z. Han, S. Cao, D. Hu, T. Zhu, Q. Shen, W. Wei, 2D-
[106] J. Ashok, Y. Kathiraser, M.L. Ang, S. Kawi, Bi-functional hydrotalcite-derived layered Ni-MgO-Al2O3 nanosheets for integrated capture and methanation of CO2,
NiO–CaO–Al2O3 catalysts for steam reforming of biomass and/or tar model ChemSusChem 13 (2020) 360–368.
compound at low steam-to-carbon conditions, Appl. Catal., B 172–173 (2015) [134] A. Bermejo-López, B. Pereda-Ayo, J.A. González-Marcos, J.R. González-Velasco,
116–128. Ni loading effects on dual function materials for capture and in-situ conversion of
[107] I.S. Omodolor, H.O. Otor, J.A. Andonegui, B.J. Allen, A.C. Alba-Rubio, Dual- CO2 to CH4 using CaO or Na2CO3, J. CO2 Util. 34 (2019) 576–587.
function materials for CO2 capture and conversion: a review, Ind. Eng. Chem. Res. [135] F. Wang, S. He, H. Chen, B. Wang, L. Zheng, M. Wei, D.G. Evans, X. Duan, Active
59 (2020) 17612–17631. site dependent reaction mechanism over Ru/CeO2 catalyst toward CO2
[108] Z. Li, Z. Wang, S. Kawi, Sintering and coke resistant core/yolk shell catalyst for methanation, J. Am. Chem. Soc. 138 (2016) 6298–6305.
hydrocarbon reforming, ChemCatChem 11 (2018) 202–224. [136] Y. Tang, Y. Wei, Z. Wang, S. Zhang, Y. Li, L. Nguyen, Y. Li, Y. Zhou, W. Shen, F.
[109] S. Tian, F. Yan, Z. Zhang, J. Jiang, Calcium-looping reforming of methane realizes F. Tao, P. Hu, Synergy of single-atom Ni1 and Ru1 sites on CeO2 for dry reforming
in situ CO2 utilization with improved energy efficiency, Sci. Adv. 5 (2019) of CH4, J. Am. Chem. Soc. 141 (2019) 7283–7293.
eaav5077. [137] H. Sun, Y. Zhang, C. Wang, M.A. Isaacs, A.I. Osman, Y. Wang, D. Rooney,
[110] Y. Chen, M. Li, Z. Li, F. Liu, G. Song, S. Kawi, Efficient syngas production via CO2 Y. Wang, Z. Yan, C.M.A. Parlett, F. Wang, C. Wu, Integrated carbon capture and
reforming and electroreduction reactions through catalyst design, Energy utilization: synergistic catalysis between highly dispersed Ni clusters and ceria
Convers. Manag. 265 (2022), 115744. oxygen vacancies, Chem. Eng. J. 437 (2022), 135394.
[111] G. Wang, Y. Guo, J. Yu, F. Liu, J. Sun, X. Wang, T. Wang, C. Zhao, Ni-CaO dual [138] F.-Q. Liu, W.-H. Li, B.-C. Liu, R.-X. Li, Synthesis, characterization, and high
function materials prepared by different synthetic modes for integrated CO2 temperature CO2 capture of new CaO based hollow sphere sorbents, J. Mater.
capture and conversion, Chem. Eng. J. 428 (2022), 132110. Chem. A 1 (2013) 8037–8044.
[112] M. Li, C. Ye, Z. Li, Q. Lin, J. Cao, F. Liu, G. Song, S. Kawi, 1D confined materials [139] H. Sun, Y. Wang, S. Xu, A.I. Osman, G. Stenning, J. Han, S. Sun, D. Rooney, P.
synthesized via a coating method for thermal catalysis and energy storage T. Williams, F. Wang, C. Wu, Understanding the interaction between active sites
applications, J. Mater. Chem. A 10 (2022) 6330–6350. and sorbents during the integrated carbon capture and utilization process, Fuel
[113] M. Li, Z. Li, Q. Lin, J. Cao, F. Liu, S. Kawi, Synthesis strategies of carbon nanotube 286 (2021), 119308.
supported and confined catalysts for thermal catalysis, Chem. Eng. J. 431 (2022), [140] F. Kosaka, Y. Liu, S.-Y. Chen, T. Mochizuki, H. Takagi, A. Urakawa, K. Kuramoto,
133970. Enhanced activity of integrated CO2 capture and reduction to CH4 under
[114] Z.X. Law, Y.-T. Pan, D.-H. Tsai, Calcium looping of CO2 capture coupled to syngas pressurized conditions toward atmospheric CO2 utilization, ACS Sustain. Chem.
production using Ni-CaO-based dual functional material, Fuel 328 (2022), Eng. 9 (2021) 3452–3463.
125202. [141] A. Bermejo-López, B. Pereda-Ayo, J.A. González-Marcos, J.R. González-Velasco,
[115] H. Sun, J. Wang, J. Zhao, B. Shen, J. Shi, J. Huang, C. Wu, Dual functional Mechanism of the CO2 storage and in situ hydrogenation to CH4. Temperature
catalytic materials of Ni over Ce-modified CaO sorbents for integrated CO2 and adsorbent loading effects over Ru-CaO/Al2O3 and Ru-Na2CO3/Al2O3
capture and conversion, Appl. Catal., B 244 (2019) 63–75. catalysts, Appl. Catal., B 256 (2019), 117845.
[116] J. Hu, P. Hongmanorom, V.V. Galvita, Z. Li, S. Kawi, Bifunctional Ni-Ca based [142] A. Bermejo-López, B. Pereda-Ayo, J.A. González-Marcos, J.R. González-Velasco,
material for integrated CO2 capture and conversion via calcium-looping dry Alternate cycles of CO2 storage and in situ hydrogenation to CH4 on Ni–Na2CO3/
reforming, Appl. Catal., B 284 (2021), 119734. Al2O3: influence of promoter addition and calcination temperature, Sustain.
[117] S.M. Hashemi, D. Karami, N. Mahinpey, Solution combustion synthesis of Energ. Fuels 5 (2021) 1194–1210.
zirconia-stabilized calcium oxide sorbents for CO2 capture, Fuel 269 (2020), [143] C.H. Lee, S.W. Choi, H.J. Yoon, H.J. Kwon, H.C. Lee, S.G. Jeon, K.B. Lee, Na2CO3-
117432. doped CaO-based high-temperature CO2 sorbent and its sorption kinetics, Chem.
[118] S. Das, J. Ashok, Z. Bian, N. Dewangan, M.H. Wai, Y. Du, A. Borgna, K. Hidajat, Eng. J. 352 (2018) 103–109.
S. Kawi, Silica–ceria sandwiched Ni core–shell catalyst for low temperature dry [144] A. Bermejo-López, B. Pereda-Ayo, J.A. Onrubia-Calvo, J.A. González-Marcos, J.
reforming of biogas: coke resistance and mechanistic insights, Appl. Catal., B 230 R. González-Velasco, Tuning basicity of dual function materials widens operation
(2018) 220–236. temperature window for efficient CO2 adsorption and hydrogenation to CH4,
[119] Y. Zhao, Y. Li, B. Jin, Z. Liang, Layered double hydroxide derived bifunctional Ca- J. CO2 Util. 58 (2022), 101922.
Fe-Mg material for integrated CO2 capture and utilization via chemical looping [145] T. Harada, T.A. Hatton, Colloidal nanoclusters of MgO coated with alkali metal
strategy, Chem. Eng. J. 431 (2022), 133826. nitrates/nitrites for rapid, high capacity CO2 capture at moderate temperature,
[120] S. Sun, Z. Lv, Y. Qiao, C. Qin, S. Xu, C. Wu, Integrated CO2 capture and utilization Chem. Mater. 27 (2015) 8153–8161.
with CaO-alone for high purity syngas production, Carbon Capture Sci. Technol. 1 [146] S. Sun, H. Sun, S. Guan, S. Xu, C. Wu, Integrated CO2 capture and methanation on
(2021), 100001. Ru/CeO2-MgO combined materials: morphology effect from CeO2 support, Fuel
[121] X. Ma, X. Li, H. Cui, W. Zhang, Z. Cheng, Z. Zhou, Metal oxide-doped Ni/CaO 317 (2022), 123420.
dual-function materials for integrated CO2 capture and conversion: performance [147] S. Akamaru, T. Shimazaki, M. Kubo, T. Abe, Density functional theory analysis of
and mechanism, AlChE J. (2021), e17520. methanation reaction of CO2 on Ru nanoparticle supported on TiO2 (101), Appl.
[122] T. Sasayama, F. Kosaka, Y. Liu, T. Yamaguchi, S.-Y. Chen, T. Mochizuki, Catal. A-Gen. 470 (2014) 405–411.
A. Urakawa, K. Kuramoto, Integrated CO2 capture and selective conversion to [148] X. Wang, Y. Hong, H. Shi, J. Szanyi, Kinetic modeling and transient DRIFTS–MS
syngas using transition-metal-free Na/Al2O3 dual-function material, J. CO2 Util. studies of CO2 methanation over Ru/Al2O3 catalysts, J. Catal. 343 (2016)
60 (2022), 102049. 185–195.
17
[149] L. Jiao, J.Y.R. Seow, W.S. Skinner, Z.U. Wang, H.-L. Jiang, Metal–organic [157] J.R. Khusnutdinova, J.A. Garg, D. Milstein, Combining low-pressure CO2 capture
frameworks: structures and functional applications, Mater. Today 27 (2019) and hydrogenation to form methanol, ACS Catal. 5 (2015) 2416–2422.
43–68. [158] S. Kar, R. Sen, A. Goeppert, G.K.S. Prakash, Integrative CO2 capture and
[150] S. Yuan, L. Feng, K. Wang, J. Pang, M. Bosch, C. Lollar, Y. Sun, J. Qin, X. Yang, hydrogenation to methanol with reusable catalyst and amine: toward a carbon
P. Zhang, Q. Wang, L. Zou, Y. Zhang, L. Zhang, Y. Fang, J. Li, H.C. Zhou, Stable neutral methanol economy, J. Am. Chem. Soc. 140 (2018) 1580–1583.
metal-organic frameworks: design, synthesis, and applications, Adv. Mater. 30 [159] S. Kar, A. Goeppert, G.K.S. Prakash, Integrated CO2 capture and conversion to
(2018) 1704303. formate and methanol: connecting two threads, Acc. Chem. Res. 52 (2019)
[151] T. Zurrer, K. Wong, J. Horlyck, E.C. Lovell, J. Wright, N.M. Bedford, Z. Han, 2892–2903.
K. Liang, J. Scott, R. Amal, Mixed-metal MOF-74 templated catalysts for efficient [160] C.M. Jens, L. Müller, K. Leonhard, A. Bardow, To integrate or not to
carbon dioxide capture and methanation, Adv. Funct. Mater. 31 (2021) 2007624. integrate—techno-economic and life cycle assessment of CO2 capture and
[152] B. Saccoccia, A.M. Bohnsack, N.W. Waggoner, K.H. Cho, J.S. Lee, D.-Y. Hong, V. conversion to methyl formate using methanol, ACS Sustain. Chem. Eng. (2019).
M. Lynch, J.-S. Chang, S.M. Humphrey, Separation of p-divinylbenzene by [161] M. Jouny, W. Luc, F. Jiao, General techno-economic analysis of CO2 electrolysis
selective room-temperature adsorption inside Mg-CUK-1 prepared by aqueous systems, Ind. Eng. Chem. Res. 57 (2018) 2165–2177.
microwave synthesis, Angew. Chem. Int. Ed. 54 (2015) 5394–5398. [162] D.A.C. Beck, J.M. Carothers, V.R. Subramanian, J. Pfaendtner, Data science:
[153] E. Sánchez-González, P.G.M. Mileo, M. Sagastuy-Breña, J.R. Álvarez, J. accelerating innovation and discovery in chemical engineering, AlChE J. 62
E. Reynolds, A. Villarreal, A. Gutiérrez-Alejandre, J. Ramírez, J. Balmaseda, (2016) 1402–1416.
E. González-Zamora, G. Maurin, S.M. Humphrey, I.A. Ibarra, Highly reversible [163] P.G. Boyd, A. Chidambaram, E. García-Díez, C.P. Ireland, T.D. Daff, R. Bounds,
sorption of H2S and CO2 by an environmentally friendly Mg-based MOF, J. Mater. A. Gładysiak, P. Schouwink, S.M. Moosavi, M.M. Maroto-Valer, J.A. Reimer, J.A.
Chem. A 6 (2018) 16900–16909. R. Navarro, T.K. Woo, S. Garcia, K.C. Stylianou, B. Smit, Data-driven design of
[154] T. Zurrer, E. Lovell, Z. Han, K. Liang, J. Scott, R. Amal, Bimetallic RuNi-decorated metal–organic frameworks for wet flue gas CO2 capture, Nature 576 (2019)
Mg-CUK-1 for oxygen-tolerant carbon dioxide capture and conversion to 253–256.
methane, Nanoscale 14 (2022) 15669–15678. [164] M. Zhong, K. Tran, Y. Min, C. Wang, Z. Wang, C.-T. Dinh, P. De Luna, Z. Yu, A.
[155] Y.-N. Li, L.-N. He, A.-H. Liu, X.-D. Lang, Z.-Z. Yang, B. Yu, C.-R. Luan, In situ S. Rasouli, P. Brodersen, S. Sun, O. Voznyy, C.-S. Tan, M. Askerka, F. Che, M. Liu,
hydrogenation of captured CO2 to formate with polyethyleneimine and Rh/ A. Seifitokaldani, Y. Pang, S.-C. Lo, A. Ip, Z. Ulissi, E.H. Sargent, Accelerated
monophosphine system, Green. Chem. 15 (2013) 2825–2829. discovery of CO2 electrocatalysts using active machine learning, Nature 581
[156] S. Kar, A. Goeppert, V. Galvan, R. Chowdhury, J. Olah, G.K.S. Prakash, A carbon- (2020) 178–183.
neutral CO2 capture, conversion, and utilization cycle with low-temperature
regeneration of sodium hydroxide, J. Am. Chem. Soc. 140 (2018) 16873–16876.
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Journal of CO2 Utilization 72 (2023) 102493

Contents lists available at ScienceDirect

Journal of CO2 Utilization

Sustainable CO2 management through integrated CO2 capture

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