ADVANCES IN ATMOSPHERIC SCIENCES, VOL.

39, AUGUST 2022, 1252–1270

• Review •

Frontiers of CO2 Capture and Utilization (CCU)

towards Carbon Neutrality※
Lingyun ZHANG1,2, Yanfang SONG1, Jialin SHI1, Qun SHEN1, Deng HU1, Qiang GAO1, Wei CHEN1,
Kien-Woh KOW2, Chengheng PANG3,4, Nannan SUN*1, and Wei WEI*1,5

1CAS Key Laboratory of Low-Carbon Conversion Science & Engineering, Shanghai Advanced Research Institute,
Chinese Academy of Sciences, Shanghai 201210, China
2Department of Chemical and Environmental Engineering, Faculty of Science and Engineering,
University of Nottingham Ningbo China, Ningbo 315100, China
3Key Laboratory for Carbonaceous Wastes Processing and Process Intensification Research of Zhejiang Province,
University of Nottingham Ningbo China, Ningbo 315100, China
4New Materials Institute, the University of Nottingham Ningbo China, Ningbo 315100, China
5School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China

(Received 6 January 2022; revised 18 March 2022; accepted 12 April 2022)

ABSTRACT
CO2 capture, utilization, and storage (CCUS) technology is a rare option for the large-scale use of fossil fuels in a low-
carbon way, which will definitely play a part in the journey towards carbon neutrality. Within the CCUS nexus, CCU is
especially interesting because these processes will establish a new “atmosphere-to-atmosphere ” carbon cycle and thus
indirectly offer huge potential in carbon reduction. This study focuses on the new positioning of CCUS in the carbon
neutrality scenario and aims to identify potential cutting-edge/disruptive CCU technologies that may find important
application opportunities during the decarbonization of the energy and industrial system. To this end, direct air capture
(DAC), flexible metal-framework materials (MOFs) for CO2 capture, integrated CO2 capture and conversion (ICCC), and
electrocatalytic CO2 reduction (ECR) were selected, and their general introduction, the importance to carbon neutrality, and
most up-to-date research progress are summarized.
Key words: carbon neutrality, carbon reduction, decarbonization, CO2, CCU

Citation: Zhang, L. Y., and Coauthors, 2022: Frontiers of CO2 capture and utilization (CCU) towards carbon neutrality.
Adv. Atmos. Sci., 39(8), 1252−1270, https://doi.org/10.1007/s00376-022-1467-x.
Article Highlights:
• CCU will play an important role for carbon neutrality by establishing a new “atmosphere-to-atmosphere” carbon cycle.
• Under the carbon neutrality scenario, several cutting-edge/disruptive CCU technologies will gain extended application
opportunities.
• Progresses and future perspectives for four cutting-edge/disruptive CCU technologies are summarized.

1. Introduction sive use has been an important supporting factor for the con-
tinuous progress of human society, but it also has resulted in
1.1. Carbon neutrality a huge amount of CO2 emissions, which has led to serious
problems such as the greenhouse effect and climate change
The history of human civilization is accompanied by (IPCC, 2014). Mitigating climate change has become one of
the exploration and utilization of fossil energies. Their exten- the most important themes in the world today, and CO2 reduc-
tion is at the central part of this issue. In this context, many
※ This paper is a contribution to the special issue on Carbon Neu- countries and regions have put forward “carbon neutrality”
trality: Important Roles of Renewable Energies, Carbon Sinks, commitments, and carbon neutrality is becoming a new bench-
NETs, and non-CO2 GHGs. mark for evaluating countries’ ambitions and actions to
* Corresponding authors: Nannan SUN, Wei WEI reduce carbon emissions (Energy & Climate Intelligence
Emails: sunnn@sari.ac.cn, weiwei@sari.ac.cn Unit, 2021).

© The Author(s) 2022. This article is published with open access at link.springer.com.
AUGUST 2022 ZHANG ET AL. 1253

Carbon peaking and neutrality correspond to major of CCUS has changed significantly. CCUS technology is
changes in production and lifestyles, and revolutionary adjust- the only option for the low carbon utilization of fossil energies
ments must be made to the existing energy structure and on a large scale, which is of great significance to energy secu-
industrial system. In this process, a new energy system charac- rity. Meanwhile, CCUS technology is a necessary solution
terized by a high proportion of renewables will undoubtedly for the decarbonization of industries that have difficulty reduc-
make decisive societal and economic contributions through ing their emissions, and it is the major option to solve the
decarbonization (IEA, 2020a). However, the reliability of problem of unavoidable “process emissions ” in industries
renewables needs further verification due to their intermit- such as steel, chemical, cement, and non-ferrous metals.
tency and high dependency on large-scale energy storage tech- CCUS technology is also the main source for the necessary
nology. Therefore, fossil energy will inevitably exist in the carbon element under the carbon neutralization scenario,
energy system in a certain proportion (5%–10%) for a long which avoids the massive exploitation and utilization of fossil
time (IEA, 2020a; Qu et al., 2020). On one hand, fossil resources. Last but not least, the negative emission effect
energy can act as a “stabilizer” by balancing the volatility of achieved by the coupling of CCUS and renewables is a guar-
renewable energy. At the same time, fossil energy is very antee for achieving the carbon neutrality target; which is
important to ensure a continuous supply of high-quality impossible to achieve by source reduction or energy-saving
energy. On the other hand, high-carbon industries such as approaches alone.
steel, chemicals, and cement are important pillars of the mod- CCUS can be further divided into CCS and CCU accord-
ern economy, but the technological processes in these indus- ing to their different approaches of CO2 abatement. In gen-
trial sectors are relatively mature, with high technological eral, CCS can provide huge capacity for direct CO2 reduction
inertia and high replacement costs. Low-carbon transforma- as suitable reservoir volumes for CO2 storage are more than
tion and structural upgrading need to be carried out in an enough to accommodate all the potential emissions. The
orderly manner, and the high-carbon characteristics of these CCU pathway, on the other hand, is significantly less efficient
industries will not change in the short term. Therefore, the for direct reduction. This is because for most CCU technolo-
use of a certain proportion of fossil energy and fossil gies, any consumed CO2 by the process will be re-released
resources will play an irreplaceable role in ensuring energy at the end of the product life-cycle (Stevenson, 2019). In
security and maintaining the integrity of the industrial chain. fact, the importance of CCU is its great potential for indirect
However, their use will inevitably lead to a certain amount reduction of CO2 emissions by avoiding the use of fossil car-
of carbon emissions, which cannot be fully absorbed bon. As such, a new “atmosphere-to-atmosphere ” carbon
through the natural carbon sinks. As a result, artificial carbon cycle can be established, while the traditional “lithosphere-
sink technology, namely CO2 capture, utilization, and storage to-atmosphere ” mode can be largely replaced (Hepburn et
(CCUS), will act as a safeguard towards carbon neutrality al., 2019). As such, the overall CO2 reduction capacity of
(IEA, 2020b). CCU is high enough to apply considerable impact on carbon
1.2. CO2 capture, utilization, and storage (CCUS) neutrality, and it is likely to create economic benefits as
well.
CCUS is a major technological option for the end treat- Nevertheless, under the carbon-neutral scenario, routes
ment of CO2 and includes three technical steps of CO2 cap- for future CCU R&D may vary significantly, but one of the
ture, CO2 utilization, and CO2 storage. CO2 capture is key features is that the necessity and application potential of
mainly used to separate and enrich CO2 from various emission some cutting-edge/disruptive CCUS technologies will
sources and even the air, and it is the beginning of the entire greatly increase. In response to the above trends, this paper
CCUS chain. CO2 utilization uses CO2 as a raw material or summarizes several cutting-edge/disruptive CCU technolo-
working medium by chemical, biological, or geological meth-
gies that are expected to play important roles in the carbon
ods, and completes carbon emission reduction at the same
neutralization process from different dimensions. The latest
time. CO2 storage injects CO2 into a certain geological envi-
progress and possible future trends are discussed to provide
ronment and isolates the CO2 from the atmosphere for a
a reference for the research layout in the CCU field.
very long period during which the CO2 may be fixed by car-
bonation reaction with underground minerals.
CCUS is a recognized technology that can achieve 2. Direct air capture (DAC) and its
large-scale emission reductions. The International Energy indispensable carbon-negative feature for
Agency (IEA) predicted that to achieve global carbon neutral-
carbon neutrality
ity by 2070, CCUS technology will not only contribute 15%
of emission reductions but also provide inevitable solutions Direct air capture (DAC), as indicated by its name, is a
to cement, steel, chemical, and long-distance transport indus- process that captures CO2 from the ambient air. This technol-
tries (IEA, 2020b). The IPCC special report “Global warming ogy is appealing because, to some extent, it de-couples the
of 1.5°C” pointed out that by 2030 and 2050, global CCUS emission source and carbon sink (i.e., the relative locations
capacity will reach 100–400 million tons yr–1 and 3–6.8 bil- of the emission source and downstream CO2 utilization/stor-
lion tons yr–1, respectively (IPCC, 2018). age sites will not be a necessary concern). Therefore, infras-
Under the new target of carbon neutrality, the positioning tructure and expenditures for long-distance transportation of
1254 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

CO2 can be avoided, resulting in the great potential to cess. At present, most DAC studies and demonstrations
reduce the cost of CO2 abatement. Additionally, DAC have focused on solid adsorbents, and only a few experiments
directly uses air as the upstream source, which is a preferred have used liquid absorbents with alkali metal hydroxide solu-
technology to address mobile emission sources (such as vehi- tion as the main component. The reason is because those
cles) and micro emission sources (such as buildings) (Sanz- solid adsorbents possess obvious advantages in terms of kinet-
Pérez et al., 2016). ics, stability, and environmental footprints (Shi et al., 2020).
DAC delivers its carbon reduction capacity by coupling Physical adsorbents (such as activated carbons, molecu-
with either CO2 conversion or CO2 storage. Firstly, CO2 lar sieves, etc.) are rarely used for DAC, mainly due to their
obtained from DAC can be used as a raw material to replace weak interaction with the CO2 molecules, which leads to
fossil resources to produce carbon-based chemicals. In this extremely low adsorption capacity and selectivity in low
context, the resulting products will be carbon neutral through- CO2 concentration environments (i.e., air). For example,
out their life cycles. Practically, this reshapes the existing Kumar et al. compared the CO2 adsorption performance of
chemical industry, leading to a disruptive impact on the four physical adsorbents and an immobilized organic amine
entire industry and supply chain. Secondly, coupling of sample, which is a typical chemical adsorbent. They found
DAC with CO2 storage has a significant carbon-negative that although the performances of these samples only
effect, and its capacity is huge if large-scale deployment and showed slight differences in 15 vol.% CO2, the CO2 adsorp-
application can be carried out. This offers a solution to the his- tion capacities of physical adsorbents are more than one
torical emissions and meets the demand of “reducing atmo- order of magnitude lower than those of chemical adsorbents
spheric CO2 concentration ” in response to climate change. in DAC conditions (Kumar et al., 2015).
Furthermore, such a carbon-negative effect may also have Compared with physical adsorbents, chemical adsor-
beneficial impacts on the energy and industrial system, pro- bents are more widely used for DAC. Among them, immobi-
moting DAC to become an important part in the new model lized organic amines are a kind of important CO2 chemical
of carbon-neutral social and economic infrastructure adsorbent. The earliest prototype of these adsorbents comes
(Goglio et al., 2020). from the “molecular basket ” material proposed by Song’s
Compared with industrial emission sources, the concen- group (Fig. 1) (Xu et al., 2002; Ma et al., 2009). Then,
tration of CO2 in the air is extremely low, only slightly Sayari’s group (Franchi et al., 2005; Sayari and
higher than 400 ppm. This means that the DAC process is Belmabkhout, 2010) and Jones’ group (Hicks et al., 2008;
very unfavourable in terms of thermodynamics. Therefore, Didas et al., 2015) systematically developed the preparation
it faces great technological challenges in aspects of method of immobilized organic amines, and in-depth studies
absorbents/adsorbents, efficiency, and energy costs. These on their adsorption behaviours and structure-performance rela-
adverse factors often cause the consumption of a large tionship for CO2 capture were performed. Due to the strong
amount of materials and energy, even achieving a level that interaction between these adsorbents and the CO2 molecules,
may offset the CO2 reduction capacity of the DAC process their application in the DAC process has attracted extensive
(Deutz and Bardow, 2021). Overall, the technological matu- attention. For example, Goeppert et al. reported that fumed
rity of DAC is still low, and its application is still in early silica supported poly (ethyleneimine) (PEI) can effectively
infancy. In recent years, related studies have mainly focused adsorb CO2 from the air (Goeppert et al., 2011). In 2011,
on high-performance absorbents/adsorbents, prototype Choi et al. (2011) used 3-aminopropyl trimethoxysilane and
demonstrations, and life cycle assessments. tetraethylorthotitanate modified PEI as the adsorption com-
ponents, which were loaded on porous SiO2, and they found
2.1. Absorbents/adsorbents for DAC that this type of material exhibited great DAC performance
Absorbents and adsorbents are the most important compo- (adsorption capacity > 2 mmol g–1) and the use of modifiers
nents of a DAC technology system, and their performance can significantly improve the stability of PEI, rendering the
directly dictates the overall cost and efficiency of the pro- material with excellent stability (Choi et al., 2011). Keller et

Fig. 1. “Molecular basket” sorbents [Reprinted from (Ma et al., 2009)].

AUGUST 2022 ZHANG ET AL. 1255

al. used carbon nanotubes as a carrier for PEI to prepare a hol- 4’-dioxidobiphenyl-3,3’-dicarboxylate). It was found that dur-
low fibre adsorbent. The adsorption capacity of CO2 ing the adsorption of CO2, there is a process of CO2 insertion
reached 1.07 mmol g–1 under DAC conditions (Keller et al., into the metal-amine bond, so the obtained CO2 adsorption
2018). In addition to the commonly used impregnation isotherm has step-shaped characteristics. This unique
method, immobilization of amines can also be achieved by behaviour makes the material possess a higher working capac-
surface grafting. Although adsorbents prepared in this way ity than other chemical adsorbents (McDonald et al., 2015).
have slightly lower CO2 uptakes under DAC conditions, Through the tunability of MOFs structure and the optimiza-
their overall stability can be significantly improved (Potter tion of external amines, CO2 adsorption capacity, kinetics,
et al., 2017; Sabatino et al., 2021). and regeneration performance under DAC, conditions can
Porous framework materials are a type of functional mate- be further improved (Lee et al., 2014; Liao et al., 2016; Kim
rials developed rapidly in recent years. The structure of et al., 2020b; Martell et al., 2020).
these materials is highly ordered and can be finely character- In recent years, some new adsorption strategies have
ized by various spectroscopic methods, thereby providing also been used for DAC processes. Based on the affinity dif-
new dimensions for studying DAC mechanisms and perfor- ference between materials to CO2 and water, researchers
mance tunning (Custelcean, 2021). For example, by the engi- have proposed the concept of moisture-swing adsorption. In
neering of ligand for metal-organic frameworks (MOFs), this process, the material captures CO2 from air in a dry envi-
Kumar et al. replaced the SiF62− pillar in SIFSIX-3-Ni mate- ronment, while the competitive adsorption of moisture in a
rial with TiF62−, which led to enhanced interaction between wet environment will liberate CO2 molecules from the adsor-
the framework and CO2, and thus the DAC performance of bent surface (Shi et al., 2016; Yang et al., 2018). Inagaki et
the material was effectively improved (Kumar et al., 2017). al. found that the aqueous solution of m-xylylene diamine
Bhatt et al. further explored possible strategies by adjusting (MXDA) can absorb CO2 in the air and generate water-insolu-
the pore size, pore shape, and surface functional groups of ble MXDA·CO2 crystals. After simple filtration and separa-
MOFs, and a CO2 adsorption capacity of 1.30 mmol g–1 tion, heating of MXDA·CO2 can release CO2 and complete
could be achieved at the condition of 400 ppm and 25°C, the regeneration of MXDA. This process avoids the large
which is on a similar level to immobilized amine-based adsor- amount of energy consumption required for the evaporation
bents (Bhatt et al., 2016). It should be noted that although of solvent water in the traditional liquid absorption method
the low-pressure CO2 adsorption performance can be signifi- (Inagaki et al., 2017). Based on a similar strategy, Brethomé
cantly improved through the optimization of MOFs struc- et al. used a cheap and easily available amino acid aqueous
ture, in general, its adsorption mechanism still relies on physi- solution to absorb CO2, and then the CO2 loaded solution fur-
cal interactions, so it is easily affected by competitive adsorp- ther reacted with guanidine compounds to form insoluble car-
tion of moisture. In fact, MOFs can also be used as carriers bonates, which regenerated the amino acids simultaneously,
to prepare amine-based DAC adsorbents (Lu et al., 2013; and then the separated carbonate can be decomposed under
Lee et al., 2014; Liao et al., 2016; Sen et al., 2019), and relatively mild conditions to release CO2 (Brethomé et al.,
under the synergistic effect of multiple functional sites, the 2018).
resulting materials may exhibit excellent DAC performance Table 1 summarizes recent research results on DAC
through several types of new adsorption mechanisms. For adsorbents. Overall, the research and development of DAC
example, McDonald et al. used N, N’-dimethylethylenedi- absorbents/adsorbents still face great challenges. In this
amine (mmen) to functionalize Mg2(dobpdc) (dobpdc4−=4, study, a model was designed to estimate the cost of DAC

Table 1. Summary of research results on DAC sorbents.

Adsorption capacity Temperature Pressure

Reference Sorbents Mechanisms (mg-CO2 g–1) (oC) (bar)
(Kumar et al., 2015) TEPA-SBA-15 chemisorption 158 20 400 ppm
Zeolite 13X physisorption 5.8 20
HKUST-1 physisorption 2.1 20
Mg-MOF-74/ physisorption 40 20
SIFSIX-3-Ni physisorption 58 20
(Goeppert et al., 2011) FS-PEI-33 chemisorption 75 25 400 ppm
(Choi et al., 2011) PEI-silica chemisorption 103 25 400 ppm
A-PEI/silica chemisorption 99 25
T-PEI/silica chemisorption 96 25
(Keller et al., 2018) CNT-PEI chemisorption 47 25 350 ppm
(Bhatt et al., 2016) NbOFFIVE-1-Ni chemisorption 57 25 400 ppm
(McDonald et al., 2015) mmen-Mg2(dobpdc) chemisorption 154 25 1000 ppm
(Kim et al., 2020b) Mg2(dobpdc) (3-4-3) chemisorption 150 90 4000 ppm
1256 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

adsorbents and the corresponding relationship between adsor-

bent performance and its highest allowable cost was studied
(Fig. 2). Based on this model, it is found that if the service
life of an adsorbent is 1000 cycles, its cost must be less than
$1 kg–1. Currently, there are hardly any adsorbents so low in
cost. Increasing adsorbent service life can reduce its highest
allowable cost; with 100 000 cycles, the allowable cost of
MOF (Diamine) materials is the highest, reaching $90 kg–1.
However, the price of MOF material is generally higher
than $10 000 kg–1, and its stability is far from the requirements
(Shi et al., 2020). This work verifies the difficulty of develop-
ing DAC adsorbents from a cost perspective, but it should
be mentioned that recently, several groups have reported sev-
eral CO2 adsorbents with excellent comprehensive perfor-
Fig. 2. Allowable price of DAC adsorbents [Reprinted from
mance, which provides new opportunities for reducing the (Shi et al., 2020)].
cost of DAC technology (Nandi et al., 2015; Yue et al.,
2017; Cavalcanti et al., 2018; Mukherjee et al., 2019; Lin et
al., 2021).
2.2. Prototype demonstrations of DAC
Devices and demonstrations are also major focuses in
the DAC field. This is because the concentration of CO2 in
the air is low, so the gas processing capacity of the DAC pro-
cess is huge, and there is little experience in an engineering
perspective to date. Over the past decade, developed countries
in Europe and America have attached great importance to
the development and application of DAC, and several small-
scale prototypes and demonstrations have been reported,
which has laid an important foundation for the future develop-
ment of DAC technology. Fig. 3. Orca plant from Climeworks [(©climeworks, 2022),
Climeworks, a company based in Switzerland, is the used with permission].
first company in the world that provides customers with
2.3. Life-cycle assessment (LCA) of DAC
CO2 captured from the air. In 2017, the company built the
world’s first commercial DAC device in Switzerland, which At present, there are still some controversies around the
adopted modular design and used 18 adsorption units. An economic and environmental benefits of DAC. Therefore,
overall capture capacity of several hundred tons of CO2 per its full life cycle assessment is also a research hotspot. By
year was achieved. In 2021, Climeworks built its latest Orca applying LCA to the actual operation data, Deutz et al.
plant in Iceland. The Orca plant has a capture capacity of found that the DAC demonstration currently carried out by
4000 t yr–1 (Fig. 3) and is the largest DAC demonstration in Climeworks has already achieved a carbon-negative effect.
the world to date. The captured CO2 is injected 700 m under- The carbon capture efficiencies of its two DAC plants
ground for mineralization and storage (Climeworks, 2021). reached 85.4% and 93.1%, respectively. However, the envi-
DAC technology from Global Thermostat uses tempera- ronmental benefits of the DAC process are closely related to
ture-swing adsorption and adopts immobilized organic energy sources. In an energy structure dominated by renew-
amine adsorbents. Global Thermostat established the first ables, it is expected that the large-scale deployment of DAC
pilot plant in 2010 and the first commercial DAC plant in technology (reaching 1% of global carbon emissions) will
Alabama in 2018. It is reported that the energy consumption not be limited by materials and energy, and related environ-
can be reduced to less than 6 GJ (t CO2)–1, which is around mental issues, if any, are relatively limited (Deutz and Bar-
the minimum for existing DAC demonstrations (Zhu et al., dow, 2021). According to calculations on carbon balance,
2021). Jonge et al. carried out LCA studies on a NaOH absorption
Carbon Engineering established its first DAC pilot DAC system, with a special focus on the life cycle carbon effi-
plant by using KOH and Ca(OH)2 solutions as absorbents in ciency. Their results also showed that the energy source is
2015, and in 2017, the company succeeded in the conversion very important to the emission reduction benefits of DAC.
of air-captured CO2 to liquid fuels. In 2019, the company In general, the utilization of renewable energy is the simplest
began to design and build a million-ton DAC demonstration and most significant way to improve the carbon efficiency
project. Its carbon capture cost is estimated to be $94–$232 of DAC at this stage (de Jonge et al., 2019).
(t CO2)–1, with an energy consumption intensity of about Terlouw and co-workers (2021b) proposed that it is nec-
8.81 GJ (t CO2)–1 (Keith et al., 2018; Engineering, 2021). essary to incorporate CO2 storage into the DAC’s LCA pro-
AUGUST 2022 ZHANG ET AL. 1257

cess in order to fully reflect the emission reduction benefits adsorption material can be realized to achieve an ultra-low
and other environmental impacts of DAC. Based on this cost CO2 capture process (Schneemann et al., 2014)
idea, the authors compared and studied the environmental (Table 2). It should be noted that the energy consumption of
impact of direct air capture and storage (DACCS) under dif- the existing carbon capture process is relatively high, often
ferent power/heat sources and a variety of technology combi- accounting for 70% of the entire CCUS technology chain.
nations. It was found that although a negative carbon effect
3.2. Light-responsive MOFs for CO2 adsorption
can be achieved in several scenarios, it is necessary to select
the best energy supply mode according to the energy infras- One of the general strategies to construct flexible
tructure of different countries and regions. This is of pivotal MOFs is to use organic linkers with light-responsive function
importance to the emission reduction capability and the envi- groups as subunits for the framework. Modrow et al. con-
ronmental impact of DAC (Terlouw et al., 2021a). structed the first porous MOF (CAU-5) with photo-switch-
It should be mentioned that DAC technology is still able linker molecules (3-azo-phenyl-4,4’-bipyridine). Under
very immature, so there are significant challenges in technol- the irradiation of UV light (365 nm), the azo-functionality
ogy evaluation. Terlouw et al. (2021b) systematically summa- switches from its thermodynamically stable trans-isomer to
rized the current LCA works for carbon-negative technologies cis-isomer (Modrow et al., 2011). Similarly, CO2 adsorption
and pointed out that existing methods may induce confusion behavior can be reversibly altered upon photochemical or ther-
between avoided emission and negative emission, resulting mal treatment in an MOF (PCN-123) with an azobenzene
in misleading conclusions. In order to better support the devel- functional group, which can switch its conformation (Park
opment of DAC technology in the future, it is necessary to et al., 2012). Sensharma et al. reported the synthesis and char-
strengthen the comprehensiveness of the evaluation and the acterization of a photoactive MOF (TCM-15), which
transparency of the methods. revealed a dynamic response upon UV irradiation, leading
to instant desorption of pre-adsorbed CO2. Based on FT-IR
3. Flexible metal-organic frameworks (MOFs) experiments and DFT calculations, the author verified that
such release of CO2 could be attributed to the structural flexi-
and ultra-low cost CO2 capture technology bility of the materials (Sensharma et al., 2019). Lyndon et al.
synthesized an MOF loaded with azo-type light-responsive
3.1. Flexible MOFs as CO2 adsorbents groups. The material showed rapid response towards CO2
Metal-organic frameworks (MOFs) are one of the emerg- adsorption during the light on-and-off switching cycles.
ing and rapidly growing focuses in material science. These This work directly verified the possibility of developing
materials are constructed from complexation of metal ions ultra-low energy consumption carbon capture technology
or metal ion clusters with bridging organic linkers, which based on flexible framework materials (Fig. 4) (Lyndon et
exhibit regular crystalline lattices with high surface area and al., 2013).
well-defined pore structures (Furukawa et al., 2013; Yuan et
al., 2018). In MOFs, both the metal nodes and the organic 3.3. Guest-responsive MOFs for CO2 adsorption
linkers can be readily adjusted. This offers an effective Interaction between MOFs and guest molecules is an
approach for the customization and delicate adjusting of the important way to stimulate flexibility. As early as 2003,
materials’ pore structure and functionalities. Therefore, Kitaura et al. introduced displacement freedom during the
MOFs can be widely applied in separation and catalysis sci- self-assembly process of rigid motifs, and they proved experi-
ence. In recent years, it was found that due to the dynamic mentally that the obtained material has a “gate-opening pres-
properties of the framework component, MOFs that are sure” for different gases, which caused the MOF material to
responsive to external stimuli (pressure, temperature, ultravio- transition from a crystalline “closed ” form into an “open ”
let light, etc.) can be synthesized (Matsuda, 2014). Based on form. The authors suggest that the reason for this flexibility
this, construction of a reversible phase transformable CO2 is the displacement of π-π stacked moieties in the material.

Table 2. Properties before and after breathing-MOF.

Trigger of
Reference Sample flexibility Properties alteration upon flexibility
(Park et al., 2012) PCN-123 UV irradiation At 1 bar pressure, CO2 adsorption decreased from 21 to 10 cm3 g–1
after UV irradiation.
(Lyndon et al., 2013) Zn(AzDC) UV irradiation Dynamic exclusion of CO2 during UV on-.and-off switching cycles.
(4,4’-BPE)0.5
(Dong et al., 2021) NTU-65 Temperature C2H4 adsorption capacity (1 bar pressure) decreased from 90 to
~0 cm3 g–1 when increase temperature from 195 to 263 K.
(Marks et al., 2020) CPL-2 and CPL-5 Rotation of the Due to lattice expansion, CO2 adsorption increased rapidly at pressure
pillar ligands lower than 20 bar.
(Taylor et al., 2018) Co(bdp) Formation of CO2 At appropriate pressure, CH4 can be largely excluded from the pores,
clathrate leading to high CO2/CH4 adsorption selectivity.
1258 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

At the same time, due to the different interactions between dif- Using NH2-MIL-53(Al) as a parent material, Bitzer et
ferent gas molecules and materials, the gate-opening pressure al. introduced Sc, V, Cr, and Fe as a second metal node to pre-
also varied in different atmospheres. For CO2, the opening pare NH2-MIL-53 (Al, M). Based on systematic characteriza-
and closing pressure are only 0.4 and 0.2 bar, respectively tions, the authors found that the flexibility of the framework
(Kitaura et al., 2003). Stavitski et al. prepared amino-modified can be effectively adjusted by the presence of the second
NH2-MIL-53(Al) and found that the modified material has metal, which further altered the CO2 capture performance of
excellent CO2 adsorption properties compared with the the resulting samples. In general, the construction of poly-
unmodified counterpart. Very interestingly, it was found metallic MOFs can easily and effectively regulate the frame-
that instead of binding CO2 chemically, the introduced work flexibility in a wide range, which has great potential in
amino groups actually played a role in adjusting the frame- future applications (Bitzer et al., 2020).
work flexibility. In this way, the CO2 adsorption capacity Ghoufi’s calculation revealed that the flexibility of MIL-
could be enhanced while the physical adsorption nature was 53 could be affected by the existence of an electric field in
not altered, and therefore, a significant increase in energy con- addition to the stimulation of the guest molecules, heat, and
sumption for desorption was avoided (Stavitski et al., 2011). external forces, with a volume change of up to 40%. At the
Using Cu as the metal center, 2,3-pyazinedicarboxylic acid same time, varying the electric field strength led to the regula-
(pzdc) as the ligand, and 4,4’-bipyridine (bpy) and 1,2-di-(4- tion of the unit cell volume. This provided a ready path for
pyridil)-ethylene (bpe) as the pillar, CPL-2 (Cu2(pzdc)2
adjusting gas adsorption, which resulted in the efficient sepa-
(bpy)) and CPL-5 (Cu2(pzdc)2(bpe)) were prepared, respec-
ration of CO2 and CH4 (Ghoufi et al., 2017).
tively. Both samples showed excellent CO2 adsorption capac-
Dong et al. prepared a flexible MOF (NTU-65), and its
ity and selectivity, and based on in situ synchrotron X-ray
flexibility is sensitive to temperature. Based on this character-
diffraction experiments, the authors showed that the chemical
interaction between CO2 and the materials triggered rotation
Quantity Adsorbed (cm3 g−1 STP)

of the pillar ligands. This distortion further introduced expan- 40 32

sion of the framework lattice, which is the key factor for the
35
high CO2 adsorption performance (Marks et al., 2020). 30

Temperature (°C)
30
Taylor and co-workers prepared a Co (bdp) (bdp2− = 1,
25 28
4 benzenedipyrazolate) MOF material with a flexible frame-
work, which showed excellent adsorption selectivity for the 20 26
separation of CO2 and CH4. Based on in situ X-ray Powder 15
Diffraction (XRD) measurements, the authors suggest that 24
10
the high selectivity originates from a “reversible guest tem- 5 22
plating” effect. That is, in the adsorption process, the frame- 0
work expanded to form CO2 clathrates, and the expended 20
framework collapsed back to the non-templated phase in the 0.0 0.2 0.4 0.6 0.8 1.0 1.2
subsequent desorption process. Based on such a mechanism, Absolute Pressure (bar)
CH4 was completely removed during adsorption of a 1:1 Fig. 4. Light-responsive capture of CO2 [Reprinted from
CO2-CH4 mixture (Fig. 5) (Taylor et al., 2018). (Lyndon et al., 2013)].
3.4. Regulating the flexibility of MOFs for CO2
adsorption
Excess gas adsorbed (mmol/g)

18
Although flexible MOFs have shown many advantages 16
in CO2 adsorption, how to regulate their flexibility to match
practical conditions is still a challenging question. 14
Based on the excellent structural flexibility and mechani- 12
cal resistance of MIL-53 series materials, Chanut et al. 10
found that when an external force is applied to the materials,
8
they gradually change from an open-pore form to a contracted
form. More importantly, the pore size of the materials can 6
be accurately controlled by the strength of the applied force. 4
Based on this idea and considering specific separation 2
objects, efficient separation of CO2/N2 and CO2/CH4 could
be achieved under optimized external force conditions. At 0
the same time, when the external force is unloaded, the mate-
0 10 20 30 40 50 60
rial structure switched back to the open form, which led to
gas desorption and material regeneration (Fig. 6). Clearly, P (bar)
such a strategy is superior to the conventional pressure- Fig. 5. Separation of CO2 and CH4 by flexible framework
swing or temperature-swing processes (Chanut et al., 2020). material [Reprinted from (Taylor et al., 2018)].
AUGUST 2022 ZHANG ET AL. 1259

Fig. 6. Flexibility regulation by external force [Reprinted from (Chanut et al., 2020)].

istic, and together with the different gate-opening pressure

of different gases, the authors successfully found a suitable
operation window for the one-step separation of multi-compo-
nent gases containing ethylene, ethane, and CO2. High
purity ethylene of polymerization grade was obtained by
this method, which may find important potential in the petro-
chemical industries (Dong et al., 2021).

4. Integration of CO2 capture and conversion

(ICCC)

4.1. General basics of ICCC

Integration of CO2 Capture and conversion (ICCC)
refers to the connection of these two processes by their com-
mon microscopic steps, that is, the interaction between CO2
and solid surface. During the new process, the captured CO2
is directly converted to a value-added product without its des-
orption and enrichment (Fig. 7) (Zhou et al., 2020). Compared
with the traditional CCUS chain, there are multiple advan-
tages of ICCC. Firstly, it avoids the energy consumption of
CO2 desorption from absorbent/adsorbent in the traditional
carbon capture process. Since this is one of the key factors
causing the high cost of CCUS, it is thus expected that
ICCC may significantly reduce the cost for CO2 abatement.
Besides, ICCC allows the disposal of CO2 at close vicinity Fig. 7. Integrated CO2 capture and conversion [Reprinted from
of its emission, which greatly reduces the demand for CO2 (Zhou et al., 2020)].
transportation, and thus provides a solution to the source-
sink matching problem. It is also possible that the products the background of carbon neutrality, methanol is expected
from an ICCC process can be readily used in downstream to become a renewable energy carrier that can replace fossil
chains or even by the original emitter, leading to decarboniza- energy. The technology of CO2 hydrogenation to methanol
tion of the energy and industrial system. The above advan- has attracted more and more attention in recent years,
tages dictate the significant application potential of ICCC in mainly because this process can greatly reduce the consump-
carbon neutralization scenarios. However, this technology is tion of fossil resources for methanol synthesis, thereby bring-
still in the stage of laboratory verification, and systematic ing a significant effect of indirect reduction of carbon emis-
investigations are needed to clarify more approaches that sion.
are suitable for the current emission sources. Reller et al. were among the earliest who investigated
methanol producing ICCC process. In their work, N, N-
4.2. ICCC for methanol production Diethylethanolamine (DEEA) and Cu/ZnO-Al2O3 catalyst
Methanol is a very important platform chemical that is were mixed, and the system was in contact with high-pressure
widely used as a fuel and a chemical raw material. Under CO2 (10−20 bar) and H2 (50−70 bar) consecutively. As
1260 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

such, CO2 was firstly absorbed by DEEA, and then CO2 from CO/syngas production is huge, and relevant industries
could be activated and converted to methanol by Cu/ZnO- are facing severe pressures under the scenario of carbon neu-
Al2O3. This experiment used high-pressure and pure CO2 in trality. In recent years, some researchers have also studied
the CO2 capture stage, so it cannot be strictly classified as the feasibility of preparing CO/syngas through the ICCC strat-
an ICCC process, but it clearly verifies the feasibility for the egy by combining CO2 capture with either its direct hydro-
conversion of captured CO2 to value-added products (Reller genation or reforming with alkanes.
et al., 2014). Ni/CaO-Al2O3 mixed oxide was prepared by Li et al.
In 2016, Prakash’s group reported capturing CO2 by using CaO for high-temperature adsorption of CO2 and
directly from the air and its conversion to methanol for the Ni as the catalyst for CO2-CH4 reforming. This system can
first time. They used pentaethylenehexamine as a CO2 efficiently convert adsorbed CO2 into syngas, but due to the
absorber and Ru-based Prince complex as a catalyst to convert sintering of CaO, the materials are gradually deactivated in
the captured CO2 to methanol under high-pressure H2. With prolonged cycles (Li et al., 2009). In Qiao’s work, γ-Al2O3
the optimal conditions, the yield of methanol reached 95% was successively impregnated with K-Ca double salts and
and could be recovered by distillation (Kothandaraman et Ni species, acting as the CO2 adsorption and catalytic compo-
al., 2016). Based on this work, a series of follow-up studies
nent, respectively. CO2 adsorption and subsequent reforming
on several principal technical difficulties were performed.
with ethane to prepare syngas were then performed success-
Firstly, in order to improve the efficiency of amine
fully (Qiao et al., 2017).
absorbent, a two-phase system was developed to simplify
Bobadilla et al. prepared FeCrCu/K/MgO-Al2O3 bi-func-
the separation of catalyst and amine, and thus the cycling sta-
tional materials, and an ICCC process was carried out based
bility of amine could be enhanced (Kar et al., 2018). Addition-
on reverse water gas shift to produce syngas. The process
ally, the authors also reported that either immobilized
amines or metal hydroxide solutions can also be used for can be operated stably under simulated flue gas conditions
CO2 capture in the process, which might provide solutions containing oxygen and steam (Bobadilla et al., 2016). Ce
to the instability issue of amine-based absorbents (Fig. 8) doped Ni-Ca composite oxides were prepared by Sun et al.,
(Kar et al., 2019; Sen et al., 2020). in which the oxygen vacancy on CeO2 can significantly
enhance the activation of CO2, and thus its ICCC stability
4.3. ICCC for CO/syngas production could be improved. When the Ca/Ni/Ce ratio is 1:01:0.033,
CO is the main component of coke-oven gas and a com- the material can achieve 100% CO selectivity and 51.8%
mon reducing gas in the metallurgical industry. In addition, CO2 conversion at the optimum temperature (650°C); no
syngas composed of CO and H2 is a widely used synthetic deactivation was observed in 20 capture-conversion cycles
building block, which can be converted to a range of chemi- (Sun et al., 2019). Fe-Co-Mg-Ca multicomponent composites
cals. At present, the preparation of CO and syngas mainly were prepared by Shao and co-workers. It was found that
takes coal as the raw material through coking and gasifica- the existence of MgO can effectively lower the sintering of
tion, respectively. The energy consumption of these processes CaO, and the synergistic effect between MgO and CaO bene-
is high, and an additional water-gas shift is needed to fulfill fited CO2 adsorption, whereas Fe and Co species can provide
the downstream requirements on H2/CO ratio for syngas, additional oxygen vacancies for CO2 activation. Therefore,
which further lowers the carbon efficiency by converting the material shows excellent ICCC performance with 90%
some CO to unusable CO2. Therefore, carbon emission CO2 conversion and nearly 100% CO selectivity. The

Fig. 8. Integrated CO2 capture and conversion to methanol [Reprinted from (Kar et al., 2019)].
AUGUST 2022 ZHANG ET AL. 1261

authors also proposed a heterojunction redox mechanism. It In contrast to the above strategies, a combination of
was considered that the newly formed Fermi level in adsorption and catalysis sites in a single material is the most
Fe5Co5Mg10CaO significantly lowered the Fe3+/Fe2+ redox straightforward way. Farrauto’s group reported on a range
potential. Therefore, electron transfer became easier, which of experiments based on this idea. The performances using
is responsible for the enhanced activity of CO2 conversion Na, K, Mg, and Ca oxides as adsorption sites and Rh, Ru,
in reverse water-gas shift (RWGS) reaction (Fig. 9) (Shao et Ni, Pt, and Co as the catalytic sites were thoroughly investi-
al., 2021). gated. Meanwhile, the influences of reaction conditions and
related mechanisms were also clarified (Duyar et al., 2015,
4.4. ICCC for CH4 production
2016; Zheng et al., 2016; Arellano-Treviño et al., 2019a, b;
CH4 has a high hydrogen content, so the carbon emission Proaño et al., 2019).
during the CH4 consumption process is relatively low. The process of continuous abatement of CO2 in simulated
Through hydrogenation reaction, CO2 can be directly con- flue gas by ICCC was reported by Zhou et al. In their work,
verted to methane under atmospheric pressure, and its reac- Ni-MgO-Al2O3 two-dimensional nanosheets were used as a
tion temperature is significantly lower than that of reforming bi-functional material. Through the optimization of reaction
and reverse water gas. Therefore, it can be better coupled temperature, capture, and conversion time interval, the
with existing industrial emission sources to realize the authors realized nearly 100% CO2 capture and conversion
ICCC process. This is also the most studied direction in the under isothermal conditions (Fig. 10). The overall efficiency
ICCC field. of the process has been greatly improved compared to the tra-
In the process of ICCC for CH4 production, the adsorp- ditional temperature-swing and pressure-swing adsorption
tion step and conversion step can be coupled in several (Zhou et al., 2020).
ways. For example, Veselovskaya et al. used tandem reac-
tors, where K2CO3/Al2O3 adsorbent was loaded in a first
reactor for CO2 capture, and 4% Ru/Al2O3 catalyst was used 5. Electro-catalytic CO2 reduction (ECR)
in a second reactor for CO2 conversion after it was purged
out from the first reactor via H2 (Veselovskaya et al., 2018). 5.1. General basics of ECR
Alternatively, potassium-containing hydrotalcite and nickel- Electro-catalytic CO2 reduction (ECR) represents the pro-
based catalyst were loaded in a single bed via a layer-by- cesses that convert CO2 via an electro-chemical way. In
layer way, and CO2 adsorption and subsequent conversion sharp contrast to the conventional thermal-catalytic process
to CH4 were then achieved at 300°C –350°C, with a yield of where high temperature and pressure are normally needed
2.36 mol CH4 kg−1 cat h−1 (Miguel et al., 2017). In Sun’s for CO2 activation and conversion, ECR processes can be
work, MgO and Ru/CeO2 were employed as adsorbent and readily carried out in much milder conditions (atmospheric
catalyst, respectively, and their physical mixture was used pressure and room temperature). Meanwhile, as the required
for the ICCC to CH4 process, however, the conversion rate energy can be largely provided in the form of electrons, the
of CO2 in such a combination is relatively low (Sun et al., ECR processes can be directly integrated with low-grade
2020). renewables, and H2O, rather than other energized molecules,

Fig. 9. Heterojunction redox mechanism for CO2 capture and conversion to syngas [Reprinted from (Shao et
al., 2021)].
1262 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

can be used as a hydrogen source. As such, ECR enables the and low carbon alcohol. However, direct reduction of CO2
transformation of renewable energies to chemical energies to *COO− involves a one-electron transfer process with a
in form of fuels and/or chemicals including CO, hydrocarbons very negative redox potential (−1.9 V versus reversible hydro-
(methane, ethylene), hydrocarbon oxygenates (formic acid, gen electrode (RHE)), which significantly inhibits the activa-
methanol, ethanol, etc.), or a mixture of them, and after tion of CO2 (Hunt et al., 2003). Therefore, suitable electrocata-
their consumption, the released CO2 can be recycled to lysts should be developed to stabilize the *COO− intermedi-
close the carbon loop (Yang et al., 2016). All these merits ate, thereby reducing the activation overpotential.
give ECR great promise for the realization of carbon neutral- Metal catalysts including Au, Ag, Zn, and Cd with both
ity. In Table 3, we summarized several representative weak hydrogen and oxygen adsorption (Uesaka et al., 2018)
results from recent publications on ECR. have been widely investigated for ECR to CO. Among them,
Ag exhibits extraordinary ECR to CO performance. For exam-
5.2. ECR to CO ple, Yang’s group reported that when an Ag nanoparticle/
Selective ECR to CO is a promising route toward indus- ordered-ligand interlayer catalyst is applied in a gas-diffusion
trial implementation because the produced CO can be used environment, a high FE of 92.6% for CO formation at a
as a chemical feedstock to produce numerous higher-value high current density of 400 mA cm–2 could be achieved. It
chemicals or fuels, such as liquid fuel, low carbon olefin, was verified that the interlayer structure facilitated the syner-
gistic effect between multiple components and is responsible
for such excellent performance (Kim et al., 2020a). Single-
atom catalysts (SACs) with individual metal atoms dispersed
on solid substrates can maximize atom utilization efficiency
and thereby enhance catalytic performance. In comparison
with bulk Ni metal that catalyses hydrogen evolution exclu-
sively under ECR conditions, the Ni single-atom counterpart
can selectively electrochemically reduce CO2 to CO. Zhang
et al. designed a methoxy group of functionalized nickel
phthalocyanine (NiPc-OMe) molecules supported on carbon
nanotubes, which catalyses the ECR to CO process with
>99.5% selectivity. The electron-donating OMe groups
could enhance the Ni-N bond strength in the Ni-N4 sites and
accelerate CO desorption, thereby improving the catalyst sta-
bility (Zhang et al., 2020).
Metal-free carbon-based materials were also found to
be effective for ECR to CO. However, the pristine, defect-
free carbon materials are less effective, and incorporating het-
eroatoms such as nitrogen into the carbon matrix is necessary
to improve activity. Su’s group reported an N-doped CNT
synthesized through the pyrolysis of mixtures of poly (diallyl
Fig. 10. Continuous capture and conversion of CO2 to CH4 dimethylammonium chloride) and oxidized CNTs. By adjust-
[Reprinted from (Zhou et al., 2020)]. ing types and contents of the used nitrogen dopants, a maxi-

Table 3. Summary of research results on ECR catalysts.

Potential jco
Reference Sample (V vs. RHE) (mA m–2) Products and FE
(Kim et al., 2020a) Ag nanoparticles −0.82 400 CO, 92.6%
(Zhang et al., 2020) NiPc-OMe −0.64 300 CO, 99.5%
(Xu et al., 2016) N-doped CNT −0.9 5.8 CO, 90%
(Dinh et al., 2018) Cu electrocatalyst −0.55 100 C2H4, 70%
(Zhong et al., 2020) Cu-Al alloy electrocatalyst −1.5 400 C2H4, 80%
(Xiong et al., 2021) Ag@Cu2O −1.2 178 ± 5 CH4, 74% ± 2%
(Yadav et al., 2022) N-doped GQDs −0.85 170 CH4, 63%
(Bai et al., 2017) Pd-Sn alloy electrocatalyst −0.43 V − HCOOH, >99%
(Yan et al., 2021) s-SnLi −1.2 1000 HCOOH, 92%
(Xu et al., 2020) Cu catalyst −0.7 1.8 C2H5OH, 91%
(Wang et al., 2020) N-C/Cu −0.68 300 C2H5OH, 52% ± 1%
(Song et al., 2017) N-C −0.56 − C2H5OH, 77%
AUGUST 2022 ZHANG ET AL. 1263

mum FE of 90% for CO formation and stable operation sity) increased linearly with amino group (NH2) content. Con-
over 60 h with total current density and FE of 5.8 mA cm–2 sequently, a maximum CH4 FE of 63% could be obtained
and 85% can be achieved, respectively. During the reaction, over the catalyst with the maximum NH2 content of 9.07
the N-containing functionalities played an important role in atomic concentration (at. %) (Yadav et al., 2022).
stabilizing the *COO− intermediate, and this is the key for
5.4. ECR to oxygenates
the sample to possess high performance (Xu et al., 2016).
Investigations on ECR to oxygenates mainly focus on
5.3. ECR to hydrocarbons formic acid (or formate) and ethanol via two electron-proton
With the combination of hydrogen from water, CO2 can and twelve electron-proton reaction processes, respectively.
be electrocatalytically converted to hydrocarbons, mainly con- Formic acid is an important product from ECR that has
taining methane (CH4) and ethylene (C2H4), via eight elec- been widely explored as a hydrogen carrier. The common
tron-proton and twelve electron-proton reaction processes, strategy for industrial production of formic acid is carbonyla-
respectively. Cu-based nanoparticles can produce hydrocar- tion of methanol, which, however, requires intensive energy
bons at moderate overpotentials. This is attributed to the input. It is thus highly desired to directly convert CO2 to
appropriate strength of CO chemisorption on Cu, and protona- formic acid via the ECR process, which was predicted to
tion or dimerization of CO is considered to be a key step have a production potential of 475 kt yr–1 by 2030 globally.
towards the formation of single- (CH4) or multi-carbon (Contentful, 2021).
(C2H4) hydrocarbons (Peterson et al., 2010) (Kortlever et al., Several metals, including Sn, In, and Bi, have been inves-
2015). During the above mechanism, the *CO coverage on tigated as electro-catalysts for selective ECR to formic acid
the catalysts can significantly influence the ECR activity or formate. Among these metals, Sn commands the most atten-
and selectivity. A high *CO coverage can readily trigger tion for its low toxicity and cost. Bai and some of the co-
C-C coupling that enhances C2H4 formation, while less authors of this paper developed a Pd-Sn alloy electrocatalyst
*CO on the catalyst surface might not be competitive for exclusive formic acid formation (FE>99%) in a 0.5 M
enough over hydrogen evolution reaction (Huang et al., KHCO3 solution. The presence of Pd modified the electronic
2017). configuration and oxygen affinity of Sn, which stabilized
In the past several years, significant progress has been the HCOO* intermediate and the subsequent formic acid for-
made in ECR to C2H4 conversion, including catalysts, elec- mation (Bai et al., 2017). Recently, Zheng’s group developed
trolytes, and electrodes. A typical example was reported by a surface-Li-doped Sn (s-SnLi) catalyst, which exhibited a
Sargent’s group where a Cu electrocatalyst at an abrupt reac- high FE of 92% and a partial current density of 1.0 A cm–2
tion interface in an alkaline electrolyte (7 M KOH) reduces for producing formate. The introduction of Li dopants into
CO2 to C2H4 with 70% FE at a potential of −0.55 V vs. the Sn lattice enabled the localization of negative charges
RHE. The remarkable performance is correlated to hydroxide and lattice strains to their neighbouring Sn atoms; thereby,
ions on or near the Cu surface, which lowered the activation both activity and selectivity of ECR to formate were
energy barriers of ECR and C-C coupling (Dinh et al., enhanced (Fig. 11) (Yan et al., 2021).
2018). A graphite/carbon NPs/Cu/PTFE electrode was further Ethanol, a kind of clean and renewable liquid fuel with
constructed to prevent flooding problems and stabilize the a heating value of –1366.8 kJ mol–1, is a preferred product
Cu catalyst surface, thereby resulting in enhanced stability from ECR. Owing to the higher energy density and ease of
over the prolonged operation for 150 h. Afterwards, they storage and transportation compared to gas products,
developed a Cu-Al alloy electrocatalyst to further improve ethanol has also been considered as one of the optimal candi-
the FE of C2H4 to 80% at a current density of 400 mA cm−2 date fuels that substitute or supplement fossils in many appli-
in 1 M KOH electrolyte. They suggested that the Cu-Al cations (Shih et al., 2018). Moreover, ethanol is also an impor-
alloys provide multiple sites and surface orientations with tant and widely used common chemical feedstock for
near-optimal CO binding for both efficient and selective organic chemicals and medical disinfectants. Based on the
ECR (Zhong et al., 2020). considerable market demand, direct conversion of CO2 to
The progress on ECR to CH4, which has the highest heat- ethanol using only water and driven by renewable energy is
ing value of 55.5 MJ kg−1 among all the ECR products, is highly desired.
far behind that of C2H4. There is still a lack of applicable cata- Cu is the only reported metal so far that can electrochemi-
lysts with satisfactory CH4 selectivity. Only very recently, cally catalyse ECR to ethanol. However, the selectivity is
Xiong et al. fabricated an Ag@Cu2O core-shell structure. extremely low due to its moderate binding energy with most
By fixing the Ag core and adjusting the Cu2O envelope size, reaction intermediates. To promote the selectivity towards
the *CO coverage and *H adsorption at the Cu surface can ethanol, manipulation of the binding strength of reaction inter-
be modulated to steer the ECR pathway towards CH4. The mediates on Cu is a commonly used strategy. Xu et al.
optimal catalyst delivered a high CH4 FE of 74% ± 2% and reported a carbon-supported Cu catalyst via an amalgamated
a partial current density of 178 ± 5 mA cm−2 at −1.2 V vs. Cu–Li method, by which most Cu is atomically dispersed
RHE (Xiong et al., 2021). Yadav and co-workers reported on the carbon surface. The high initial dispersion of single
an amine functionalized N-doped GQDs for efficient ECR Cu atoms favors the selective ECR to ethanol with FE reach-
to CH4. It revealed that the CH4 yield (partial current den- ing ~91% at –0.7 V vs. RHE and outstanding durability of
1264 FRONTIERS OF CCU TOWARDS CARBON NEUTRALITY VOLUME 39

16 h. However, the current density (around 1.8 mA cm–2) is recently reported to be capable of ethanol production from
still below the industrial level (Xu et al., 2020). Based on ECR, which delivered comparable catalytic activities to Cu-
recent investigations, the improvement of current density is based catalysts and even better durability. Song and co-work-
at the expense of ethanol FE. For instance, Sargent’s group ers developed a metal-free cylindrical mesoporous nitrogen-
coated a nitrogen-doped carbon (N-C) layer on a Cu surface doped carbon as a robust catalyst for selective ECR to
to build a confined reaction volume, which promoted C-C ethanol. The synergy of nitrogen heteroatoms and highly uni-
coupling and suppressed the breaking of the C-O bond in form cylindrical channel structures dramatically boosted
HOCCH*, thereby promoting ethanol selectivity in ECR. C−C bond formation in ECR. Therefore, the catalyst
Under a current density of 300 mA cm–2, an ethanol FE of enabled efficient production of ethanol with a high FE of 77%
(52 ± 1) % is achieved on 34% N-C/Cu (Wang et al., 2020). at –0.56 V vs. RHE in 0.1 M KHCO3 (Song et al., 2017).
Metal-free nitrogen-doped carbon materials have also been Inspired by the potential of adjusting the nanostructure of

Fig. 11. Scheme illustrations of (a) electrochemical lithiation preparation of the s-SnLi catalyst, and (b) its
function mechanism for ECR to formate [Reprinted from (Yan et al., 2021)].

Fig. 12. The demonstration system of CO2 electrolysis for syngas production [Reprinted from (Carbon
Energy Technology Co. LTD, 2020)].
AUGUST 2022 ZHANG ET AL. 1265

the catalyst to acquire multi-carbon compounds, the group fur- Flexible MOFs are a type of smart materials that can
ther developed a hierarchical porous N-doped carbon with potentially alter the landscape of many applications. When
micropores embedded in the channel walls of N-doped they are used as CO2 adsorbents, their reversible breathing
ordered mesoporous carbon. By controlling the micropore behavior toward external stimuli may change the fundamental
content, the ethanol formation rate is improved by one order thermodynamic driving force for adsorbent regeneration
of magnitude compared to that of the counterpart without and thus enable less energy-intensive strategies over tradi-
medium micropores. These reports have provided new tional temperature-swing and pressure-swing processes. Low-
insights for designing highly efficient electrocatalysts for ering the cost of CO2 capture by flexible MOFs is of particular
ECR to ethanol in the future (Song et al., 2020). importance to facilitate the large-scale application of CCUS,
which in turn guarantees carbon neutrality to be achieved.
However, the performance of the reported flexible MOFs can-
6. Summary
not meet the requirement of practical application. Further
Clearly, CCUS will play an important role in reaching research, including design of a suitable process, is needed.
the carbon neutrality target, not just at its current stage, but ICCC technology represents a new way of carbon recy-
more so after future development. In particular, deep decar- cling, which may promote the formation of low-carbon mod-
bonization requires a considerable revolution of the current els and processes of the industrial system. This is of
energy and industrial infrastructure. Therefore, cutting-edge promise as decarbonization of industrial departments is con-
/disruptive CCUS technologies are becoming increasingly siderably difficult. Compared with existing CCUS technolo-
important and influential. gies, ICCC has obvious advantages in terms of cost reduc-
In this paper, we reviewed four technologies that are tion, source-sink matching, and so forth. Nevertheless,
regarded as frontiers of CCUS. In Table 4, their relevance ICCC is still in the laboratory verification stage. How CO2
to carbon neutrality over other low-carbon technologies, capture and its conversion can be efficiently combined, how
advantages over regular CCUS technologies, and difficulties value-added products can be obtained, and how the process
for future development are summarized. can be adjusted to match practical application scenarios are
DAC is one of the rare technologies that is able to offer still questionable at this stage.
negative emission, and very uniquely, DAC also provides a Recently, ECR has been one of the most eye-catching
solution to historical emissions. Both characteristics are neces- areas in catalysis. Due to its natural connection with renew-
sary to suppress climate change. When comparing with able electricity, the process manages to close the carbon
other CCUS technologies, localization of DAC is highly flexi- loop of fuels and chemicals by storing the low-grade renew-
ble. Therefore, the necessity for CO2 transportation can be able energy. Therefore, large-scale deployment of ECR can
minimized by deployment of DAC in close vicinity of CO2 effectively avoid consumption of fossil fuels and thus con-
emitters and/or downstream utilization/storage sites. Based tribute carbon reduction in an indirect way. Compared with
on such a feature, DAC is an ideal approach for distributed, other CO2 conversion technologies, the ECR process can be
mobile, and small-scale emitters. Currently, DAC is an imma- carried out under very mild conditions. Additionally, ECR
ture technology, and the process cost is relatively high. Effi- can be readily modularized, which greatly facilitates its scal-
cient absorbents/adsorbents, coupling with renewable ener- ing up. The primary technical difficulties of ECR include
gies, process engineering, and scaling-up are among the the design and preparation of the catalyst with high activity
most urgent issues to be solved. and selectivity and engineering challenges related to coupling

Table 4. Summary of selected CCUS technologies.

Relevance to carbon
neutrality over other Advantages over regular CCUS
Technology low-carbon technologies technologies Technological difficulties
DAC • Negative emission effects • Flexibility in localization • High-performance adsorbents/
• Solution to historical • Minimize transportation demand absorbents
emissions • Solution to dispersed and small-scale • Coupling with renewable energies
emission sources • Process engineering
• Scaling-up
Flexibilt MOFs • Enable low-cost CCUS • Lowering energy consumption for • High-performance materials
for carbon neutrality carbon capture • Process engineering
ICCC • A new way of carbon • Lowering CCUS cost • Efficient coupling of absorption and
recycling • Source-sink matching conversion process
• Re-shape industrial • Extension of products
system • Matching with application scenarios
ECR • Avoiding fossil fuels • Milder conditions • High-performance catalysts
• Storing low-grade • Easy to scale-up • Coupling with low-grade renewable
renewable energies energy
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Science and Technology Committee (Grant Nos. 21692112200 perature. Scientific Reports, 8, 112827, https://doi.org/10.
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Open Access This article is licensed under a Creative Commons
ical pressure. Nature Communications, 11, 1216, https://doi.
Attribution 4.0 International License, which permits use, sharing,
org/10.1038/s41467-020-15036-y.
adaptation, distribution and reproduction in any medium or format, Choi, S., M. L. Gray, and C. W. Jones, 2011: Amine-tethered
as long as you give appropriate credit to the original author(s) and solid adsorbents coupling high adsorption capacity and regen-
the source, provide a link to the Creative Commons licence, and indi- erability for CO2 capture from ambient air. ChemSusChem,
cate if changes were made. The images or other third party material 4, 628−635, https://doi.org/10.1002/cssc.201000355.
in this article are included in the article’s Creative Commons Climeworks, 2021: Direct air capture: a technology to remove
licence, unless indicated otherwise in a credit line to the material. CO2. Available from https://climeworks.com/co2-removal.
If material is not included in the article’s Creative Commons Custelcean, R., 2021: Direct air capture of CO2 via crystal engineer-
licence and your intended use is not permitted by statutory regulation ing. Chemical Science, 12, 12 518−12 528, https://doi.org/
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or exceeds the permitted use, you will need to obtain permission
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directly from the copyright holder. To view a copy of this licence,
and M. A. J. Huijbregts, 2019: Life cycle carbon efficiency
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