Journal of CO2 Utilization 51 (2021) 101640

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Journal of CO2 Utilization

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Review Article

A review of microbial electrosynthesis applied to carbon dioxide capture

and conversion: The basic principles, electrode materials, and bioproducts
Shixuan Zhang a, b, Jiwei Jiang a, b, Haonan Wang a, b, Fengxiang Li a, b, *, Tao Hua a, b, *,
Wei Wang a, b
a
College of Environmental Science and Engineering, Nankai University, 38 Tongyan Road, Jinnan District, Tianjin, 300350, China
b
Key Laboratory of Pollution Process and Environmental Criteria, Ministry of Education, China Tianjin Engineering Center of Environmental Diagnosis and
Contamination Remediation, Tianjin, 300350, China

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

Keywords: Atmospheric carbon dioxide (CO2) concentrations are currently rising at an unstoppable rate, and it is urgent to
CO2 capture curb this trend for a stable and sustainable atmospheric environment. Under this adverse situation, microbial
CO2 conversion electrosynthesis (MES) applied to CO2 capture and conversion has received increasing attention in recent years
Microbial electrosynthesis
for mitigating greenhouse effects while biosynthesizing higher-value products. Research on the CO2 capture and
Electrode materials
Bioproducts
conversion in MES has been increasing in recent years, in 2020 alone, there has been more than 1400 papers
concerning the bioelectrochemical CO2 capture and conversion. In this review, the basics of bioelectrochemical
systems are first briefly summarized to provide an overall understanding about them. Then, several commonly
used electrode materials such as carbonaceous materials, metallic materials, and carbonaceous-metallic mate­
rials, along with their advantages and disadvantages, are illustrated. Additionally, the features of pure/mixed
cultures are discussed in this review. In particular, many biobased products obtained from CO2 conversion via
MES are proposed systematically according to their respective carbon chain lengths. Finally, perspectives on how
to improve the MES performance and enable this process to be more suitable and feasible for the industrialization
of CO2 capture and conversion are presented here.

1. Introduction floods occurs. All these disasters will have a major impact on human life
and the global economy. According to the Intergovernmental Panel on
Carbon dioxide (CO2) plays an important role in the ecological Climate Change, to maintain global warming at 1.5 ◦ C for the rest of the
environment and is an indispensable part of the global carbon cycle. In 21 st century, approximately 100 to 1,000 Gt of CO2 must be removed
addition, CO2, as one of the main greenhouse gases, helps regulate the from the atmosphere [4], which means that CO2 emissions must be
temperature of our planet and is at the heart of climate change [1]. restricted.
However, CO2 emissions have grown so rapidly that they have reached As a result of this dire situation, many efforts have been undertaken
unprecedented levels since the industrial revolution [2]. Exhaust emis­ to reduce the excess CO2 discharged into the atmosphere, such as CO2
sions from factory chimneys in industrial production, vehicle emissions, capture and storage and CO2 capture and utilization [5,6]. CO2 storage
and fossil fuel combustion in modern life are the main contributors. In mainly includes underground storage, marine storage, and forest storage
addition, deforestation has made this trend even worse. Too much of the [5]. Underground reservoirs for CO2 storage often require sizable eco­
sun’s heat is being trapped by the excessive CO2, and the earth is nomic investments and may lead to geological instability [7]; marine
becoming hotter via the “greenhouse effect” [3]. Under the influence of storage runs the risk of impacting the marine ecological environment
the greenhouse effect, extreme weather is becoming increasingly and lacks suitable technology; and, finally, the capacity for forest stor­
frequent, sea levels continue rising, and global desertification is age is limited owing to the shrinking of forest areas, preventing this last
becoming more severe. As CO2 drives global weather systems, aspects approach from being used as a common storage method, despite its
such as global agricultural output are impacted, and devastating lower cost [8]. For these reasons, the application of CO2 capture and
destruction of lives and property through hurricanes, extreme heat, and storage is relatively limited. In the context of the shortage of fossil fuels,

* Corresponding authors at: College of Environmental Science and Engineering, Nankai University, 38 Tongyan Road, Jinnan District, Tianjin, 300350, China.
E-mail addresses: lifx@[Link] (F. Li), huatao@[Link] (T. Hua).

[Link]
Received 28 April 2021; Received in revised form 19 June 2021; Accepted 30 June 2021
Available online 9 July 2021
2212-9820/© 2021 Elsevier Ltd. All rights reserved.
S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

CO2 capture and utilization can be a practical and feasible method since microorganisms, and electrode materials of BESs to better understand
it not only reduces the amount of atmospheric CO2 but also has the the impact of system configurations on their performance. Additionally,
potential to relieve the energy crisis and avoid the problems caused by we systematically review the products synthesized by MES using CO2 as
CO2 storage. CO2 capture can be achieved by chemical, physical, or substrate according to their respective carbon chain lengths. In addition,
biological processes and their combinations [9]. Although chemical and this paper summarizes the status quo of MES as applied to CO2 capture
physical processes, such as absorption [10], adsorption [11], and conversion, as well as the future perspectives of the large-scale
photo-chemical [12], and electrochemical processes [13], have made application of MES for CO2 capture and conversion.
great progress (for instance, with electrochemical processes allowing
synthesis of higher-value chemicals such as oxalic acid, which are not 2. Basics of BESs applied to CO2 capture
possible biologically [14]), these technologies usually require high en­
ergy inputs, have leaching toxicities and a short life cycle, and higher Bioelectricity refers to the commonplace electrical phenomenon that
requirements for electrode materials [15]. CO2 is a gas with a special occurs among biological organisms in the micro world during physio­
structure consisting of three atoms, namely, one carbon atom and two logical activities and represents the basis of bioelectrochemical tech­
oxygen atoms, which are in a symmetric double-bond arrangement and nology. Bioelectrochemical technology is an emerging technology and
in the highest oxidation state [16]; accordingly, CO2 is chemically stable has been widely studied in recent years since it can be used to degrade
and requires a high activation energy to carry out chemical reactions. organic pollutants and to capture CO2, as well as simultaneously pro­
This means that CO2 only undergoes simple state changes without duce electricity and high-grade chemicals, based on electroactive mi­
changes in valence or value-added compound production through croorganisms. In a typical bioelectrochemical system, there are two
chemical or physical methods. Biological processes including algal chambers, the cathode chamber and the anode chamber, which are
cultivation, gas fermentation, and microbial electrosynthesis (MES) separated with a cation exchange membrane (CEM) [24]. The anode
have emerged as prominent alternatives for producing multicarbon chamber undergoes microbial metabolism to degrade organic materials
chemicals for CO2 utilization [17]. In MES, these nonspontaneous CO2 and produce large amounts of electrons, which can be delivered to the
reduction reactions can be stimulated efficiently with little energy input anode electrode directly or through specific electron mediators
by employing favorable functional microbial communities as bio­ including H2, formate, NH3, sulfide, nanowires, etc. [25]. Next, the
catalysts. MES is widely applied to capture and reduce CO2 since the electrons spontaneously travel to the cathode chamber or are conducted
electroactive microorganisms on the cathode are capable of using CO2 as forcibly to produce a reduction reaction through the external circuit or
a substrate for synthesis reactions with the assistance of an external to output energy. The anode chamber likely undergoes hydrolysis re­
reducing power supply under mild conditions [16]. Compared to actions and produces stoichiometric amounts of protons and electrons,
chemical or physical methods, biological CO2 capture has been regarded while the cathode chamber undergoes electrosynthesis reactions to
as a cost-effective and environmentally benign approach to reduce the produce biochemicals.
concentration of CO2 discharged into the atmosphere by converting CO2 BESs include microbial fuel cells (MFCs), microbial electrolysis cells
into other organics. Due to their obvious advantages, such as readily (MECs), microbial electrosynthesis (MES) systems, and microbial carbon
available raw materials, mild operating conditions without the capture cells (MCCs) in most cases. Among these technologies, the MFC
involvement of toxic substances, and environmental sustainability [18], is mostly used to degrade organic pollutants in sewage [26–28], with
MES is an attractive and promising method for CO2 capture and con­ oxygen commonly used in the cathode chamber as an electron acceptor.
version and can help contribute to global carbon neutrality [19]. MFCs are hardly ever applied to CO2 capture and conversion since ox­
Global research on bioelectrochemical CO2 capture and conversion ygen as the oxidant reacting with protons and electrons is a spontaneous
has grown rapidly and has advanced in recent years due to the obvious reaction and can be accelerated by a cathodic catalyst, while the
advantages of MES and the dire situation concerning CO2 emissions reduction of CO2 is a nonspontaneous reaction and requires additional
(Fig. 1). energy input [16]. Therefore, to reach the goal of capturing or reducing
To date, there have been several reviews about MES being applied to CO2, it is necessary to input external energy into the system to stimulate
CO2 capture and conversion in terms of electroconversion of CO2 to low- the CO2 reduction reaction. The most commonly used method entails an
carbon methane [20], energy consumption [21], microbial CO2 fixation external power supply, along with a CO2 reduction reaction catalyzed by
techniques [22], economic feasibility [16], biobased products [22,23], a metal catalyst or biocatalyst using electric energy as a reducing power.
etc. However, much research on this topic has emerged in recent years, The MES, which is a derivative of the MEC, has been intensively
and a comprehensive summary of these advances is needed. Further­ studied in recent years due to its ability to synthesize a variety of usable
more, a systematic summary of CO2-derived bioproducts is relatively high-value chemicals from CO2 by employing electroactive microbes as
lacking. Herein, we provide an updated review of the current working catalyst and using external electric energy as a driving force [29]. MES
principles of bioelectrochemical systems (BESs), cathode functional has been specifically designed for cathodic CO2 conversion and can

Fig. 1. (a) The number of papers published on biological capture and conversion of CO2 [17] (source: Web of science; key words: Biological CO2 conversion or
Biological CO2 capture, CO2 conversion or CO2 capture, as on date: 06/06/2021); (b) OECD (2021), Air and GHG emissions (indicator). doi: [Link]
10.1787/93d10cf7-en (Accessed on 06 June 2021).

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

utilize CO2 as substrate and convert it into biochemicals and biofuels input. Both the MCC and MES can achieve CO2 conversion under the
under the catalysis of electroactive microorganisms, which not only catalysis of dehydrogenase after CO2 is captured by an enzyme such as
conforms with the concept of CO2 emission reduction but also achieves carbonic anhydrase, which is able to enhance the solubility of CO2 and
the recycling of CO2. In MES, electrons are supplied by an external the efficiency of its further conversion [33]. Compared with MES, the
power source to overcome the thermodynamic barrier and then are used MCC system does not require external power input; however, the MCC
for CO2 conversion to biochemicals and biofuels at the cathode, showing has a low biomass yield due to the nutrient limitations [34], and
promise for electricity-driven bioproduction from CO2. Compared with correspondingly, its CO2 fixation efficiency is also low.
the MEC system, which focuses more on anodic organic oxidation, MES In BESs, CO2 can be effectively captured and reduced by MES in most
focuses more on cathodic CO2 conversion. cases. In most of the research, MES is also utilized to convert CO2 into
Recently, the MCC has attracted increasing attention in the fields of bioproducts. Thus, most of the bioproducts mentioned in this article are
CO2 capture, wastewater treatment, electricity generation, and synthesized by MES from CO2; a simplified description of the principles
biochemical production, and has emerged as a novel technology of three major types of BESs, namely, MFC, MES, and MCC, are shown in
combining MFC and MES systems with photosynthetic, microorganism- Fig. 2.
assisted cathodes [30]. The MCC combines the functions of MFC and In BESs, the inside of the microorganism is the core of metabolism,
MEC systems and simultaneously achieves CO2 capture, biochemical and the utilization and generation of electrons all happen inside the
production, wastewater treatment, and electricity generation [31]. In its microorganism while electron receptors are set outside the microor­
anodic chamber, organics are degraded to produce CO2, electrons, and ganism and mostly exist in the form of solid which cannot enter the
protons, among which CO2 is transported to the cathode chamber as a microorganism. To link the internal electron transfer of microorganisms
reduction substrate through an external pipeline [32]. The electrons are with the macroscopic electrodes, then we have to come to the extra­
transferred to the cathode through an external circuit to provide cellular electron transfer (EET) which matters in electron delivery be­
reducing power and generate electricity at the same time. Protons enter tween microbes and electrodes. Efficient extracellular electron transfer
the cathode chamber through the CEM. In the cathodic chamber, can improve the efficiency of electron transmission and utilization, and
photosynthetic microorganisms are employed as functional microor­ enhance the performance of the BESs so that to improve the efficiency of
ganisms for electrocatalytic reactions, and O2 generated by photosyn­ electricity generation or the efficiency of CO2 capture and conversion.
thesis acts as an electron acceptor. Under light conditions, CO2 is Therefore, EET efficiency plays a crucial role in BES. There are two main
captured by photosynthetic microorganisms, and reduced bioproducts EET pathways: direct electron transfer (DET) pathway and mediated
are obtained the same as in plants. In an MCC system, due to the addition electron transfer (MET) pathway. The DET pathway refers that the
of photosynthesis, CO2 capture, biochemical production and wastewater electroactive microorganisms directly obtain electrons from the surface
treatment can be accomplished simultaneously without extra electrical of the cathode electrode which can enter into the microbial body and be

Fig. 2. A simplified description of the principles of three major types of BESs. (a) MFC for transforming chemical energy in organics into electricity; (b) MES for
reducing CO2 to reduced bioproducts; (c) MCC for CO2 capture, wastewater treatment, and biochemicals production.

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

used for reduction reactions directly or electrons generated by the costs. Compared with pure cultures, mixed cultures possess more intri­
oxidation of organics inside electroactive microorganisms are directly cate microbial communities and more versatile metabolic pathways [21]
transferred to the electrode attached by the microbes through the and thus can be domesticated and adapted to various substrates more
intracellular substances such as NADH delivering enzyme, coenzyme Q, easily. Therefore, they also have a high tolerance to fluctuant environ­
ubiquinone [35] and the extracellular electron acceptors such as cyto­ mental conditions and offer more flexibility towards operational pa­
chromes [36], nanowires [37], and membrane vesicles [38]. For rameters [53]. Based on these features, mixed cultures can be used to
example, in Shewanella oneidensis MR-1, an electron transport network study the performance-floating of MES influenced by varying parame­
constructed by a variety of cytochrome proteins is distributed in its cell ters and conditions such as temperature, pH, reactor configurations,
membrane and periplasmic space, showing an excellent electron trans­ electrode materials, or hydraulic residence time due to their robust
port performance [39]. Some microorganisms lacking the ability for DET adaptability. At the same time, there are many bioproducts due to
utilize an indirect way to transfer electrons. MET pathway mostly takes various microbial synthesis pathways controlled by various enzymes,
place mediated by the diffusion of redox mediators and electron shuttles while the products of pure cultures are relatively limited. Regarding CO2
[40] which include flavins and phenazines [41], neutral red and meth­ capture and conversion, both pure cultures and mixed cultures have a
ylene blue [42], anthraquinone, thionin, methyl viologen or anthra­ role to play in terms of biocatalysts. In Table 2, we can see that the yield
quinones [43] to achieve electron transfer. Addition of redox mediators of bioproducts and the power density of MES are different under
is required to improve electron transfer efficiency via MET, however, the different biocatalysts and operational conditions. As shown in Fig. 3, an
presence of these substances will have slight toxic effects on microor­ intuitive comparison of the advantages of pure cultures and mixed cul­
ganisms. These two EET pathways are not isolated from each other, and tures is presented.
a microorganism may have both EET modes at the same time since the
complexity of the underlying mechanisms behind electron transfer 4. Bioelectrode materials
involved [44]. DET pathway is more efficient compared with MET
because it avoids the conversion of intermediates and can reduce the loss Bio-electrodes are usually conductive solid materials attached by
of electrons which is an ideal extracellular electron transfer pathway. huge amount of microbials with the ability to provide or remove elec­
Meanwhile, electrode properties such as specific surface area, biocom­ trons through Van der Waals, steric, and electrostatic interaction [54].
patibility, and conductivity are also concerned since the electroactive An excellent electrode needs to possess physicochemical properties like
microorganisms are in direct contact with the electrode. high active biocompatible surface, high chemical stability, high electron
transfer rate and high hydrophilicity [55,56]. If applied to CO2
3. Functional microbial communities attached to the electrode bioconversion, the electrode must also have the characteristic of low
in MES CO2 mass transfer resistance so that CO2 can be fully utilized and ach­
ieve a higher productivity of CO2-based bioproducts.
Electroactive microorganisms serve as core components of bio­ Bio-electrodes materials have been receiving increasing attention
electrochemical systems. Those microorganisms that can consume CO2 since the properties of the electrode have a great impact on the perfor­
as their main carbon source from the atmosphere play a particularly mance of BESs, such as extracellular electron transfer and interaction
essential role in the normal functioning of these systems. The metabolic between microbes and electrode [55]. The cathode serves as an electron
properties and electron uptake abilities of electroactive microorganisms source for microorganisms to reduce CO2 to different kinds of bio­
influence the sustainability, productivity, and energy conversion effi­ products and its status is irreplaceable. Many studies have been carried
ciency of the entire MES system. These microorganisms are mostly out on electrode optimization to attain a better performance in
chemoautotrophic bacteria that can directly take up electrons from bio-products synthesis and organic pollutants removal, such as the
electrodes, but in certain instances, to enhance interfacial electron introduction of reticulated vitreous carbon [57], the utilization of
transfer between microbes and electrodes, several electrochemically granular graphite bed as the cathode [58] as well as carbon fabric / felt
active redox mediators such as neutral red, 2-hydroxy-1,4-naphthoqui­ coated with functional groups or enhanced by gas diffusion [59,60].
none, or hydroquinone are also required [45]. In the case of CO2 cap­ Bioelectrodes that have been extensively investigated can be divided
ture and conversion, microbials with the ability to utilize CO2 as their into three categories, namely carbonaceous materials, metallic mate­
C-source are a prime requisite. rials, and carbon-metallic materials, respectively. Due to the different
Some CO2-utilizing microorganisms, mainly methanogens and ace­ properties of these materials, the performance of them is slightly
togens, have been intensively tested in MES as pure cultures or enriched different. This part generally summarizes the electrode materials
in mixed cultures for methane and acetate production [46–48]. Different commonly used in MES, and lists the latest new electrode materials or
functional microbial communities on the electrode will be divided into electrode forms. An outline of some common-used electrode materials in
pure cultures or mixed cultures, and they possess different advantages MES are presented in Fig. 4 to provide a clearer comprehension about
and disadvantages. Pure cultures can be obtained by various selection the types of electrode materials. The specific properties and performance
and enrichment methods using various media. More specifically, pure of these electrode materials are not discussed in this paper as it has been
cultures are obtained after separation and purification of mixed cultures. reviewed in detail [61].
Pure cultures can achieve highly selective production of certain products
including methane, acetate, etc. [16,47], from CO2 conversion. 4.1. Carbonaceous materials
Furthermore, such cultures might lead to higher coulombic efficiency
than that of mixed cultures, where the formation of side products de­ Carbonaceous materials have a high specific surface area and pro­
creases the electron flux to the target product [49]. Pure cultures are vide sufficient attachment for microorganisms owing to their porous
commonly employed to specifically synthesize specific simple products, structures; apart from these qualities, their chemical stability is unpar­
which subsequently can be utilized directly in practical applications. alleled due to their idiographically stable electron distribution of carbon
These cultures can also be subjected to genetic and metabolic engi­ atoms. Carbonaceous materials are most widely employed as bio­
neering to obtain genetically tractable modified strains. Adaptation of electrodes in MES, and some prefabricated carbonaceous electrodes
engineered cultures for bioelectrode applications will help to target such as carbon cloth/fabric/felt, carbon rods, carbon sticks, carbon
more valuable long-chain organics and will be a very promising process blocks [56] and carbon brushes [62,63] are commonly used since they
with the development of genetics. Applying mixed cultures to bio­ are readily available, cost-effective and currently commercially avail­
electrodes as biocatalysts has also been widely studied in MES [50–52] able. Carbon cloth/fabric/felt are more flexible than the other materials
since they are easy to culture and grow, resulting in lower operating and can be refined to any shape consistent with different reactor

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

Fig. 3. Analysis of the advantages of pure cultures and mixed cultures.

Fig. 4. An outline of common-used electrode materials in MES.

configurations to realize optimal performance. Apart from the above abundant surface for bacterial adhesion and effective electrode inter­
several carbon-based materials, graphite-based materials are an excel­ action for the microbiome.
lent class of electrode and demonstrate superior performance to Performance in bioproduct synthesis is closely related to microbe-
carbon-based materials in terms of current output [64,65]. electrode interactions and extracellular electron transfer; to promote
Many other carbonaceous electrodes such as biochar [66] and gas microbe-electrode interactions and extracellular electron transfer,
diffusion-activated carbon [59,67] have also been employed as biocat­ modification of carbon-based electrodes has been adopted [58,71].
alyst carriers. For instance, in the experiment of Yasuhito Nakasug et al., However, the mechanical strength of carbon materials is relatively low
carbonized coconut shell was adopted as the electrode material due to its and is easily diminished during operation, so it is necessary to
advantages such as low cost, high surface area and chemical stability strengthen carbonaceous electrodes by developing novel materials
compared with those of prefabricated carbonaceous electrodes, with a supplemented with carbonaceous electrodes.
maximum methane production rate of 340 mmol/m3/d when cultivated
at 55 ◦ C [68]. Carbonized coconut shells applied to electrodes can not
only achieve higher productivity but also realize the recycling of waste. 4.2. Metallic materials
Hence, reusing carbonaceous waste as electrodes in MES is a promising
approach for future sustainable development. Compared with carbonaceous electrodes, metallic electrodes have
In addition to using a single carbonaceous material, plating other higher mechanical strength and, therefore, tend to be sturdier. Due to
carbonaceous materials with better properties such as graphene, carbon the absence of large numbers of freely moving electrons in metals, the
nanotubes and carbon nitride onto the surface of raw carbon electrodes conductivity of metallic materials is unparalleled, and many researchers
is an efficacious way to achieve higher productivity. For example, Aryal have explored a variety of metal electrodes in MES in recent years, such
Nabin et al. developed a 3D-graphene-modified carbon felt composite as stainless steel [72,73], iron [74], platinum [75], palladium, gold [76],
cathode that was able to increase the electrosynthesis rate of acetate molybdenum [77], rubidium [78], and nickel [79], and these materials
from CO2 by 6.8-fold, given that this novel electrode possesses a faster all exhibit good electron conduction performance. In addition, metal
electron transfer rate and 2-fold higher specific surface area than that of foams, such as copper foam and nickel foam, may be used as electrodes
untreated carbon felt [69]. Moreover, a nitric acid-treated graphite [80]. Although possessing excellent conductivity, most metal-based
granular cathode makes sense for further improving the properties of the electrodes have poor corrosion resistance because of electrochemical
cathode, such as a better electron transfer rate and higher specific sur­ corrosion electrolyte solution, which leads to metal leaching, and can be
face area [58]. In addition to these fixed-shaped carbon electrode ma­ toxic to microorganism growth. At the same time, the biocompatibility
terials, there are several other unique electrodes. For example, the high and specific surface area of metallic electrodes are relatively low in
acetate production rate reported by Marshall et al. [70] can be linked to comparison with those of carbonaceous materials. Moreover,
the use of a granular graphite bed as the cathode, resulting in an metal-based electrodes may lead to higher cost. Carbonaceous materials
have relatively superior properties compared to pure metal materials

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and are preferable in practical applications. 5. Bioproducts from CO2 capture and conversion via MES

4.3. Carbon-metallic materials So far, there has been a considerable amount of literature about the
products synthesized by functional microbials in MES. The typical bio­
Pure materials may have some limitations such as poor electro­ based products from the bioelectrochemical transformation of CO2 are
activity associated with carbon and the high cost of metal. Therefore, divided into several categories according to the number of carbon atoms
combining carbon with metal in novel ways to optimize the properties of in the product, e.g., C1, C2, C3, and C4, and are systematically sum­
bioelectrodes would be valuable. Carbon-metallic electrodes have larger marized and discussed in this section. A brief description of the synthesis
specific surface areas and better catalytic effects than ordinary carbon process of value-added bioproducts on the surface of the cathode is
electrodes, as well as higher power density. Some typical metals such as provided below (Fig. 5).
Pt [81], Fe [82], Ni [83], Au [76], and Pd [77] can be doped onto carbon
electrodes to synthesize electrode materials with improved electro­
chemical activity performance. In addition, carbon materials modified 5.1. C1-bioproducts from CO2
with metal nanoparticles to enhance electrode surface properties can be
beneficial for the formation of biofilms on electrodes [55]. Apart from Various C1 chemicals have been observed in MES studies using pure
using pure metals, metal oxides can be employed to optimize electrodes. cultures or mixed cultures, including methane (CH4), formic acid
For example, C. Cruz Viggi et al. were able to increase the yield of ac­ (HCOOH), and methanol (CH3OH). Among these C1 compounds,
etate production by up to 8.5-fold by using a graphite rod supplemented methane has been one of the most widely reported products in BES
with magnetite nanoparticles since the magnetite nanoparticles could studies and has recently been reviewed extensively [87]. Methane, the
catalyze microbiologically driven hydrogen production and promote simplest organic compound, is the main component of natural gas and
direct electron transfer processes [84]. Furthermore, Dayakar Thati­ biogas and can be used not only as a fuel but also as a raw material to
kayala and Booki Min adopted copper ferrite-supported reduced gra­ produce hydrogen (H2), acetylene (C2H4), and formaldehyde (HCHO); it
phene oxide as a cathode to enhance the microbial electrosynthesis of is generally produced by anaerobic digestion or fermentation of biode­
volatile fatty acids from CO2, generating bimetal-doped carbon mate­ gradable organics. In MES, methanogens are able to synthesize methane
rials [85]. In this way, the high conductivity of metallic materials and at the cathode through a direct or indirect electron transfer pathway
high surface area of carbonaceous materials were combined to obtain [68] under the assistance of an external power source. The reactions and
superior bioelectrochemical CO2 capture and conversion performance. detailed substrates in the anode and cathode chambers are as follows:
In turn, metallic materials can also be utilized as electrode main bodies
Anode: H2O → H+ + OH−
and then coated with carbonaceous materials to simultaneously endow
composite electrodes with high conductivity, excellent biocompatibility, Cathode: CO2 + 8H+ + 8e− → CH4 + 2H2O (DET pathway)
and good mechanical strength. For example, the study by De-Chun Xu
et al. developed a graphite-coated stainless-steel electrode, and the Or 2H+ + 2e− → H2
current density of the system was increased 20-fold with the aid of a
CO2 + 4H+ → CH4 + 2H2O (IET pathway)
graphite coating layer [72] (Table 1). The advantages and disadvantages
of discussed electrode materials are summarized in Table 1. In this process, CO2 is the final electron acceptor, while H2 or elec­
trode is the electron donor. Methanogens at the cathode are able to
catalyze the methane production process from CO2 conversion. Metha­
nogens include many different species such as Methanococcus vannielii,
Table 1 Methanococcus maripaludis, Methanolacinia petrolearia, Methanobacterium
Overview of different kinds of electrode materials with their advantages and
congolense, and Methanoculleus submarinus, and among these strains,
disadvantages.
Methanococcus maripaludis is the most resource-efficient methane pro­
Advantages and Electrode materials Reference ducer according to Mayer, F. et al. [25]. To increase the rate of CH4
Disadvantages
formation from CO2 conversion in a mixed-culture biocathode, Yang
High specific surface
Carbon cloth/felt/fabric [59,60] Hou-yun et al. introduced neutral red and anthraquinone-2,
area
6-disulfonate, resulting in biocathode CH4 formation rates 5.8- and
Inexpensive and
readily available
Carbon rod/stick/block [56] 3.5-fold higher than those of unaltered cathodes, respectively; this
High conductivity phenomenon was attributed to enhanced extracellular electron transfer
Carbon brush [62,63]
Carbonaceous and flexible by microbes and a reduction in internal resistance [88]. With the aim of
materials Less corrosion Biochar [66] converting CO2 bioelectromethanogenesis from laboratory-scale to
Less active surface Graphene [69]
pilot-scale, Franziska Enzmann et al. first developed a scaled-up 50-L
Highly rigid Activated carbon [59,67]
Poor electroactivity Reticulated vitreous reactor based on theory similar to that using Methanococcus mar­
and mechanical carbon [86] ipaludis, which was the largest pure culture bioelectromethanogenesis
strength … experiment reported thus far and achieved the highest total methane
High conductivity Stainless steel [72,73]
production rate of 11.7 mmol/d [49]. This study established the theo­
High surface activity Iron [74]
High mechanical
retical basis and potential for the future practical and large-scale
Platinum [75] application of bioelectromethanogenesis systems. Research by
strength
Metallic
materials
Corrosive and toxic Gold [76] Beese-Vasbender et al. has demonstrated that a pure culture of the
High cost Nickel [79] marine lithoautotrophic Methanobacterium-like archaeon strain IM1 is
Metal leaching Molybdenum [77]
capable of utilizing electrons from graphite cathodes for highly selective
Less specific surface
area
… production of methane, without hydrogen serving as a
Carbon electrodes cathode-generated electron carrier with a coulombic efficiency of 80 %
High specific surface
area
doped with Pt, Mn, Fe, [81,85] and production rates of 350 nmol/d/cm2 after 23 days of incubation
Carbon-metallic Ni, Au, Pd, etc. [89]. However, it is worth noting that the global warming potential of
materials Good catalytic effects Metallic materials
coated with [72,84]
methane, which is the third most important greenhouse gas [90], is 25
High power density times that of CO2 [91], so efforts should be made to avoid methane
carbonaceous materials
leakage into the atmosphere during bioelectromethanogenesis by

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Fig. 5. A brief description of the synthesis process of value-added bio-products on the surface of cathode.

inhibiting the activity of methanogens. including alcohols or long-chain fatty acids. Acetate can be prepared by
Formic acid, the simplest carboxylic acid, can be used as an organic artificial synthesis or biosynthesis, and many microorganisms have the
chemical raw material as well as a disinfectant and preservative. It is capacity to convert a variety of organic material into acetic acid through
widely used in the production of pesticides, leather, dyes, medicine, fermentation. Acetic acid can be used as an acidity regulator or acidu­
rubber, and other industries. Quang Anh Tuan Le et al. employed a lant. At the same time, it can also be a good antimicrobial agent, mainly
Shewanella oneidensis MR-1 whole-cell biocatalyst with a formidable due to its ability to lower the pH to below the optimal pH required for
electron transfer system for the synthesis of formic acid from gaseous the growth of many microorganisms. Similar to methane production,
CO2 for the first time. Their average conversion rate of formic acid acetate production can be achieved directly or through a
synthesis in optimal medium over a period of 72 h was 3.8 mM/h/g wet- hydrogen-mediated mechanism via the acetyl-coenzyme A pathway
cell [92]. In addition, in a study by Linpeng Yu et al., formate was [57]. To pursue higher acetate production rates, it is a key requirement
synthesized via immobilization of a thermophilic microbe at 55 ◦ C, to inhibit methanogenic activity [57]. The detailed equations are as
which involved formate dehydrogenase for CO2 capture and conversion, follows [96].
achieving an electrosynthesis rates of 63.2 mmol/m2/d [93]. The use of
CO2 + 7H+ + 8e− → CH3COO- + 2H2O
thermophilic microbes in this study enhanced the production rate
through an increase in PDH activities caused by temperature. 2H+ + 2e− → H2
Methanol is the simplest saturated monohydric alcohol synthesized
from CO2. This alcohol can be used as a chemical reagent directly or as a CO2 + 4H2 → CH3COO− + H+ + 2H2O
precursor for organic products such as acetic acid, methyl chloride, or
There are many autotrophic bacteria that have been reported for the
pesticides. Previous studies have found that methane-oxidizing bacteria
successful production of acetate from CO2, such as Sporomusa ovata,
containing methanol dehydrogenase, formaldehyde dehydrogenase, or
Sporomusa silvacetica, Sporomusa sphaeroides, Clostridium ljungdahlii,
formate dehydrogenase are able to reduce CO2 to methanol through a
Clostridium aceticum, and Moorella thermoacetica [97]. Furthermore, Pau
multienzymatic bioconversion using sequential immobilization of en­
Batlle-Vilanova et al. achieved acetate production from CO2 in contin­
zymes under mild conditions [94]. In detail, the mechanism behind
uous mode via MES. To obtain a high acetate titer, the authors employed
methanol formation from CO2 involves formate dehydrogenase, form­
2-bromoethanosulfonate to inhibit the methanogenic activity during
aldehyde dehydrogenase, and methanol dehydrogenase, which can
influent preparation, and in this study, acetate was continuously pro­
convert CO2 to formate, formaldehyde, and methanol, respectively.
duced from CO2 at a maximum production rate of 0.98 mmol C/LNCC/d
Sometimes, formaldehyde may exist as a byproduct in MES, and it is an
[96]. Different microbial strains, electrode materials, applied voltages,
important chemical raw material; at a concentration of 30 %–40 % in
operational environments, and reactor configurations can lead to vari­
aqueous solution, formaldehyde is also called formalin, which has
ations in acetate production. These variables can be adjusted to satisfy
antiseptic and sterilization properties and is often used in the medical
practical and industrial demands. By supplementing with magnetite
field.
nanoparticles, the microbial electrosynthesis of acetate from CO2 could
be enhanced since magnetite nanoparticles can divert electrons away
5.2. C2-bioproducts from CO2 from methanogenesis [98]. Recently, Jiang yong et al. integrated MES
with membrane electrolysis and achieved a 179 % increase of acetate
The main C2 bioproducts of MES for CO2 capture and conversion production while employed powder-activated carbon as cathode [99].
include but are not limited to acetate (CH3COOH), ethanol (C2H5OH), This result shows the possibility and feasibility of combining MES with
dimethyl ether (CH3OCH3), and ethylene (C2H4). These compounds can other systems to increase product yield. However, from an economic and
be used directly as fuels or can be used to further generate high-carbon practical standpoint, acetate production is not very economically ad­
fuels or bioplastics. As mentioned above, methane is a major bioproduct vantageous due to its low market price.
from CO2; another major product from direct CO2 bioconversion is ac­ Ethanol and dimethyl ether are isomers of each other, and both can
etate, and since acetogens are flexible an can exhibit both autotrophic be employed as clean fuels. At the same time, these compounds play a
and heterotrophic metabolism [95], they can grow under abnormal unique and significant role in the pharmaceutical, fuel, and pesticide
conditions such as acidic, alkaline, saline or hot environments. Acetate industries in which ethanol and dimethyl ether are needed in large
also represents a crucial intermediate for further processes, such as quantities. Ethanol can be produced from acetate reduction at lower pH
secondary fermentation, to produce more valuable compounds,

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

when undissociated acids exist [48], and the bioelectrochemical expand the product family of MES. In addition to the above products,
pathway also works [100]. In addition, ethanol can be generated from lactate (C3H6O3) is another useful 3-carbon organic compound gener­
maltose utilization while introducing CO2 as an electron acceptor to ated from the intermediate products of CO2 reduction through the Krebs
achieve in situ CO2 fixation [101]. Ethanol can also be produced by MES, cycle [111]. Apart from the above C3 products, glycerol produced from
indicating the large application potential of MES. Sandipam Srikanth the reduction of CO2 was proposed by Soussan et al. [112]. According to
et al. applied gas diffusion electrodes to enhance the bioavailability of this study, the authors employed G. sulfurreducens as the biocatalyst,
CO2 in MES, accumulating alcohols at a concentration of 21 g/l over 90 which could produce glycerol from CO2 in the presence of succinate
days with a coulombic efficiency of 49 %, of which ethanol accounted converted from fumarate [113], thereby further widening the applica­
for 45 % [102]. Haixia Liu et al. employed an anaerobic, acetogenic tion prospects of MES.
bacterium called Clostridium scatologenes ATCC 25775T, which is capable
of fixing CO2 through the Wood–Ljungdahl pathway in MES to convert
CO2 into high value-added products; they obtained an ethanol produc­ 5.4. C4-bioproducts from CO2
tion rate of 0.015 g/L combined with other organics [103]. Ethylene is
the core of the petrochemical industry, and it is a standard against which The longer the carbon chain of a product, the higher its use value,
to measure the level of a country’s chemical industry; however, most of and hence, it is an attractive option to conduct bioelectrochemical chain
the ethylene used in industry is derived from gas produced by petroleum elongation, which refers to microorganisms that can catalyze the elon­
refining plants or petrochemical plants, which comes at a relatively high gation of short-chain fatty acids to medium-chain fatty acids in MES
cost [104,105]. Therefore, ethylene production from the bio­ [16]. In addition to chain elongation, the production of C4 compounds
electrochemical conversion of CO2 is an attractive method and has been directly from CO2 has been reported. Butyrate (CH3(CH2)2COOH),
considered a sustainable process to produce ethylene and achieve en­ butanol (CH3(CH2)3OH), isobutyrate ((CH3)2CHCOOH), and succinate
ergy savings. Although the electrochemical conversion of CO2 to ([CH2COOH]2) are several common products of bioelectrochemical CO2
ethylene has been reported in aqueous electrolytes using Cu electrodes conversion. Herein, a brief introduction to these C4 compounds is
[106] or with other substrates instead of CO2, direct ethylene production presented.
from CO2 in bioelectrochemical conversion has not been reported to Thermodynamically, CO2 or bicarbonate can be reduced to butyrate
date, and ethylene-forming enzyme systems have not yet been clearly at a cathode potential of -0.37 V vs SHE under biological conditions
defined [23]. In the near future, the synthesis of ethylene directly from [23]; butyrate can also be directly produced from CO2 via the Wood­
CO2 is expected to be achieved through genetic or metabolic engineering –Ljungdahl pathway, which is the most energetically efficient pathway
in order to impart the electroactive recipient strains with an ethylene known for CO2 conversion coupled with acetyl-CoA reduction [114].
production system or by combining with other secondary technologies; According to R. Ganigue et al., who were the first to achieve the bio­
for example, methane produced in MES can be used as a feedstock in electrochemical production of butyrate from CO2 as a sole carbon
syngas platforms to produce ethylene [107]. source, CO2 reduction to butyrate is a hydrogen-driven process [115].
Early in 2014, butyrate was synthesized from CO2 by Toshiyuki Ueki
5.3. C3-bioproducts from CO2 et al. with an engineered strain of the acetogen Clostridium ljungdahlii as
the catalyst by introducing plasmids with butyrate production genes into
Diverse C3 chemicals are reported to be produced utilizing CO2 as a the Clostridium ljungdahlii chromosome [116]. Later, by adjusting the
substrate in MES, including but not limited to propionate CO2 feeding strategy and hydraulic retention time [117], Ludovic
(CH3CH2COOH), which can be further converted to ordinary triols such Jourdin et al. achieved increasing selectivity towards butyrate over ac­
as propanol (CH3CH3CH2OH), isopropanol ((CH3)2CHOH), and glycerol etate, with a high production rate of 2.0 ± 0.1 g/L/d (max 3.1 g/L).
(CH2OHCHOHCH2OH). Propionate, is an antifungal agent and is widely Isobutyrate is an isomer of butyrate, and it can also be produced at a rate
used in the agricultural, food, and pharmaceutical industries, and it can of 0.63 mM/d from the conversion of CO2 using graphite felt as a
be produced by carbonylation of ethylene and methanol from synthetic cathode via mixed anaerobic culture, according to Sovik Das et al. [118].
gas. Recently, bioproduction of propionate from adequate CO2 in the By introducing innovative electrode materials such as copper ferrite
flue gas has been gaining increasing attention due to its sustainability. supported reduced graphene oxide [85], the production rate of iso­
Chao Ma et al. engineered a sophisticated strain, utilizing the chromo­ butyrate reached 35.37 g/m2/d because of the large surface areas of the
somal incorporation of heterologous L-threonine deaminase, permease, materials and the synergistic effects of bimetals. In addition, 2,3-butane­
and acyl-CoA thioesterase, the deletion of branch pathways and the diol has a place in the bioelectrochemical product spectrum [119].
overproduction of the endogenous branched-chain alpha-keto acid de­ Butanol is widely used in chemical production and is sometimes
hydrogenase complex; they achieved high-purity propionate production accompanied by the production of butyrate at low pH values and high
of 0.6 g/L/h without apparent byproducts [108], which indicates that concentrations of undissociated organic acids [115]. According to San­
the engineering of microbial strains is meaningful and is full of promise dipam Srikanth et al., butanol can be synthesized through a direct
for obtaining better bioconversion with higher purification and electron transfer pathway utilizing selectively enriched mixed culture
selectivity. biofilms and taking CO2 as the substrate [120].
Propanol can be oxidized to produce propionaldehyde and further Succinate, existing widely in a variety of plants and animal tissues,
oxidized to produce propionic acid. In MES, propanol can be obtained by can be used as in medicines or food additives or as an important inter­
the reduction of propionic acid under the catalysis of dehydrogenase mediate in organic synthesis, and it can also be used to prepare five-
through a microbial metabolic pathway on the surface of the cathodic membered heterocyclic compounds such as succinic anhydride, allow­
electrode. Compared to propanol, isopropanol is a more common bio­ ing succinate to play a major role in industrial production. Therefore,
product. Isopropanol was first reported to be produced stably with a the bioelectrochemical synthesis of succinate is of great practical sig­
production rate of 1.17 ± 0.34 g/m2/d from CO2 using a mixed culture nificance in. Succinate can be generated by the hydrolysis of high-
by Arends et al., expanding the range of bioelectrochemical products energy thioester bonds in succinyl CoA catalyzed by succinate thio­
and opening up possibilities for secondary alcohol production in MES kinase [121]. To date, most succinate production has been performed by
[109]. Regrettably, the mechanisms behind the formation of iso­ genetically engineered bacteria such as engineered Escherichia coli
propanol remain unclear. In addition, 1,3-propanediol was reported to [122], or by metabolically engineered bacteria such as the type I
be synthesized using engineering technology that enables cyanobacteria methanotroph Methylomonas sp. DH-1 [123]. Among the currently
to directly produce valuable multicarbon organic compounds from CO2 existing studies, Escherichia coli is the most commonly used recipient
[110]. In this study, a synthetic metabolic pathway was introduced to strain because of its diversified metabolic pathways.

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

5.5. Bioproducts longer than C4 from CO2 of multicarbon, biobased products. Compared to short-chain fatty acids,
medium-chain fatty acids have superior physical properties as pre­
The potential for MES to produce medium-chain organic compounds cursors to fuels and chemicals [124]. Microbial electrosynthesis of
has been extensively explored in recent decades due to the higher value multicarbon chemicals has greatly expanded the practical application

Table 2
Value-added bio-products from MES using CO2 as a substrate.
Carbon chain Products Production rate Total Coulombic Types of functional microorganisms The types Cathode materials Reference
length of the efficiency of culture
product

Thermophilic microorganisms originated Mixed Carbonized coconut

340 mmol/m3/d —— [68]
from a subsurface formation culture shells
Hydrogenotrophic methanogens in the Mixed
Methane —— 64.30 ± 4.83 % Carbon felt [88]
mixed culture culture
8.81 ± 0.51 Methanococcus maripaludis in the pure Pure
58.9 ± 0.8 % Graphite rods [25]
C1 mmol/m2/d culture culture
Shewanella oneidensis MR-1 in the pure Pure
0.59 mmol/h —— Copper plates [92]
culture culture
Formic acid 2
63.2 mmol/m / Thermophilic Moorella thermoautotrophica Pure
65 % Carbon cloth [93]
d in the pure culture culture
Methanol —— —— Multi-enzymatic catalysis —— —— [94]
58.2 mmol/m2/ Thermophilic Moorella Pure
65 % Carbon cloth [93]
d thermoautotrophica in the pure culture culture
Mixed Reticulated vitreous
0.78 g/L/h 35 % Acetogenic microbiome [86]
culture carbon foam cathode
Acetate Mixed
1.06 g/L/d 63 % Mixed microbial community Carbon felt [96]
culture
Electro-autotrophic microorganism Graphite stick placed
Mixed
35.8 g/m2/d —— culture enriched from an anaerobic between two graphite [128]
C2 culture
sludge felts
Pure
1.46 g/L/h —— Engineered Saccharomyces cerevisiae —— [101]
culture
Mixed
Ethanol 8.46 g/m2/d 49 % Selective mixed culture Gas diffusion electrodes [102]
culture
T Pure
0.015 g/L 84 % Clostridium scatologenes ATCC 25775 Carbon felt [103]
culture
Ethylene 17 μmol/cm2/h —— —— —— Copper mesocrystal [106]
Pure
Propionate 0.6 g/L/h —— Engineered Pseudomonas putida —— [108]
culture
Mixed Carbon-based electrode
Propanol 0.4 mM/L/d —— Mixed Sulfate-reducing bacteria culture [129]
culture materials
1.17 ± 0.34 g/ Mixed
C3 Isopropanol 34 ± 19 % Modified homoacetogenic medium Carbon felt [109]
m2/d culture
Pure
Lactate 2.5 g/L/h —— Engineered Escherichia coli —— [111]
culture
Geobacter sulfurreducens in the pure Pure
Glycerol 6.0− 9.0 mM/d —— Polarized stainless steel [112]
culture culture
2
1.9 ± 0.6 g/m / Mixed
35 ± 12 % Modified homoacetogenic medium Carbon felt [109]
d culture
Mixed
0.54 g/L/d 58.90 % Mixed microbial culture solid-state electrode [130]
culture
Butyrate
Mixed
3.3 ± 0.2 g/L/d 69.8 ± 2.8 % Mixed microbial culture Carbon felt [117]
culture
Mixed
1.82 mMC/d 32.00 % Enriched carboxidotrophic mixed culture Carbon cloth [115]
culture
Mixed
Isobutyrate 0.63 mM/d —— Mixed anaerobic cultures Graphite felt [118]
C4 culture
Plain graphite plate
Mixed
Butanol 2 g/L/d 84.87 % Mixed anaerobic cultures loaded with carbon [120]
culture
powder
Pure
1.3 g/L/h —— Engineered Escherichia coli —— [122]
culture
Metabolic engineering of the type I Pure
Succinate 134 mg/L —— —— [123]
methanotroph Methylomonas sp. DH-1 culture
1.10 mol/mol Pure
50.70 % Engineered Escherichia coli. Carbon cloth [121]
glucose culture
Mixed
Valerate 1324 mg/L 109 % Waste activated sludge Carbon cloth [125]
culture
Mixed
2.0 ± 0.1 g/L/d 69.8 ± 2.8 % Mixed microbial culture Carbon felt [117]
culture
Caproate
Mixed
>C4 739 mg/L 45 % Mixed anaerobic cultures Graphite felt [126]
culture
Mixed
Caprylate 36 mg/L 45 % Mixed anaerobic cultures Graphite felt [126]
culture
Isoamyl Metabolically engineered Saccharomyces Pure
2.1 mg/L —— —— [127]
alcohol cerevisiae culture

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S. Zhang et al. Journal of CO2 Utilization 51 (2021) 101640

potential of MES through chain elongation, which can be initiated to combine the advantages of different strains through genetic or metabolic
synthesize up to C4 products such as caproate [117], valerate [125], and engineering [22], for example, combining naturally electroactive mi­
caprylate [126], as well as isoamyl alcohol [127]. Most of these medium crobes with model bacteria with mature synthetic biology tools in order
carbon chain compounds were produced not directly from CO2 but to equip electrically inactive microbes with electrical activity [16] to
rather from some simple CO2-derived products [57]. For example, Van acquire a specific product accumulation. Taking the study of Zaiqiang
Eerten-Jansen et al. first reported the chain elongation of acetate to Wu et al. as an example, the electron transfer pathway from S. oneidensis
caproate using a cathode as the electron donor [126]. In addition to was employed to confer electrical activity to Escherichia coli and,
acetate, methane can be used as a substrate in syngas platforms to thereby, confer the ability to capture CO2 and produce long-chain
produce other valuable products, e.g., ethylene, through multistage products [121]. Another priority is to clarify the detailed production
biotransformation [21]. Apart from microbial chain elongation, engi­ mechanism of a given product so that production of the target product
neering technologies play an important role in long-chain bioproduct can be controlled by artificially designing synthesis pathways and
formation by editing a specific metabolic pathway, which is an emerging reorganizing related enzymes. In addition to expanding the variety of
research field among MES. At the same time, discovering or selecting products, improving product purity is a consideration. Therefore,
novel microbial strains that possess medium-chain compound synthetic placing product separation and purification technology after the pro­
pathways also makes sense in production processes. The summary of duction process to improve production efficiency and product purity for
value-added bio-products from MES using CO2 as a substrate are illus­ industrial applications and long-term operation of MES will be an
trated in Table 2. effective method. Compared to conventional fuel cells, MES operate
under relatively mild conditions without using expensive precious
6. The status quo and future perspectives of bioelectrochemical metals as catalysts, and relatively few variables need to be controlled,
CO2 conversion which brings convenience to system performance optimization. From an
application point of view, bioconversion of CO2 is an attractive option
Bioelectrochemical CO2 transformation techniques are currently for the production of industrially relevant renewable biocommodities
taking the lead. These approaches consume a reduced amount of energy and is expected to reach large-scale application if the economic benefits
compared to conventional chemical reduction techniques and can be brought about by the value-added products can compensate for prior
operated under atmospheric pressure and ambient temperature, thereby investment.
decreasing system maintenance costs and improving safety. These
techniques can capture and reduce CO2 into high-quality bioproducts 6.2. Enrichment of CO2 for better capture efficiency
and fuels and transform excess CO2 into renewable energy, which makes
them an environmentally friendly solution to control the atmospheric Fluctuations in CO2 concentration in the flue gas might bring vari­
CO2 concentration, consistent with the sustainable development of ations in CO2 utilization performance [131] and become a limiting
world energy. factor in the multi-carbon compounds production process via MES.
Although MES theoretically possesses high energy conversion effi­ Hence, a low concentration of flue gas CO2 may lead to a low cell density
ciency, in real-world applications, owing to changing environmental in the cathodic chambers and, accordingly, a low system production
factors and operating conditions, the performance of the systems will be rate. Enrichment of CO2 in the gas stream, combined with bio­
affected to varying degrees. In addition to certain impacting factors electrochemical CO2 capture and conversion, is also a challenge to be
outside the system, microorganisms inside the systems have an impact solved. Therefore, porous electrodes can be introduced for direct gas
due to differences in microorganism type and corresponding metabolic delivery and, thus, theoretically achieve faster mass transfer and a
pathways. Microorganisms have a low absorption rate of electrons from higher CO2 concentration in electrolytes. Besides, CO2 membrane sep­
extracellular electrodes, as well as low current density, low product aration technology is also a promising emerging technology in CO2
synthesis efficiency, and low product quality, which limit the industrial capture [132], combining CO2 membrane separation technology with
application of MES. Limited by the current types of microorganisms and MES will improve CO2 capture efficiency and further improve CO2
their metabolic pathways, the products are mostly short-chain fatty conversion efficiency.
hydrocarbons. Moreover, the cost of constructing bioelectrochemical
CO2 capture and conversion reactors is relatively high, which is a limi­ 6.3. Strengthen the electron transfer efficiency based on the mechanisms
tation to expanding beyond the laboratory scale, so the obvious core
issues regarding large-scale application are how to effectively decrease The extracellular electron transfer efficiency of electroactive micro­
construction and operating costs and to increase the economic benefits organisms is low, resulting in insufficient electrocatalytic ability, which
of the bioproducts. On the other hand, due to the low concentration of is the main bottleneck restricting the application of electroactive mi­
CO2 in the atmosphere, it is hard to achieve a high enough yield and croorganisms. The low electron transfer efficiency hinders the further
production rate to balance the initial energy input. Moreover, CO2 engineering improvement of MES and the diversity of synthetic prod­
conversion and capture efficiency of these bioelectrical systems are al­ ucts. Electrode material optimization also plays a vital role in the
ways relatively low and limit their application in real-world projects. development of MES, and research on electrode materials is always
Based on the above considerations, we can also gain some insights for advancing since many new materials with excellent performance and
improving the performance of MES and for expanding the spectrum of breakthrough technologies are endlessly emerging. Electrode material
bioproducts. modification has led to considerable development in CO2 capture and
conversion in MES. Applying these new materials to the electrode proper
6.1. Widen product spectrum and improve the purity may lead to better electron transfer efficiency and microbial growth and
adhesion effect [20]. Based on the specific mechanism, the electron
Improving the efficiency of CO2 capture and microbial electrosyn­ transfer efficiency can be strengthened in a purposeful way. A deep
thesis and expanding the categories of bioconversion products are the understanding of microbial EET is crucial to understand the processes
key breakthrough directions for future research in this field. Isolating driving operation of MES and boost bioproduct production [42]. How­
and selecting high-quality microorganisms that possess faster CO2 fixa­ ever, the detailed mechanisms behind electron transfer and exchange
tion pathways and plentiful product synthesis pathways would be an remain unclear.
efficacious method. In addition, the biofilms forming on the surface of
the cathode must be stable enough over a long period to sustain a long
life cycle. Another method to widen the product spectrum would be to

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