RSER

Renewable and Sustainable Energy Reviews 156 (2022) 111997
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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser
Electron donors and mediators in the thermodynamics and kinetics of

CO2 bioreduction
Mohsin Kazmi a, b, Muhammad Irfan a, b, Lei Zhou a, Shan Yuan a, Hira Fatima c, Li-Yiang Tian a,
Yang-Li Ye a, Qian-Shan Lu a, Xiao-Yang Lu a, Shi- Zhong Yang a, Ji-Dong Gu d, Bo-Zhong Mu a, e, *
a
State Key Laboratory of Bioreactor Engineering and School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai,
200237, PR China
b
Department of Chemical, Polymer and Composite Materials Engineering, University of Engineering & Technology, KSK Campus, Lahore, 54890, Pakistan
c
Department of Chemical Engineering, Curtin University of Technology, Perth, Western Australia, 6845, Australia
d
Environmental Engineering, Guangdong Technical Israel Institute of Technology, Shantou, Guangdong, 515063, PR China
e
Engineering Research Center of Microbial Enhanced Oil Recovery, East China University of Science and Technology, Shanghai, 200237, PR China
A R T I C L E I N F O A B S T R A C T
Keywords: Carbon dioxide (CO2) accumulation in the environment, due to various thermochemical activities, is the primary
Thermodynamics reason for drastic global climatic changes. For dealing with the large CO2 volume with low concentration,
Kinetics bioreduction to various valuable products seems a viable option. Certain factors including microbes, electron
Biotransformation
donors, and their thermodynamic and kinetic behavior are critical for this process. However, there is very rare
CO2
Synthrophy
literature available focusing on these aspects. In this review, a systematic classification of electron donors has
Electron donors been presented to better understand their role in CO2 bioreduction (C2R). A thermodynamic framework has been
discussed to analyze the effect of abundantly available electron donors on the thermodynamics of C2R. The effect
of the electron donors’ phase on the kinetics of C2R has been elucidated using classical two-film theory.
Hydrogenotrophic syntrophic C2R has been presented as a special case.
relatively longer-term, ongoing, and slow solution and requires short-

term support from the other two options. Carbon capture and storage
1. Introduction
provide the solution of CO2 reduction with a lot of economic burdens but
without the production of any valuable products. Therefore, researchers
Thermodynamically, CO2is a stable compound with carbon in its
have been more interested in the conversion of CO2 to value-added
maximum oxidation state (+4). This stability is the main reason why
products instead of just keep storing them. No doubt, the cost of CCC
CO2 has been accumulating in the environment due to the imbalance of
would be higher than CCS, but this approach has the potential to provide
CO2 fixation by the natural processes e.g., photosynthesis and oceanic
a sustainable solution to the problem under consideration [1–7].
absorption; and rate of CO2 production by various thermochemical hy
In order to economically convert CO2 to value-added products, the
drocarbon conversion processes including petrochemicals production,
application of a catalyst is indispensable [1,2,8–12]. Based on the nature
power generation, and domestic activities. According to an estimation,
of the catalyst, the CO2 conversion processes can be broadly categorized
the CO2 is 3.9% in excess of its natural utilization and the overall con
into two routes namely (1) chemical reduction (2) bioreduction [2,13,
centration in the ambient is about 385 ppm compared to 200 ppm a
14]. In route (1), catalysts are made of transition metals while route (2)
couple of centuries ago. According to an estimate by international panel
involves the application of microorganisms. Both routes help the CO2
on climate change (IPCC), it is expected that the concentration of CO2
conversion kinetics by lowering the activation energy. Each route offers
may reach up to 570 ppm resulting in a 1.9 ◦ C increase in global tem
its pros and cons. Although, CO2 conversion by chemical route offers
perature by the start of the next century [1,2].
rapid kinetics it usually takes place at higher temperature and pressure
To avoid the catastrophic consequences, a few broader approaches in
and requires expensive catalysts [2]. These catalysts are sensitive to any
practice are (1) forestation (2) carbon capture and storage (CCS), and (3)
impurities, the reactants may carry. On the contrary, biochemical
carbon capture and conversion (CCC). Among these, option (1) is a
* Corresponding author. State Key Laboratory of Bioreactor Engineering and School of Chemistry and Molecular Engineering, East China University of Science and
Technology, Shanghai, 200237, PR China.
E-mail address: bzmu@ecust.edu.cn (B.-Z. Mu).
https://doi.org/10.1016/j.rser.2021.111997
Received 1 April 2021; Received in revised form 15 November 2021; Accepted 9 December 2021
Available online 7 January 2022
1364-0321/© 2021 Elsevier Ltd. All rights reserved.
M. Kazmi et al. Renewable and Sustainable Energy Reviews 156 (2022) 111997
List of abbreviations TA Thermodynamic analysis

VAP Value added products
Abbreviation PP Partial pressure
C2R CO2 Bioreduction MWCNTs Multiwalled carbon nanotube
IPCC International panel on climate change DNA Deoxyribonucleic Acid
CCS Carbon capture and storage LEDs Liquid Electron donors
CCC Carbon capture and conversion SEDs Solid electron donors
PEM Proton exchange membrane NADH Reduced nicotinamide adenine dinucleotide
PEDs Primary electron donors FADH2 Flavin adenine dinucleotide
SEDs Secondary electron donors FD Ferredoxin
EPS Extracellular protein substances SC2R Syntrophic CO2 reduction
SPPEDs Solid-phase primary electron donors Fdh Formate dehydrogenase
MEC Microbial electrolytic cell Ftr Formyl-methanofuranse
GPPEDs Gas phase primary electron donors H4MPT Tetramethanopterin
LPPEDs Liquid phase primary electron donors Fwd Formyl-MFR dehydrogenase
EDs Electron donors Hdr Heterodisulfide reductase
SEDs Secondary electron donors Mcr Methyl coenzyme reductase
LPSEDs Liquid phase secondary electron donors CoM Coenzyme M
BEC Bio-electro-chemical EETM Extracellular electron transfer mechanisms
COD Chemical oxygen demand DIET Direct interspecies electron transfer
SHE Standard hydrogen electrode MIET Mediated interspecies electron transfer
ADQS Anthraquinone-2,6-disulfonic acid disodium salt IIET Indirect interspecies electron transfer
conversion (route (2)) offers a cost-effective solution for CO2 conversion electron donor sources like water, wastewater, acetate, etc. are oxidized
as these processes can be operated on waste streams using inexpensive and hydrogen ions are generated in the anode compartment while
microorganisms. However, the main disadvantage of the pure electrons are transferred to the anode. The electrons move through the
biochemical route is the slow kinetics in terms of longer start-up time external circuit and reach the cathode while hydrogen ions move to
and lower CO2 conversion. One solution to this problem is the applica wards the cathode and cross the proton exchange membrane (PEM) if
tion of voltage to the rate of the biochemical reactions [7,13,15–17]. present. Table 1 shows the reduction of CO2 to valuable products and the
Fig. 1 shows a typical setup for CO2 bioelectrochemical reduction or number of electrons required to make them [18–21]. In such a system
simply C2R. It consists of two electrodes called anode and cathode, the microorganisms exist in two ways i.e., (1) biofilm and (2) planktonic
usually, representing two compartments separated by a proton exchange cells. Both forms of microorganisms behave differently with respect to
membrane [7]. Oxidation half-reaction takes place in the anode electrons acceptance and hence C2R. Biofilms can accept electrons
compartment. This section may or may not have any microorganisms. A directly from the electrode surface while planktonic cells may receive
reduction half-reaction takes place in the cathode compartment. In CO2 electrons with the aid of mediators such as H2 or by microbial syntrophy
biotransformation this section has microorganism(s) as single isolated [13,19,22–24]. High power is invested to increase the C2R kinetics
culture, co-culture, or mixed culture. During the normal operation, and/or to drive thermodynamically unfavorable reactions that can be
supplied from sustainable energy options like solar energy, wind energy,
etc. [25–28]. In literature diverse compounds have been used as the
electron donors and mediators for C2R. Choice of electron donors/me
diator play a vital role in deciding thermodynamics and kinetic of C2R.
However, no systematic classification of the electron donor has been
proposed so far. Therefore, core objective of this review article is to
present systematic classification of the electron donors/mediators and
provide an insight into their role in the thermodynamics and kinetics of
the bioreduction of CO2 to value-added products s.
2. Electron donors and mediators
Electron donors are the species that readily give up electrons. They
are also called the primary substrate for microorganisms. Usually, the
process of electron donation and acceptance takes place as an oxidation
and reduction couple. These processes generate energy that is consumed
in the microorganisms’ growth. In a typical anaerobic microbial respi
ration process, an electron donor is generally an organic compound such
as hydrogen, water, wastewater, acetate, formate, etc. However, some
inorganic compounds such as zero-valent metals (Feo, Mno) also act as
electron donors.
2.1. Classification of electron donors and mediators
C2R has become a wide topic of interest as indicated by hundreds of

Fig. 1. Basic structure of microbial electrolytic cell for CO2 bioreduction. research articles being published every year. In literature, the term
2
Table 1
Important value-added products by CO2 bioreduction.
Item Product Name Chemical formulae (Oxidation State) No. electrons required for Transformation Cathode Potential
Fuel Carbon C 4 − 0.627

Carbon Monoxide CO 2 − 0.106
Methane CH4 8 − 0.244
Ethene CH2=CH2 12 0.064
Volatile Fatty Acids Formic Acid HCOOH 2 − 0.43
Acetic Acid CH3COOH 8 − 0.29
Propionic Acid CH3CH2COOH − 0.29
Butanoic Acid CH3CH2CH2CH3COOH 20 − 0.28
Alcohols Methanol CH3OH 6 − 0.39
Ethanol CH3CH2OH 12 − 0.335
Propanol CH3CH2CH3OH 24 − 0.30
Butanol CH3CH2CH2CH3OH 24 − 0.30
Other Oxalic Acid COOH–COOH 2 − 0.5
Formaldehyde HCHO 4 − 0.07
Glycerol C3H8O3 − 0.39
electron donor has been used for three basic types of the species viz, (1) exogeneous electron donors is enormous, however, in this review, we
substances donating electrons to the microorganism (2) substances shall discuss only widely studied exogeneous electron donors such as
donating electrons to electrode (3) electrode donating electrons to the hydrogen, electrode, metals, minerals, water, and wastewater [31,41,
microorganisms (4) mediators [13,29–36]. Option (1) describes the 43–50].
typical anaerobic digestion where microorganisms break down the A basic framework for the classification of exogenous electron do
complex organic compounds and gain electrons for their anaerobic nors has been developed as shown in Fig. 2. Primarily, microorganisms
respiration and utilize CO2 as the electron acceptor. The options (2), (3) accept electrons in two ways i.e., (1) directly as the electrons from the
and (4) indicate the electrosynthesis of the different value-added prod electrode (2) indirectly as H2 or formate [10,37,48,51,52]. Therefore,
ucts by C2R [3,4,20,37–39]. In many experiments, multiple compounds electrodes and H2/formate have been termed as the primary electron
in different phases may act as electron donors and in the absence of no donors (PEDs). All the remaining compounds like acetate, water,
definite classification, their role becomes quite ambiguous to wastewater, zerovalent metals, etc. have been classified as secondary
understand. electron donors (SEDs) as they produce the PEDs, i.e., either hydrogen or
To classify electron donors, it’s important to make a frame of refer electrons or both. In literature, H2 and formate are sometimes also called
ence to avoid any confusion. If we consider microorganisms as the sys mediators as they act as the carrier of electrons from PEDs to the mi
tem under consideration where CO2 transformation takes place, then crobes [11]. In the case of mixed culture, extracellular protein sub
there are two broad types of electron donors: (1) endogenous electron stances (EPS) also act as an important mediator [39]. Such compounds
donors (2) exogenous electron donors [28,40]. Examples of endogenous not only facilitate extracellular electron transfer but also intracellular
electron donors include flavin and ferroixde, enzymes of methano metabolism. Intracellular mediators are not the focus of this study.
genesis, etc. [41,42]. These are the compounds that are found in the
microorganism and act as electron donors in different pathways. On the 2.2. Primary electron donors
contrary, exogenous electron donors are those who are outside of the
microorganisms and interact directly or indirectly with them. List of PEDs are those electron donors that directly interact with the
Fig. 2. A proposed framework for electron donor classification for CO2 bioreduction where primary electron donors, interact directly with the cell membrane, are
produced by secondary electron donors also called electron donor source.
3
microorganisms and transfer the electrons. They can be classified ac 2.3. Secondary electron donors
cording to their state as solid, gas, or liquid (solution) as shown in Fig. 2.
It is important to involve the state of electron donors in the classification SEDs are those donors that don’t interact directly with the microbes’
because, kinetics and thermodynamics of any process are strongly cell wall to supply reducing equivalents. They are the compounds that
influenced by the state of the electron donor. - act as the source for those entities (e− and H+) which are easily
Numerous studies show that microorganisms can receive electrons acceptable for the microorganism for C2R. Like PEDs, SEDs can also be
from solid-phase primary electron donors (SPPEDs) directly or indirectly classified based on their phase. A brief description of a few important
[10,53–58]. Minerals, zero-valent metals, and cathodes are the widely secondary electron donors has been given below.
studied examples of SPPEDS [41,55,59]. The interest in SPPEDS was Among metals, iron is the widely used electron donor for C2R to
triggered when about a decade ago, Cheng et al. (2009), observed that different products. It is found to be an abundant, inexpensive, and non-
microbes can directly convert CO2 to CH4 at the expense of electricity. toxic element [15]. Generally, it is used in two oxidation states as the
Later, it was shown that it was possible to reduce CO2 to various value electron donor, (1) zero-valent iron (Feo), and (2) Fe2+. Zero valent iron
added products by controlling voltage and other conditions like sub can be produced by the reduction of iron ores, iron milling, vapor
strate, culture type, etc. [3,20,38,60]. In this part of the article, impor deposition [1]. In literature, various metals in their zerooxidation state
tant solid electron donors namely, cathode, minerals, and zero-valent have been used as electron donors like Alo, Zno, and Nio [67].
metals will be discussed. As indicated in the LPPEDs, if formate, methanol, etc. are used as the
In C2R, value-added chemicals are produced in the cathode LPPEDs, then C2R may not be favored due to kinetic resistance. How
compartment in a two-section configuration. In 2009, Cheng et al. ever, they can be effectively utilized for C2R reduction if used as LPSEDs
showed that CO2 can be biotransformed to CH4 by directly accepting in MEC setup. Therefore, formate, acetate, and methanol have been
electrons from the carbon cathode at a voltage less than − 0.7 V using a classified as potential LPSEDs. Other important LPSEDs include water,
two-chamber electrochemical reactor containing an abiotic anode, bi wastewater. In most of the studies on C2R, water has been used as the
otic cathode, and without any precious metal catalyst. They found very electron donor due to its abundance and being cheap. The advantage of
high efficiencies of CO2 conversion to CH4 i.e., 96%. In microbial elec using water as the electron donor in the dual chamber is that it produces
trolytic cell (MEC) operation, microbes may exhibit two behaviors in the hydrogen ions for the C2R in the cathode compartment and oxygen in
cathode compartment i.e., (1) biofilm (2) planktons. In the case of bio the anode compartment which may have some commercial value.
film, microbes accept electrons directly from the electrode surface However, the application of water as an electron donor generates some
through c-type cytochrome and hydrogenase or via pili [61]. In such a challenges to deal with. First, the dissociation of water requires a lot of
case, the diffusional limitation faced by electron donors (H2) is not faced energy which can be compensated by renewable energy sources i.e.,
[25]. However, planktons need some mediators to receive electrons solar energy, wind energy, etc. The second important aspect while using
indirectly from the cathode. \One of the major costs in setting the MEC is water as electron donor is the O2 permeability through the cation ex
the cost of cathode material. Therefore, many researchers have focused change membrane towards the cathode compartment where anaerobic
on the use of the inexpensive carbon-based cathode [43,61]. Conductive culture performs C2R. The third problem is the corrosion of the anode
minerals like hematite, lemonite, ferrite, etc. have been shown to act as which may be addressed by using inert metal anode [9,29,30].
SPPED electrons in both biochemical and bioelectrochemical CO2 Short-chain fatty acids-based electron donors like formate, acetate, and
transformations. These minerals act as an electrical network in many alcohols like methanol and ethanol are all can act as electron donor. All
anaerobic situations and help to transfer electrons among the microbes. of these compounds are water-soluble and can be consumed by various
This phenomenon has been termed electric syntrophy or direct inter acetogens as well as methanogens as the sole energy sole. Also, not all
species electron transfer. Recently, it has also been investigated those bacteria can grow on formate due to its antibacterial effects [30].
synthetic carbon-based conductive materials also act as conduits for Therefore, it finds some limitations. However, in their pure state, it may
electron transfer [62]. The role of minerals and conductive materials has not be economical to use them as electron donors, rather they are
been shown to be synergetic to C2R resulting as compared to the simple valuable potential C2R products due to their wide industrial application.
bioreduction. Many industrial wastewaters contain fatty acids and alcohol. For
Hydrogen and Carbon monoxide are two potential gas phase primary instance, aluminum formate has better coagulant properties than other
electron donors (GPPEDs) [30]. However, All the biochemical trans aluminum salts like aluminum sulphate and aluminum chloride. Simi
formations without any application of electricity, are carried out by larly, sodium formate is used to prepare reducing agents like sodium
supplying hydrogen. During the CO2 bioreduction, CO may be produced dithionite and sodium dithionate [68]. In the brewery industry, ethanol
as an intermediate. Like hydrogen, carbon mono oxide can be generated is the primary waste [51]. Its metabolism produces acetic acid with the
by different renewable (electrochemical, photochemical) and chemical release of electrons as under:
methods (gasification). Acetogens prefer to consume CO than Hydrogen.
CH3 CH2 OH + H2 O→CH3 COOH + 4H+ + 4e−
Its toxic and flammable gas [30]. Anaerobic microbes cannot uptake
complex compounds as electron donors in the liquid state. There are Due to low price, abundance, and growing ecological awareness,
only a few liquid phase primary electron donors (LPPEDs) that can wastewater of such industries can be used as the desirable electron
directly interact with the microbes and supply listing formate, acetate, donor in both biochemical and bioelectrochemical (if external energy is
and methanol [36,56,64]. All these compounds are miscible in water. required to overcome thermodynamic barriers) setups. Like industrial
They can be used by the microbes through different pathways not only as wastewater, simulated domestic wastewater has also been tested by
an electron donor but also as a carbon source. Therefore, if they are Zeppilli et al. in the anode compartment of bio-electro-chemical (BEC)
made directly in contact with microbes, as in the case of a typical setup and they found steady current [18,31,45,69,70]. Application of
biochemical arrangement, the uptake of CO2 may not be preferred due wastewater in BEC setup revealed two-fold benefits, (1) higher columbic
to different kinetic resistances as discussed in section 4 [65]. Another efficiencies (2) reduction of chemical oxygen demand (COD) (3) even
aspect regarding acetate and methanol is that their application may very dilute wastewater can be used [7].
result in the production of more CO2 on the net instead of using it [51, Hydrogen gas can be generated from various processes, including
66]. Therefore, the role of liquid compounds i.e., acetate and formate chemical, biochemical, and electrobiochemical [29,63]. Each process
are salts as EDs may not be as supportive as in the case of SPEDs or has its pros and cons. Bioelectrochemical has emerged as a promising
GPEDs for C2R. method if renewable energy acts as the basic source [7]. Hydrogen is
non-toxic but highly explosive. Nevertheless, it is the most discussed
donor in the literature C2R literature. H2 mediated extracellular electron
4
transfer is the dominating mode of C2R above − 0.41 V vs SHE without Usually, the bioelectrochemical reactions are reversible in nature as
having any negative effect on microbial performance. Hydrogen gas is given by the general reaction equation (4) specifically for C2R to value
the most investigated gas-phase electron donor as it can be produced added products (VAP).
readily by abiotic reduction at the electrode surface [30].
CO2 + bED→cVAP (4)
2.4. Mediators where a, b, and c are stoichiometric coefficients and ED represents
electron donor. For such a process, an equilibrium constant “K” can be
Mediators are the compounds that facilitate the transfer of electrons defined as under:
between electrode and microorganisms. In the cathode compartment,
they are reduced by the electrode and give up electrons on interaction [VAP]c
K= (5)
with microbes and are being regenerated. They can be used to stimulate [CO2 ]a [ED]b
the growth of microorganisms in the start-up phase. In the case of mixed
It is possible to relate the equilibrium constant “K” to the standard
culture, extracellular polymer substances (EPS) act as mediators any
Gibbs energy as given by equation (6).
there may not be any need for external compounds as the mediators.
However, in the case of single culture different compounds like neutral ΔGo = − RT lnK (6)
red, anthraquinone-2,6-disulfonic acid disodium salt (ADQS), methyl
vilogen, etc. may be used as the mediator [25]. where “R” is the ideal gas constant (8.314 J/mol. K) and T is the absolute
standard temperature. Usually, 25 ◦ C and 1 atm are the standard con
3. Electron donors and C2R thermodynamics ditions. Usually, the operating conditions of temperature and pressure
being studied for C2R are very close to standard conditions. Therefore,
Thermodynamic analysis (TA) provides a theoretical evaluation of a on comparing equations (2) and (6) a simplified relationship between
transformation i.e., whether a reaction is feasible or not. Usually, a Eocell and K is given by equation (7).
feasible reaction is represented by the negative Gibbs energy change, an
RT
indication of an exergonic process. An unfavorable reaction shows the o
Ecell = lnK (7)
nF
positive Gibbs energy change. However, TA does not tell how the re
action will occur as it does not provide any idea about the activation For T = 25 ◦ C = 298 K, the equation (7) can be simplified as under:
energy. The thermodynamics of a reaction can be understood as a RT 8.314 × 298
boundary within which reaction kinetics plays a vital role in any
o
Ecell = lnK = lnK
nF n × 96486
transformation. The thermodynamics of C2R strongly depends on the
choice of an electron donors as it is the main reactant of the trans o
Ecell = 0.0266 lnK (8)
formation [25]. Therefore, the purpose of this section is to discuss the
Similarly, we can write
important thermodynamic concepts being used for C2R and then how
different electron donors affect the favorability of C2R. Also, factors that o
ΔG = − RT lnK = − 8.314 × 298 lnK
affect the role of electron donors in these biotransformation’s have been
briefly discussed. ΔGo = − 2477.57 lnK (9)
Thermodynamically, C2R processes can be categorized as either
3.1. Theoretical background
spontaneous or non-spontaneous depending upon whether the trans
formation in the direction of value added products formation is
Gibbs free energy is a fundamental concept to analyze the thermo
exothermic or endothermic. The spontaneous reactions have a negative
dynamics of any chemical or biochemical transformations. Itis a state
value of ΔGo and are called favorable reactions and unfavorable for the
function, and depends on the initial and final equilibrium states, not the
vice versa. A detailed thermodynamic favorability or unfavourability
path through which the change occurs. The general expression of Gibbs
criteria has been given in Fig. 3.
free energy being applicable to biochemical as well as bio
electrochemical reactions, at standard conditions, is given by the
expression (1) [71]: 3.2. Effect of electron donor on C2R thermodynamics
ΔGo = ΔH o − TΔSo (1) To demonstrate the effect of electron donors on the thermodynamics
where ΔHo is the change in enthalpy (the total energy contents of the
system) and ΔSo is the change in entropy (the measure of system dis
order). In the case of an electrochemical system, the total work done by
the system can be calculated as under:
ΔGo = − n FEcell
0
(2)
where “n” is the number of moles of electrons given by the electron

donor to the acceptor involved in the reaction and F is the Faradaic
constant having a value 0.64855 × 104 C/mol. e. Therefore, in any CO2
biotransformation, the total charge transfer from electron donors to CO2
is nF. The negative sign in equation (2) represents that the work is done
by the system on the surrounding.
As C2R is non-spontaneous in nature, therefore, Eocell represents the
standard applied external voltage. It is the electromotive force between
two half cells i.e., Cathode half-cell or Eocathode and Anode half cell or
Eoanode as under by the equation (3):
Fig. 3. A thermodynamic framework to investigate the effect of electron donor
o
Ecell o
= Ecathode o
− Eanode o
= EC2R reduction −
o
EED (3)
Oxidation
on CO2 bioreduction to valuable production.
5
Table 2
Effect of electron donor on the thermodynamics of the C2R to VAPs.
SED Anode Potential (V) Fatty Acids
HCOOH CH3COOH Butyrate Oxalic Acid
ΔGo ΔEcello K ΔGo ΔEcello K ΔGo ΔEcello K ΔGo ΔEcello K
Water 0.82 241.21 − 1.25 0.91 856.79 − 1.11 0.71 2547.20 − 1.10 0.36 254.72 − 1.32 0.90
Wastewater − 0.29 27.02 − 0.14 0.99 0.00 0.00 1.00 − 23.16 0.01 1.01 40.52 − 0.21 0.98
Fe(II) − 0.672 − 46.7 0.242 1.02 − 294.86 0.38 1.13 − 907.73 0.39 1.44 − 33.19 0.17 1.01
Biofuels
C Methane Ethene CO
Water 0.82 558.46 − 1.45 0.80 821.28 − 1.06 0.72 875.31 0.70 20613.06 − 106.82 0.00
Wastewater − 0.29 130.06 − 0.34 0.95 − 35.51 0.05 1.01 − 409.87 0.35 1.18 20398.86 − 105.71 0.00
Fe(II) − 0.672 − 17.37 0.05 1.01 − 330.36 0.43 1.14 − 852.16 0.74 1.41 20325.14 − 105.33 0.00
Alcohols
CH3OH CH3CH2OH CH3CH2CH3OH CH3(CH2)2CH3OH

Water 0.82 0.82 700.48 − 1.21 1337.28 − 1.16 0.58 2593.52 − 1.12 0.35 2593.52 − 1.12 0.35
Wastewater − 0.29 − 0.29 57.89 − 0.10 52.10 − 0.05 0.98 23.16 − 0.01 0.99 23.16 − 0.01 0.99
Fe(II) − 0.672 − 0.67 − 163.25 0.28 − 390.19 0.34 1.17 − 861.42 0.37 1.42 − 861.42 0.37 1.42
of the C2R a simple and widely used combination of PEDs and SEDs was dependent on the concentration of minerals. It has been investigated
taken under consideration [1,6,9,17,60]. Usually, water, wastewater that in the iron water system, the Fe3O4 layer develops on the anode
(acetate), minerals (Fe) are employed as the SEDs in the studies, and through the following oxidation reaction [31]:
Cathode is used as the PED. The selected value added products were
3Fe+2 + 4H2 O→Fe3 O4 + 8H+ + 2e− (10)
from four different classes i.e., biofuels, fatty acids, alcohols, and other
important compounds as given in Table 1. The value of ΔGo calculated In this system, the anode potential (Eoanode ) is given by the following
for the C2R to value added products applies to whether the reduction equation:
process is biochemical or bioelectrochemical. Table 2 represents the
effect of electron donors on the C2R to the value added products based E = 0.98 − 0.236pH − 0.0886 log[Fe2+ ] (11)
on the framework shown in Fig. 3. It demonstrates that, if the electron Equation (11) shows that Eoanode
not only depends on the Fe(II) ionic
donor is changed for C2R to the same product, not only the extent of concentration. For 1 M Fe(II) solution at 7 pH, the Eoanode would be
reaction but also the feasibility of the biotransformation process may − 0.672 V. However, the actual potential would be greater than this due
alter. For example, if the water is used as the secondary electron donor, to anode overpotential problem. This overpotential is represented as the
the process of C2R to formate is unfavorable and thermodynamically not reaction activation loss. Similarly, Fe(II) concentration also affects the
possible without the expenditure of external voltage. However, if microbial function as well in biochemical reactions as discussed in the
instead of water, Fe(II) containing iron salt is used, the process becomes kinetic section.
feasible and it can be done without the application of the external Partial pressure (PP) of the gases is an important thermodynamic
voltage. A similar trend has been observed for almost all the products. In parameter as it affects many aspects. PPH2, whether as a supplied GPPED
some cases, like the effect of wastewater on the C2R to acetic acid, shows as well as in case of syntrophic interaction in which case electron donor
some values 0,0 and 1 corresponding to ΔGo , Eocell and K, respectively. is produced as the metabolic intermediate product, is very significant.
This is because, generally, the wastewater is simulated as acetic acid. It The low partial pressure of intermediate electron donors indicates a
means, if we use the same compound as the electron donor in the anode favorable situation for the upstream generation process as well as the
compartment and target the same compound in the cathode compart downstream consumption process for C2R [57]. Also, the solubility of a
ment, then theoretically, speaking no reaction will take place. But in gas in the water is a strong function of its partial pressure in the gas
practice, wastewater is not just acetic acid and it has many other in phase. In this case, higher partial pressure is important to ensure a
gredients and some values of the aforementioned parameters may be greater amount of gas in the liquid phase.
observed. As the values, of K, are near to the 1 in almost all the cases, The solubility of H2 (a GPPED) and CO2 is a very important param
which means the calculations being performed are near to the eter in C2R. It indicates the availability of the gases for the
equilibrium.
3.3. Factors affecting the role of electron donors in C2R thermodynamics
As already, discussed that the thermodynamic favorability is not

absolute, rather it strongly depends on the type of the electron donor.
Similarly, there are many intensive and extensive properties related to
electron donors which can affect the spontaneity of a biochemical re
action. For example, let us take the case of syntrophic biodegradation of
complex organic molecules to methane. if the methanogens don’t
maintain a low partial pressure of H2 (a GPPED), the syntrophic bacteria
cannot perform their degradation. Keeping in view, the phase of electron
donor and their effect on C2R, the following properties have been briefly
discussed: 1) minerals concentration, 2) partial Pressure of H2, 3)
diffusivity of CO2 and H2, and 4) solubility.
In C2ER, the role of anode potential (Eoanode ) is very important as it
drives the electron towards the cathode. This potential is strongly Fig. 4. Effect of temperature on diffusivity of electron donors.
6
bioconversion to the products. The amount of gas dissolved in the water according to the classical two film theory [72] which states that, CO2
is a function of its partial pressure in the overhead gas and temperature pass through the liquid-gas interphase followed with the travel in be
as given by Henry’s law as under: tween the gas film. As the water absorbs CO2, its density increases and
moves away from the interphase, and is replaced by the water with low
P
Swater = (12) CO2 concentration. Initially, the rate of absorption of CO2 would be fast
KH
and tends to slow as the water gets saturated with CO2. For practical
where Swater is the solubility of the gas in water, P is the partial pressure purpose, it can be assumed that gas-liquid interphase once saturated,
of the gas and KH is Henry’s constant. Solubility is also strongly remain saturated. The solubility of CO2 is a strong function of temper
dependent on the nature of the gas, and therefore, different gases have ature [35] and increases with the decrease in temperature. In bulk, the
different KH under the same conditions of partial pressure and temper decrease in CO2 concentration depends on its utilization. However, the
ature. The solubility of CO2 in the water at 25 ◦ C is 1.4 g. Kg/water and phenomenon is slower as the diffusion coefficient of CO2 is 0.0000177
H2 is 0.00155 g/Kg/water. cm2/s [73]. As far as, C2R value added products is concerned, two
While diffusion is a kinetic phenomenon, the diffusion coefficient prominent places for CO2 utilization can be identified in bulk liquid
depends on thermodynamic parameters like temperature. Fig. 4 shows namely (1) Planktonic cells (2) Biofilm as explained in the following
the effect of temperature, from 10 ◦ C to 35 ◦ C, on the diffusion of some sections. Most of the biocatalysts operate better in the range of 30–60 ◦ C,
important gases like H2, CH4, and CO2. It shows that on increasing the which is contrary to the CO2 solubility as already discussed in the
temperature the diffusivity of the gases increases almost linearly which thermodynamic section. Zhen et al. (2018) tested five different types of
may be due to an increase in the kinetic energy of the gas molecules. CO2 cathode and in each cathode, they sparged CO2 after every 24 h. It was
and CH4 have almost the same gas diffusivities across all the tempera found that this step was responded by a peak in the electron flow and
ture range while H2 shows the diffusivities more than twice due to being hence, more CH4 formation was observed. Also, in this study, the lag
low in molecular weight. phase was very negligible. This could be due to the fact that CO2 was the
only substrate and daily CO2 sparging ensured the presence of a suffi
4. Electron donors and C2R kinetics cient quantity of substrate required in the initial growth phase. Other
wise, a clear lag phase is usually observed in the C2R to CH4.
The thermodynamic study considers the energy of the reactants and
products at equilibrium. It is the job of the kinetic study to shed light on 4.2. C2R kinetics with gas-phase primary electron donors and mediators
the pathway, reactants are converted into products, and the dynamic
limitations [3]. As discussed in the thermodynamics, the selection of an Hydrogen is the most common GPPED. It can be produced biotically
electron donor may alter the overall favorability of the reaction, in this or abiotically within the system or can be supplied externally. Fig. 5
section, we shall explore the effect of an electron donor on the kinetics of shows that it follows similar kinetic steps as CO2 from the gas as the
C2R to value added products. In this context, the state of the electron solubility of hydrogen is far less than that of CO2 as represented by the
donor plays a vital role. Therefore, this section has been organized based dimensionless Henry’s Constant (HH2 = 50) compared to CO2 (HCO2 =
on the physical state of the electron donor. 1.8). It means whether the hydrogen is produced in situ or supplied ex-
situ, most of H2 will be present in the gas phase and hence the con
4.1. CO2 mass transfer kinetics sumption of a limited amount of H2 in the liquid phase may be much
faster than CO2 as the diffusivity DH2 is much higher than DCO2 [74].
Regardless of the phase of the electron donor and mediator, the ki Based on the hydrogen being produced and utilized two basic types
netics of CO2 remains the same. Fig. 5 shows the effect of the physical of extracellular electron transfer mechanisms can be identified, viz, (1)
state of the electron donor on the C2R kinetics. In all cases, the transport direct electron transfer (2) indirect electron transfer [21 [34],37,75]. In
of CO2 to the liquid media is the fundamental step that can be explained direct electron, transfer hydrogen is consumed in H+ form along with e−
Fig. 5. Role of electron donor phase and mechanisms in the CO2 bioreduction kinetics. In case of microbial electrolytic cell, solid phase primary electron donor is a
cathode and connected to an anode via an external circuit. Without electricity, cathode compartment acts a typical biochemical cell.
7
Table 3
Effect of primary and secondary electron donors on the kinetics of CO2 bioreduction.
Culture Primary Electron Secondary Important Lag Phase Log Phase Mechanism Ref.
Donor Electron Parameters (time)
Products Rate (as Performance
donor
published) Indicator
Mixed Culture Carbon Stick (CS) Water − 1.1V Minimal CH4 20.1 mL L− 1 DET and DIET [32]
d− 1
CS with carbon Minimal CH4 24.1 mL L− 1
fiber d− 1
CS wrapped in Minimal CH4 75.8.0 mL 90% CO2
graphite felt L− 1 d− 1 Capture
CS twined with Ti Minimal CH4 29.9 mL L− 1
Wire d− 1
CS with carbon Minimal CH4 47.4 mL L− 1 H2 IET
cloth d− 1
Mixed Culture Reticulated Water − 1.1 3–20 days Acetate 1330 g m− 2 Co.E 99% BioH2Mediated ET [46]
vitreous carbon d− 1
electrode
Mixed Culture Carbon felt Water, Na- − 1.1 V Nil Acetate 171.4 mmol C.E 65% DIET and MIET [92]
Acetate m− 2 d− 1
CH4 0.31 L CH4. 82% of
g− 1 COD Theoretical
removed
Propionate Very low
Formate Very low
Acetobacterium Hydrogen Gas – Submerged Nil Acetate 148 g L− 1 d− 1
H2 mediated [47]
woodii Membrane Electron Transfer
Reactor
1
Clostridium Graphite felt and Water − 0.9 V Nil Acetate 2.4 mM d− C.E. 89.23% DET [93]
ljungdahlii stainless steel H2 Mediated ET
assembly,
H2 (7% head
space)
1
Mixed Culture Graphite felt and Water − 1.1 V 25 days Acetate 1.35 mM d− C.E. 49.91% Mediated ET [93]
stainless steel CH4 10% Head H2 Mediated ET
assembly space
Mixed Culture Carbon felt K4 [Fe(CN)6] − 0.9 V 30 days CH4 0.096 ± 0.01 CoE DET [94]
enrichment mmol. h− 1 19.13–73.94%
⋅3H2O VFA
(Acetate, N.D H2 Mediated ET
Propionate
Mixed Culture MWCNT Water − 0.85 V 7 days Acetic Acid 685 ± 30 g. CoE 100% BioH2Mediated ET [95]
m− 2.d− 1
1
Mixed Culture Carbon felt, H2 Acetate, − 1.1 V Nil CH4 101.9 mL d− 80–90% H2 Mediated ET [75]
Water − 1.15 V Nil Acetic Acid 129.32 mL DET
d− 1
Sporomusa ovata Graphite, H2 Water − 0.4 V Nil Acetate N.D 86% DET [10]
2- N.D
oxobutyrate
by the microbes as shown in Fig. 5. Usually, in this mechanism, the supplied at the start of the experiment. It is important to note from
microbe is in direct contact with another microbe or with the SPPEDs, Table 3 that the performance of the microbes in the lag phase may be
called biofilm. This mechanism usually requires less energy to take more dependent on the availability of CO2 and electron donor (H2) and
place. For instance, in the case of C2R to CH4 -0.244 V V SHE is required. lesser dependent on the surface area of the cathode. However, after the
However, this process yields low rates of value added products pro lag phase, the surface area of the cathode seems to dominate as we can
duction due to various diffusional resistances as explained in SPPEDs. In see that multiwalled carbon nanotube (MWCNTs) showed the highest
the case of mixed culture, there could be a generation of some biogenic flow rate of value added products and at higher columbic efficiencies.
Hydrogen. But the lateral process is very slow and at low voltage, its role
is usually negligible. The in-direct mechanism takes place at a potential
more negative than − 0.51 V V SHE. In this case, H+ takes up an electron 4.3. C2R kinetics with solid-phase electron donors and mediators
and is converted to H2 gas shown in Fig. 5 and can be taken up by the
planktons. Though this process requires much more energy than direct Microbes (archaea and bacteria) exhibit different behavior if some
electron transfer, higher production rates of the value added products interphase is present in the system [22]. In the case of solid electron
have been observed as shown in Table 3. Another way of indirect elec donors and mediators like cathode, minerals, etc., the microbes tend to
tron transfer in the absence of electrical energy would be the supply of form a biofilm on the solid surface, which represents, not only, a diverse
H2 gas as the electron donor along with CO2. In this case, the typical form of life, but also, an important kinetic resistance as shown in Fig. 5.
kinetics steps from the gas phase to the liquid phase are the same as This phenomenon is dominant in the case of a mixed culture. The biofilm
described in the case of CO2 according to the two-film theory. In com stops growing when the supply of nutrients is difficult for the inner
parison to CO2, H2 is a nonpolar gas, and therefore, its solubility is 100 microbes. The development of biofilm on the solid electron donors,
times less than that of CO2. However, being the smaller molecule, H2 whether primary or secondary, strongly depends on the physicochem
diffuses about 3.5 times faster than CO2. ical characteristics of the system, electron donor’s surface free energy,
Table 3 also reveals that the lag phase may be avoided if H2 is and hydrophilicity [76].
The process of biofilm development on the electron donor surface
8
comprises five distinct stages namely (1) reversible attachment on SED process complex and difficult to identify the rate-controlling step.
(2) irreversible attachment on SED (3) growth of microcolonies (4) Therefore, before deciding which of the kinetic steps in C2R is limiting
mature biofilm (5) detachment of cells. Among these five stages, the SED the production of value added products, there is a need to first specify
surface is important in the first two stages, while in the lateral stages the system and its condition. In this review, two basic CO2 conversion
extracellular polymer substances (EPS) plays the dominant role. processes have been discussed i.e., biochemical transformation with and
Generally, the number of EPS has been observed. EPS not only keeps the without applied voltage. Both processes have distinct rate-limiting steps.
biofilm intact but also acts as the mediator for electron transport across In the case of C2R without applied voltage, the overall rate-controlling
the solid electron donors. By composition, EPS comprises DNA, proteins, step is the production of reducing equivalent i.e., H+/e− or H2, and is
and polysaccharides [76–78]. shown by a long lag phase ranging from days to months. However, in the
Biofilm represents a region in the MEC where microbe-the biocata case of C2R with applied voltage, the microbes still require some time to
lyst, exists in a very high population in a varied situation. The microbes adapt to the situation and a lag phase exists ranging from hours to days.
which are at the outer rim of the biofilm have relatively easy access to However, the transfer of electrons is usually considered to be rate-
CO2 but transport of reducing equivalent is limited as the diffusion limiting [80]. Another rate-controlling aspect is the low solubility of
coefficient of EPS is much lower than that of water [78]. On the con H2. The situation becomes worse when the solution contains various
trary, the microbes which are directly attached to the surface of solid salts and the temperature is usually not ambient for optimum microbes’
electron donors, the reducing equivalent are readily available to them, performance. Therefore, to evaluate the rate-limiting step one needs to
but CO2 will not be easily accessible. The microbes which are placed in consider the reacting species as well as their conditions.
between may have optimized access of both CO2 and reducing equiva
lents. It may be due to this reason, the rate of production of value-added 5. Syntrophic CO2 bioreduction
products like CH4, acetic acid, etc. is not very high when operated near
respective, equilibrium conditions. These kinetic resistances may also Syntrophy can be defined as a thermodynamically interphylums
contribute to the lag phase of the biochemical reactions. The phenom and/or intraphylum dependent process in which microbial-breakdown
enon is complex as it has been seen that agitation does not add any of complex hydrocarbons (electron source or secondary electron do
important value to the production of the products because shearing nors) takes place only when the degradation-end-products (hydrogen,
disturbs the biofilm formation. Bajracharaya et al. (2016) first applied formate, and acetate) are maintained at low concentration by the
the CO2 diffusion cathode. in this modification, both reducing equiva following species [36,81,82]. This section is dedicated to syntrophic CO2
lents and CO2 were introduced from the middle of the electrolytic cell bioreduction (SC2R). SC2R can only be found in the anoxic environment
and resulted not only result in a higher percentage of the CO2 gas but consisting of one or more fermentation steps followed by methano
also in higher production of acetic acid and alcohols. genesis [82]. Nevertheless, it is important to point out that SC2R takes
Table 3 also shows an overview of the literature review using place in the proximity of nitrate, sulphate, and iron syntrophic reduction
different SED. It shows that Extensive studies have been carried out in nature [63,83]. It is a special type of interspecies interaction in which
using carbon materials as the electron donor. The addition of minerals as each species performs an ecologically important step that keeps the
the electron donors acts as the solid conductor and has been found to overall process favorable to occur in nature. In SC2R, metabolically
facilitate the diverse syntrophic microbial interaction as given in Fig. 5. distinct partners from different phylums i.e., bacteria and archaea, work
It is important to note that not all minerals may facilitate the C2R pro in harmony to survive in natural or artificial ecosystems under diverse
cess. it has been found that only conductive and semiconductive min conditions of substrates, temperature, and pH. The important organisms
erals do this job [79]. in this phenomenon are found in syntrophacea and methanogens
(methanobacteriales, methanomicrobiales, and methanosarcinales) or
4.4. C2R kinetics with liquid phase electron donors and mediators ders in the anaerobic environment [84]. The bacterial syntrophic
members often appear to be highly adaptive as indicated by the unique
In comparison to solid and gas phases, the liquid phase is relatively multiple membrane complexes and reduced genomic inventories
convenient for the microbes to consume electron donors as PED as there (acyl-CoA synthases, hydrogen, or formate-evolving/producing de
are relatively lesser kinetic resistances. While solids (minerals and hydrogenases and reductases) [84,85]. Syntrophs work in H2 deficient
electrodes) are being employed as the PED in the literature, LED can be environments to ferment complex substrates (propionate and butyrate
either primary or secondary. Examples of LEDs include formate, acetate, etc.) to CO2 and hydrogenotrophic methanogens, which are physiolog
methanol, ethanol. These LEDs can be used as SED in the MEC setup as ically specialized, are accountable for keeping H2 concentrations small.
well. In this section, we shall discuss their role as PED as well as SED. This metabolic relationship cannot be overruled by the addition or
Fig. 5 indicates the typical kinetics of a LED. However, a major problem subtraction of some nutrient or co-substrate. In nature, syntrophic in
with LED is that they also act as the source of carbon for the biotrans teractions produce educts in different phases (solid, liquid, and gas) but
formation to different products, due to which the consumption of CO2 in this section, we will focus on hydrogenotrophic methanogenesis as
may not occur. One of the most important examples, in this case, is the this is the most occurring and discussed the process in the literature.
production of methane from CO2 only if the hydrogenotrophic mecha During syntrophic interactions, diverse types of compounds
nism is followed. However, in the case of mixed culture, if along with including reducing equivalents (hydrogen, formate, acetate), organic,
CO2, LED like formate and acetate or alcohols are present then other sulfur, and nitrogen-based and toxic compounds are produced and
mechanisms like acetoclastic and methylotrophic pathways may be exchanged. The methanogens consume the reducing equivalents in two
preferred due to low kinetic hindrance. Although the energetic of these prominent pathways i.e., (1) acetotrophicc (2) hydrogenotrophic. In
pathways are relatively less favorable as compared to hydrogenotrophic. nature, the contribution of acetotrophic mechanism is 2/3 although the
CO2/N2 environment is provided in almost all the research work related hydrogenotrophic mechanism is thermodynamically more favorable.
to anaerobic culturing. But usually, the kinetics of CO2 are not shown However, as explained in sections 2,3, and 4, acetotrophic is kinetically
which is a big drawback of the literature available so far. There is a need easy to take place and hence, it dominates in nature. In this section,
to focus on the C2R using various LEDs. hydrogenotrophic mechanism will be further discussed as the electron
donor as its role is fundamental in nature [86,87].
4.5. Rate-limiting step
5.1. Thermodynamics of syntrophic CO2 reduction
In C2R, multiple kinetic processes including mass transfer, charge
transfer, and microbial growth take place simultaneously, making the Energetic constraints are the driving force for the microorganisms to
9
have syntrophic relationships across different phylums or different or 5.3. Syntrophic hydrogenotrophic CO2 bioreduction
ders of the same phylum. This strategy results in changing the thermo
dynamics of the intermediate reactions. Let us take the example of H2 While syntrophic bacteria may utilize relatively complex electron
production which is a key electron donor in all the SC2R. The standard donors and substrates, methanogens grow on simple or PEDs as
Gibbs energies for the production of hydrogen gas (H2) from ferredoxin, explained in section 2. The methanogens can be categorized as (i)
reduced nicotinamide adenine dinucleotide (NADH), formate, and flavin hydrogenotrophic: these are the microbes that do not have cytochromes
adenine dinucleotide FADH2 are respectively, + 3, +18, − 3, and +37 kJ and grow on CO2, H2, or formate; (ii) acetoclastic: these have cyto
mol− 1. However, under an H2 deficient environment i.e., at 1 Pa H2, the chromes and grow on acetate and; (iii) methylotrophic: these also have
ΔG value turned negative ferredoxin (FD (− 26 kJ mol− 1), NADH (− 11 cytochromes and grow on methanol [90]. Although in nature, 2/3
kJ mol− 1)), or more negative (formate (− 32 kJ mol− 1)) or less positive methane production is by the acetolactic mechanism, from syntrophic
FADH2 (+8 kJ mol− 1) compared to the nonsyntrophic H2 production, all point of view, the role of hydrogenotrophic methanogens is more
showing an increased favorability of the production of reducing equiv important. As already explained, the job of hydrogenotrophic metha
alent (H2 in this case) during syntrophic process. This strategy reduces nogens is to maintain low partial pressure of the H2 to ensure the
the use of resources, enhances the longevity of survival, proliferation, energetically possibility of the syntrophic bacteria’s performance.
and provides important electron donors for the methanogens. However, Therefore, it can be said that, in SC2R, the rate-controlling step is the
regardless of the hydrogen concentration the, hydrogenotrophic C2R is hydrogenotrophic reduction of CO2. There are two possible hydro
thermodynamically favorable with ΔG = − 32.7 kJ mol− 1. However, genotrophic mechanisms termed direct electron transfer and indirect
studies have shown that in natural environments as well as anaerobic electron transfer as already explained in section 4. In addition to H2,
digester, higher temperature (55–65 ◦ C) may be due to kinetic (activa formate can also be used by the hydrogenotrophic methanogens to
tion energy) requirements [82,88]. produce methane. The only difference in the hydrogenotrophic mecha
In nature and lab experiments, it has been observed that the rate of nisms utilizing formate and H2 is that CO2 is reduced to formate external
syntrophic CH4 production cannot be explained merely based on H2 to methanogens by the bacteria using formate dehydrogenase. In
only. Formate is another important syntrophic metabolite that facilitates hydrogenotrophic C2R, several enzymes (energy-converting hydroge
methane production in two ways i.e., (1) as electron shuttle (2) syn nase (Eha), formate dehydrogenase (Fdh), F420-reducing hydrogenases
trophic substrate. The pathway adopted by the formate to produce CH4 (Fru and Frc), formyl-methanofurnase (Ftr), tetramethanopterin
is the same as H2 and thermodynamically favorable with ΔG = − 130 kJ (H4MPT) formyltransferase, formyl-MFR dehydrogenase (Fwd), heter
mol− 1. However, this phenomenon is dependent on the type of microbial odisulfide reductase (Hdr), etc), and coenzymes (methyl coenzyme
community [82,88]. reductase, (Mcr), coenzyme M (CoM), coenzyme B(CoB), sulfhydryl
coenzyme M (HS-CoM), sulfhydryl coenzyme B (HS–CoB), hetero
5.2. Kinetics of electron donor production in syntrophy disulfide coenzymes (CoM-S-S-CoB), etc) takes part in the trans
formation [91].
Syntrophic CO2 reduction is a result of a series of intermicrobial and
intramicrobial biological reactions. Kinetically, there are two major 5.4. Electron transfer mechanisms
steps of the overall SC2R (1) kinetics of the electron donor production
(2) kinetics of electron donors utilization. Therefore, it’s inevitable that Syntrophic Microbes conserve energy by complex intra and extra
the rate of reactions is slower in the case of SC2R. cellular electron transfer mechanisms. The important intracellular
In a syntrophic environment, different factors participate through mechanisms which ensure the production of electron donors are reverse
different mechanisms to produce electron donors like H2 and formate, electron transfer, electron bifurcation, and electron confurcation. The
etc. Some important factors which affect SC2R rate are discussed as important extracellular electron transfer mechanisms (EETM) are direct
under including substrate and pathway, coenzymes, and metabolites. interspecies electron transfer (DIET) and mediated interspecies electron
Microbes are well known for their substrate specificity. In SC2R, not transfer (MIET) [56,58]. While intraspecies electron transfer is some
only the substrate concentration, but its type is also very important and what intrinsic in nature and quite reproducible as long as the H2 partial
governs the biochemical reactions. There are many substrates that may pressure is low, the performance of the syntrophic process depends on
be used by the syntrophic consortia; however, a few notable substrates the way interspecies electron takes place. Therefore, in this part, we
are butyrate, propionate, acetate, and formate. The detailed pathways shall discuss EETM.
can be found elsewhere. One mole of, each, propionate, and butyrate DIET can be considered as a conductive method of electron transfer
syntrophic oxidation produces 3 and 2 mol of H2, respectively. One mole between the cells as it does not require any electron carrier, like H2 or
of formate syntrophic oxidation produces 1 mol of H2 [82,89]. Enzymes formate, to transfer reducing equivalents from syntrophic bacteria to
and coenzymes play fundamental roles in the syntrophic oxidation of the methanogen archaea. It is celebrated for its relatively low energetic
substrate to produce electron donors (H2 mainly). They have a specific requirements. In this mechanism, the two microbes are in physical
activation site that ensures a definite biological pathway occurs. contact and the reducing equivalents are transferred in three ways: (1)
Although there are various proposed pathways for propionate and cell to cell contact (2) via pili (3) via conductive materials including
butyrate syntrophic oxidation to ED and other metabolites. However, biochar, carbon cloth, granular activated carbon, minerals, etc. as
the role of coenzyme A is relatively fundamental. In the syntrophic shown in Fig. 6.
oxidation of propionate notable coenzymes are reduced coenzyme MIET is also referred to as indirect interspecies electron transfer
(HS-CoA), Propionyl CoA, methylmalonyl CoA, succinyl CoA, and acetyl (IIET) by H2 and/or formate and is the prominent pathway in syntrophic
CoA. In this pathway, 1st molecule of H2 is produced in the conversion of degradation of complex molecules and SC2R. Between, H2 and formate,
Sccucinate to fumarate, 2nd malate to oxaloacetate, and 3rd pyruvate to MIET with H2 is considered better by the researchers keeping in view the
acetyl Co-A. Similarly, in the syntrophic oxidation of butyrate important diffusion perspectives. In the context of MIET, according to Fick’s law,
coenzymes are reduced coenzyme (HS-CoA), butyryl – CoA, crotonyl – the rate of diffusion (or mass or molar flux, q) of electron donor is
CoA, 3-hydroxybutyryl – CoA, acetoacetyl – CoA, and acetyl – CoA. In directly proportional to the electron donor concentration difference
this pathway, the 1st H2 molecule is produced in butyryl – CoA to cro (ΔC), inversely proportional to between the syntrophic partners and the
tonyl – CoA and 2nd in the conversion of 3-hydroxybutyryl – CoA to proportionality constant is the diffusivity as under [82]:
acetoacetyl – CoA [82].
ΔC
q= − D ×
d
10
Fig. 6. Mechanisms in syntrophic hydrogenotrophic CO2 bioreduction.
where D is diffusivity and d is the distance for ΔC As the molecular optimization. In syntrophic C2R, the process becomes more complex and
weight of formate is 15 times higher than H2, therefore, the H2 diffusion a lot of research is required to enhance the role of the hydrogenotrophic
is around 4 times quicker than formate making it more suitable for process as the acetoclastic mechanism is more favorable. In this aspect,
electron transfer (as per Garaham’s Law). In syntrophy, the role of the role of the cation exchange membrane may be tested and optimized.
concentration difference may not be exploited to enhance the rate of
electron donor diffusion, the distance between the syntrophic partner is 7. Conclusion
another important parameter that can be shortened to improve the rate
of syntrophic process. Many researchers have investigated mixing, C2R is an emerging method to produce fuels and chemicals in a
producing flocks, and aggregates to reduce the interspecies distance. sustainable manner. This review article discussed several critical aspects
of this process which is rarely discussed in the previous literature.
6. Challenges and future recommendations Electron transfer between CO2 and electron donors is a complex process
involving various Intra and extracellular electron transfer mechanisms.
Environmental problems resulting from the combustion of non- Systematic classification of the electron donors into primary and sec
renewable energy sources and the production of synthetic ondary electron donors as well as based on phase, help better under
hydrocarbon-based chemicals have put human survival in danger. The stand the transfer of electrons for C2R. While the type of electron donor
development of sustainable fuels and synthetic chemicals with zero net has a strong influence on the thermodynamic favorability of the C2R on
emissions is being targeted to avoid human sophistication at the expense a theoretical basis, the kinetics of the C2R provides the real picture of the
of environmental deterioration. In this connection, C2R to value added process. syntrophic CO2 reduction is a special case of C2R and offers a
products has received immense attention through the last decade as this feasible route to utilize complex hydrocarbons as electron donors for
biotransformation offers not only a sustainable solution to our hydrogenotrophic CO2 reduction.
industrialization-based ecological problems but also an economical
route to provide materials to fulfill our domestic and industrial raw Declaration of competing interest
materials requirements. In biochemical reactions, the transfer of elec
trons is a complex process and various substances act as electron donors The authors declare that they have no known competing financial
on a relative basis. Despite, the breakthroughs, this field is still in its interests or personal relationships that could have appeared to influence
infancy and there is a strong need to standardize the different aspects of the work reported in this paper.
research in this area. This review provides a framework for the basic
classification of electron donors valid for biochemical processes with or Acknowledgement
without the application of voltage to better understand their role in CO2
reduction. Electron donors are the key constituent of the C2R perfor This work was supported by the National Science Foundation of
mance as they not only act as an important reactant but also influence China (Nos. 52074129, 42061134011, 41530318), the Natural Science
different regimes of microbial growth and production rate. In these Foundation of Shanghai (No. 21ZR1417400), the Fundamental Research
steps, usually, the rate-controlling step is the extracellular transfer of the Funds for the Central Universities, China (No. 222201817017) and
electrons by the electron donors. Usually, direct electron transfer is University of Engineering and Technology Lahore, Pakistan.
considered to be thermodynamically a low energy process and hence an
attractive option. But kinetically, this process involves different diffu References
sional resistances depending upon the phase of the electron donor.
Similarly, in an attempt to convert CO2 to value added products, re [1] Müller K, Mokrushina L, Arlt W. Thermodynamic constraints for the utilization of
searchers need to visualize the system with clear identification of PEDs CO2. Chem Ing Tech 2014;86:497–503.
[2] Mikkelsen M, Jørgensen M, Krebs FC. The teraton challenge. A review of fixation
and SEDs. There is a need to deal with the kinetics of SEDs and PEDs and transformation of carbon dioxide. Energy Environ Sci 2010;3:43–81.
separately, particularly, in the case of bioelectrochemical processes. [3] ElMekawy A, Hegab HM, Mohanakrishna G, Elbaz AF, Bulut M, Pant D.
This may help better understand the C2R process for future Technological advances in CO2 conversion electro-biorefinery: a step toward
commercialization. Bioresour Technol 2016;215:357–70.
11
[4] Wang H, Gao P, Zhao T, Wei W, Sun Y. Recent advances in the catalytic conversion [37] Ma L, Zhou L, Ruan M-Y, Gu J-D, Mu B-Z. Simultaneous methanogenesis and
of CO2 to value added compounds. Sci China Chem 2015;58:79–92. acetogenesis from the greenhouse carbon dioxide by an enrichment culture
[5] Jiang Y, May HD, Lu L, Liang P, Huang X, Ren ZJ. Carbon dioxide and organic supplemented with zero-valent iron. Renew Energy 2019;132:861–70.
waste valorization by microbial electrosynthesis and electro-fermentation. Water [38] Reddy MV, Sun X. Bioelectrosynthesis of various chemicals and evaluation of their
Res 2019;149:42–55. microbiological aspects. Microb Electrochem Technol: Elsevier 2019:757–76.
[6] Li Z, Fu Q, Kobayashi H, Xiao S. Biofuel production from bioelectrochemical [39] Kumar M, Sundaram S, Gnansounou E, Larroche C, Thakur IS. Carbon dioxide
systems. Bioreactors for microbial biomass and energy conversion; 2018. capture, storage and production of biofuel and biomaterials by bacteria: a review.
p. 435–61. Bioresour Technol 2018;247:1059–68.
[7] Geppert F, Liu D, van Eerten-Jansen M, Weidner E, Buisman C, Ter Heijne A. [40] Luo X, Zhang F, Liu J, Zhang X, Huang X, Logan BE. Methane production in
Bioelectrochemical power-to-gas: state of the art and future perspectives. Trends microbial reverse-electrodialysis methanogenesis cells (MRMCs) using thermolytic
Biotechnol 2016;34:879–94. solutions. Environ Sci Technol 2014;48:8911–8.
[8] Logan BE, Rabaey K. Conversion of wastes into bioelectricity and chemicals by [41] Sousa FL, Preiner M, Martin WF. Native metals, electron bifurcation, and CO2
using microbial electrochemical technologies. Sci 2012;337:686–90. reduction in early biochemical evolution. Curr Opin Biotechnol 2018;43:77–83.
[9] Christodoulou X, Okoroafor T, Parry S, Velasquez-Orta SB. The use of carbon [42] Thauer RK, Kaster A-K, Seedorf H, Buckel W, Hedderich R. Methanogenic archaea:
dioxide in microbial electrosynthesis: advancements, sustainability and economic ecologically relevant differences in energy conservation. Nat Rev Microbiol 2008;
feasibility. J CO2 Util 2017;18:390–9. 6:579–91.
[10] Nevin KP, Woodard TL, Franks AE, Summers ZM, Lovley DR. Microbial [43] Liu W, Wang L, Gao L, Wang A-J. Hydrogen and methane production in
electrosynthesis: feeding microbes electricity to convert carbon dioxide and water bioelectrochemical system:: biocathode structure and material upgrading. Microb
to multicarbon extracellular organic compounds. mBio 2010;11:e00103–10. Electrochem Technol: Elsevier 2019:921–53.
[11] Karimi IA, Kawi S. Technoeconomic perspectives on sustainable CO2 capture and [44] Zabranska J, Pokorna D. Bioconversion of carbon dioxide to methane using
utilization. Environ Sci Pollut Res 2016;23:22223–5. hydrogen and hydrogenotrophic methanogens. Biotechnol Adv 2018;36:707–20.
[12] Visentin C, da Silva Trentin AW, Braun AB, Thomé A. Lifecycle assessment of [45] Zeppilli M, Mattia A, Villano M, Majone M. Three-chamber bioelectrochemical
environmental and economic impacts of nano-iron synthesis process for system for biogas upgrading and nutrient recovery. Fuel Cell 2017;17:593–600.
application in contaminated site remediation. J Clean Prod 2019;231:307–19. [46] Jourdin L, Grieger T, Monetti J, Flexer V, Freguia S, Lu Y, et al. High acetic acid
[13] Enzmann F, Mayer F, Rother M, Holtmann D. Methanogens: biochemical production rate obtained by microbial electrosynthesis from carbon dioxide.
background and biotechnological applications. Amb Express 2018;8:1–22. Environ Sci Technol 2015;49:13566–74.
[14] Lovley DR. Powering microbes with electricity: direct electron transfer from [47] Kantzow C, Mayer A, Weuster-Botz D. Continuous gas fermentation by
electrodes to microbes. Environ. Microbiol Rep 2011;3:27–35. Acetobacterium woodii in a submerged membrane reactor with full cell retention.
[15] Vyrides I, Andronikou M, Kyprianou A, Modic A, Filippeti A, Yiakoumis C, et al. J Biotechnol 2015;212:11–8.
CO2 conversion to CH4 using Zero Valent Iron (ZVI) and anaerobic granular sludge: [48] Marshall CW, Ross DE, Fichot EB, Norman RS, May HD. Long-term operation of
optimum batch conditions and microbial pathways. J CO2 Util 2018;27:415–22. microbial electrosynthesis systems improves acetate production by autotrophic
[16] Fu B, Conrad R, Blaser M. Potential contribution of acetogenesis to anaerobic microbiomes. Environ Sci Technol 2013;47:6023–9.
degradation in methanogenic rice field soils. Soil Biol Biochem 2018;119:1–10. [49] Kouzuma A, Kato S, Watanabe K. Microbial interspecies interactions: recent
[17] Mateos R, Escapa A, Vanbroekhoven K, Patil SA, Moran A, Pant D. Microbial findings in syntrophic consortia. Front Microbiol 2015;6:477.
electrochemical technologies for CO2 and its derived products valorization. Microb [50] Ma L, Zhou L, Mbadinga SM, Gu J-D, Mu B-Z. Accelerated CO2 reduction to
Electrochem Technol 2019:777–96. Elsevier. methane for energy by zero valent iron in oil reservoir production waters. Energy
[18] Xiang Y, Liu G, Zhang R, Lu Y, Luo H. High-efficient acetate production from 2018;147:663–71.
carbon dioxide using a bioanode microbial electrosynthesis system with bipolar [51] Rotaru A-E, Shrestha PM, Liu F, Shrestha M, Shrestha D, Embree M, et al. A new
membrane. Bioresour Technol 2017;233:227–35. model for electron flow during anaerobic digestion: direct interspecies electron
[19] Bajracharya S, Yuliasni R, Vanbroekhoven K, Buisman CJ, Strik DP, Pant D. Long- transfer to Methanosaeta for the reduction of carbon dioxide to methane. Energy
term operation of microbial electrosynthesis cell reducing CO2 to multi-carbon Environ Sci 2014;7:408–15.
chemicals with a mixed culture avoiding methanogenesis. Bioelectrochemistry [52] Ganigué R, Puig S, Batlle-Vilanova P, Balaguer MD, Colprim J. Microbial
2017;113:26–34. electrosynthesis of butyrate from carbon dioxide. Chem Commun 2015;51:3235–8.
[20] Jiang Y, Zeng RJ. Expanding the product spectrum of value added chemicals in [53] Cheng S, Xing D, Call DF, Logan BE. Direct biological conversion of electrical
microbial electrosynthesis through integrated process design—a review. Bioresour current into methane by electromethanogenesis. Environ Sci Technol 2009;43:
Technol 2018;269:503–12. 3953–8.
[21] Rojas MdPA, Zaiat M, Gonzalez ER, De Wever H, Pant D. Effect of the electric [54] Leng L, Yang P, Singh S, Zhuang H, Xu L, Chen W-H, et al. A review on the
supply interruption on a microbial electrosynthesis system converting inorganic bioenergetics of anaerobic microbial metabolism close to the thermodynamic
carbon into acetate. Bioresour Technol 2018;266:203–10. limits and its implications for digestion applications. Bioresour Technol 2018;247:
[22] Flemming H-C, Wuertz S. Bacteria and archaea on Earth and their abundance in 1095–106.
biofilms. Nat Rev Microbiol 2019;17:247–60. [55] Siegert M, Yates MD, Call DF, Zhu X, Spormann A, Logan BE. Comparison of
[23] Lee H-S. Electrokinetic analyses in biofilm anodes: ohmic conduction of nonprecious metal cathode materials for methane production by
extracellular electron transfer. Bioresour Technol 2018;256:509–14. electromethanogenesis. ACS Sustainable Chem Eng 2014;2:910–7.
[24] Ghangrekar M, Chatterjee P. A systematic review on bioelectrochemical systems [56] Tremblay P-L, Angenent LT, Zhang T. Extracellular electron uptake: among
research. Curr Pollut Reports 2017;3:281–8. autotrophs and mediated by surfaces. Trends Biotechnol 2017;35:360–71.
[25] Rabaey K, Rozendal RA. Microbial electrosynthesis—revisiting the electrical route [57] Rotaru A-E, Shrestha PM, Liu F, Markovaite B, Chen S, Nevin KP, et al. Direct
for microbial production. Nat Rev Microbiol 2010;8:706–16. interspecies electron transfer between Geobacter metallireducens and
[26] Schuchmann K, Müller V. Direct and reversible hydrogenation of CO2 to formate by Methanosarcina barkeri. Appl Environ Microbiol 2014;80:4599–605.
a bacterial carbon dioxide reductase. Sci 2013;342:1382–5. [58] Lee J-Y, Lee S-H, Park H-D. Enrichment of specific electro-active microorganisms
[27] Gildemyn S, Rozendal RA, Rabaey K. A Gibbs free energy-based assessment of and enhancement of methane production by adding granular activated carbon in
microbial electrocatalysis. Trends Biotechnol 2017;35:393–406. anaerobic reactors. Bioresour Technol 2016;205:205–12.
[28] Van Lingen HJ, Plugge CM, Fadel JG, Kebreab E, Bannink A, Dijkstra J. [59] Belay N, Daniels L. Elemental metals as electron sources for biological methane
Thermodynamic driving force of hydrogen on rumen microbial metabolism: a formation from CO2. Antonie Leeuwenhoek 1990;57:1–7.
theoretical investigation. PLoS One 2016;11:e0161362. [60] Nelabhotla ABT, Dinamarca C. Electrochemically mediated CO2 reduction for bio-
[29] Di Capua F, Pirozzi F, Lens PN, Esposito G. Electron donors for autotrophic methane production: a review. Rev Environ Sci Bio Technol 2018;17:531–51.
denitrification. Chem Eng J 2019;362:922–37. [61] Yu Y-Y, Zhai D-D, Si R-W, Sun J-Z, Liu X, Yong Y-C. Three-dimensional electrodes
[30] Claassens NJ, Sánchez-Andrea I, Sousa DZ, Bar-Even A. Towards sustainable for high-performance bioelectrochemical systems. Int J Mol Sci 2017;18:90.
feedstocks: a guide to electron donors for microbial carbon fixation. Curr Opin [62] Kato S, Igarashi K. Enhancement of methanogenesis by electric syntrophy with
Biotechnol 2018;50:195–205. biogenic iron-sulfide minerals. Microbiologyopen 2019;8:e00647.
[31] Martinez CM, Alvarez LH. Application of redox mediators in bioelectrochemical [63] Conrad R. Contribution of hydrogen to methane production and control of
systems. Biotechnol Adv 2018;36:1412–23. hydrogen concentrations in methanogenic soils and sediments. FEMS Microbiol
[32] Zhen G, Zheng S, Lu X, Zhu X, Mei J, Kobayashi T, et al. A comprehensive Ecol 1999;28:193–202.
comparison of five different carbon-based cathode materials in CO2 [64] Cord-Ruwisch R, Seitz H-J, Conrad R. The capacity of hydrogenotrophic anaerobic
electromethanogenesis: long-term performance, cell-electrode contact behaviors bacteria to compete for traces of hydrogen depends on the redox potential of the
and extracellular electron transfer pathways. Bioresour Technol 2018;266:382–8. terminal electron acceptor. Arch Microbiol 1988;149:350–7.
[33] Kondaveeti S, Min B. Bioelectrochemical reduction of volatile fatty acids in [65] Sleutels TH, Hamelers HV, Rozendal RA, Buisman CJ. Ion transport resistance in
anaerobic digestion effluent for the production of biofuels. Water Res 2015;87: microbial electrolysis cells with anion and cation exchange membranes. Int J
137–44. Hydrogen Energy 2009;34:3612–20.
[34] Rosenbaum M, Aulenta F, Villano M, Angenent LT. Cathodes as electron donors for [66] Ragsdale SW, Pierce E. Acetogenesis and the wood–Ljungdahl pathway of CO2
microbial metabolism: which extracellular electron transfer mechanisms are fixation. Biochim Biophys Acta Protein Proteonomics 2008;1784:1873–98.
involved? Bioresour Technol 2011;102:324–33. [67] Modestra JA, Mohan SV. Microbial electrosynthesis of carboxylic acids through
[35] Beiron J. Assessment of enhanced carbon dioxide absorption in water-The impact CO2 reduction with selectively enriched biocatalyst: microbial dynamics. J CO2
of carbonic anhydrase and pH regulation. 2017. Util 2017;20:190–9.
[36] McInerney MJ, Sieber JR, Gunsalus RP. Syntrophy in anaerobic global carbon [68] Selvaraj H, Aravind P, Sundaram M. Four compartment mono selective
cycles. Curr Opin Biotechnol 2009;20:623–32. electrodialysis for separation of sodium formate from industry wastewater. Chem
Eng J 2018;333:162–9.
12
[69] Saheb-Alam S, Singh A, Hermansson M, Persson F, Schnürer A, Wilén B-M, et al. [83] Lau MC, Kieft TL, Kuloyo O, Linage-Alvarez B, Van Heerden E, Lindsay MR, et al.
Effect of start-up strategies and electrode materials on carbon dioxide reduction on An oligotrophic deep-subsurface community dependent on syntrophy is dominated
biocathodes. Appl Environ Microbiol 2018;84. by sulfur-driven autotrophic denitrifiers. Proc Natl Acad Sci Unit States Am 2016;
[70] Schievano A, Goglio A, Erckert C, Marzorati S, Rago L, Cristiani P. Organic waste 113:E7927–36.
and bioelectrochemical systems: a future interface between electricity and methane [84] Sieber JR, McInerney MJ, Gunsalus RP. Genomic insights into syntrophy: the
distribution grids. Detritus 2018;1:57. paradigm for anaerobic metabolic cooperation. Annu Rev Microbiol 2012;66:
[71] Thakur IS, Kumar M, Varjani SJ, Wu Y, Gnansounou E, Ravindran S. Sequestration 429–52.
and utilization of carbon dioxide by chemical and biological methods for biofuels [85] McInerney MJ, Rohlin L, Mouttaki H, Kim U, Krupp RS, Rios-Hernandez L, et al.
and biomaterials by chemoautotrophs: opportunities and challenges. Bioresour The genome of Syntrophus aciditrophicus: life at the thermodynamic limit of
Technol 2018;256:478–90. microbial growth. Proc Natl Acad Sci Unit States Am 2007;104:7600–5.
[72] Karlsson H, Svensson H. Rate of absorption for CO2 absorption systems using a [86] Chauhan A, Ogram A, Reddy K. Syntrophic-methanogenic associations along a
wetted wall column. Energy Proc 2017;114:2009–23. nutrient gradient in the Florida Everglades. Appl Environ Microbiol 2004;70:
[73] Bajracharya S, Vanbroekhoven K, Buisman CJ, Pant D, Strik DP. Application of gas 3475–84.
diffusion biocathode in microbial electrosynthesis from carbon dioxide. Environ [87] Demirel B, Scherer P. The roles of acetotrophic and hydrogenotrophic
Sci Pollut Res 2016;23:22292–308. methanogens during anaerobic conversion of biomass to methane: a review. Rev
[74] Dupnock TL, Deshusses MA. Detailed investigations of dissolved hydrogen and Environ Sci 2008;7:173–90.
hydrogen mass transfer in a biotrickling filter for upgrading biogas. Bioresour [88] Thauer RK, Jungermann K, Decker K. Energy conservation in chemotrophic
Technol 2019;290:121780. anaerobic bacteria. Bacteriol Rev 1977;41:100.
[75] Jiang Y, Su M, Zhang Y, Zhan G, Tao Y, Li D. Bioelectrochemical systems for [89] Wallrabenstein C, Schink B. Evidence of reversed electron transport in syntrophic
simultaneously production of methane and acetate from carbon dioxide at butyrate or benzoate oxidation by Syntrophomonas wolfei and Syntrophus
relatively high rate. Int J Hydrogen Energy 2013;38:3497–502. buswellii. Arch Microbiol 1994;162:136–42.
[76] Renner LD, Weibel DB. Physicochemical regulation of biofilm formation. MRS Bull [90] Sieber JR, Sims DR, Han C, Kim E, Lykidis A, Lapidus AL, et al. The genome of
2011;36:347–55. Syntrophomonas wolfei: new insights into syntrophic metabolism and biohydrogen
[77] Kumar M, Sundaram S, Gnansounou E, Larroche C, Shekhar I, Thakur IS. Carbon production. Environ Microbiol 2010;12:2289–301.
dioxide capture, storage and production of biofuel and biomaterials by bacteria. [91] Lie TJ, Costa KC, Lupa B, Korpole S, Whitman WB, Leigh JA. Essential anaplerotic
A Rev Bioresour Technol 2017. role for the energy-converting hydrogenase Eha in hydrogenotrophic
[78] Sheng G-P, Yu H-Q, Li X-Y. Extracellular polymeric substances (EPS) of microbial methanogenesis. Proc Natl Acad Sci Unit States Am 2012;109:15473–8.
aggregates in biological wastewater treatment systems: a review. Biotechnol Adv [92] Xafenias N, Mapelli V. Performance and bacterial enrichment of
2010;28:882–94. bioelectrochemical systems during methane and acetate production. Int J
[79] Kato S, Hashimoto K, Watanabe K. Methanogenesis facilitated by electric Hydrogen Energy 2014;39:1864–21875.
syntrophy via (semi) conductive iron-oxide minerals. Environ Microbiol 2012;14: [93] Bajracharya S, Ter Heijne A, Dominguez Benetton X, Vanbroekhoven K,
1646–54. Buisman CJN, Strik DPBTB, Pant D. Carbon dioxide reduction by mixed and pure
[80] Blasco-Gómez R, Batlle-Vilanova P, Villano M, Balaguer MD, Colprim J, Puig S. On cultures in microbial electrosynthesis using an assembly of graphite felt and
the edge of research and technological application: a critical review of stainless steel as a cathode. Bioresour Technol 2015;195:14–24.
electromethanogenesis. Int J Mol Sci 2017;18:874. [94] Yang HY, Bao BL, Liu J, Qin Y, Wang YR, Su KZ, Han JC, Mu Y. Temperature
[81] Morris BE, Henneberger R, Huber H, Moissl-Eichinger C. Microbial syntrophy: dependence of bioelectrochemical CO2 conversion and methane production with a
interaction for the common good. FEMS Microbiol Rev 2013;37:384–406. mixed-culture biocathode. Bioelectrochemistry 2018;199:180–8.
[82] Stams AJ, Plugge CM. Electron transfer in syntrophic communities of anaerobic [95] Jourdin L, Freguia S, Flexer V, Keller J. Bringing High-Rate, CO2-based microbial
bacteria and archaea. Nat Rev Microbiol 2009;7:568–77. electrosynthesis closer to practical implementation through improved electrode
design and operating conditions. Environ Sci Technol 2016;16:1982–9.
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Renewable and Sustainable Energy Reviews 156 (2022) 111997

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

Electron donors and mediators in the thermodynamics and kinetics of

relatively longer-term, ongoing, and slow solution and requires short-

List of abbreviations TA Thermodynamic analysis

2. Electron donors and mediators

2.1. Classification of electron donors and mediators

C2R has become a wide topic of interest as indicated by hundreds of

Fuel Carbon C 4 − 0.627

where “n” is the number of moles of electrons given by the electron

HCOOH CH3COOH Butyrate Oxalic Acid

ΔGo ΔEcello K ΔGo ΔEcello K ΔGo ΔEcello K ΔGo ΔEcello K

CH3OH CH3CH2OH CH3CH2CH3OH CH3(CH2)2CH3OH

3.3. Factors affecting the role of electron donors in C2R thermodynamics

As already, discussed that the thermodynamic favorability is not

Fig. 6. Mechanisms in syntrophic hydrogenotrophic CO2 bioreduction.

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