Opinion
Constructing the electricity–
carbohydrate–hydrogen cycle for
a sustainability revolution
Y.-H. Percival Zhang1,2 and Wei-Dong Huang1,3
1
Biological Systems Engineering Department, Virginia Tech, 304 Seitz Hall, Blacksburg, Virginia 24061, USA
2
Gate Fuels Inc., 2200 Kraft Drive, Suite 1200B, Blacksburg, VA 24060, USA
3
Current address: Environmental Division, College of Earth and Space Science, University of Science and Technology of China,
Hefei, China 230026
In this opinion, we suggest the electricity–carbohydrate–
hydrogen (ECHo) cycle which bridges primary energies
and secondary energies. Carbohydrates are sources of
food, feed, liquid biofuels, and renewable materials and
are a high-density hydrogen carrier and electricity stor-
age compounds (e.g. >3000 Wh/kg). One element of this
ECHo cycle can be converted to another reversibly and
efficiently depending on resource availability, needs
and costs. This cycle not only supplements current
and future primary energy utilization systems for facili-
tating electricity and hydrogen storage and enhancing
secondary energy conversion efficiencies, but also
addresses such sustainability challenges as transporta-
tion fuel production, CO2 utilization, fresh water con-
servation, and maintenance of a small closed ecosystem
in emergency situations.
ECHo cycle
We propose the construction of the electricity, carbohy-
drate (CH2O, common shorthand) and hydrogen (ECHo)
cycle (Figure 1) as a means to supplement current and
future primary energy utilization systems for efficient
energy storage, distribution and utilization. In this cycle,
electricity is a universal high-quality secondary energy
produced from nonrenewable primary energy sources
(e.g. fossil fuels – coal, oils, natural gas, and nuclear fission
energy) and renewable primary energy sources (e.g. solar,
wind, biomass, geothermal, tidal, and waves) [1,2]. How-
ever, electricity distributed relatively easily by grids is
difficult to store on a large scale [1,3,4]. Hydrogen can
be converted to electricity by high-efficiency proton ex-
change membrane fuel cells (PEMFCs) without the gener-
ation of significant pollutants, but it is difficult and costly
to store and distribute [1,5–7]. Carbohydrates (also called
sugar) produced from plants or artificial photosynthesis
offer an alternative solution. They are storable chemical
compounds so that they can be easily and safely distributed
based on available infrastructure [1,7].
The ECHo cycle consists of six unidirectional high-
energy-efficiency conversions among three elements
(Figure 1). Between electricity and hydrogen, PEMFCs
Corresponding author: Zhang, Y.-H.P. (ypzhang@vt.edu).
Keywords: artificial photosynthesis; biofuels; cascade enzyme factories; CO2
utilization; electricity storage; hydrogen carrier.
0167-7799/$ – see front matter ß 2012 Elsevier Ltd. All rights reserved. doi:10.1016/j.tibtech.2012.02.006 Trends in Biotechnology, June 2012, Vol. 30, No. 6
and water electrolysis can convert hydrogen to electricity
and electricity to hydrogen, respectively. From sugar to
hydrogen, theoretical hydrogen yield (i.e. 12 H2 per glucose
unit) has been achieved by a new biotechnological platform;
cascade enzyme factories that assemble many enzymes
and/or coenzymes to synthetic pathways for implementing
complicated biological reactions under modest reaction
conditions [8–10]. Via this conversion, carbohydrates are
proposed to be high-density hydrogen carriers with a gravi-
metric density of 8.33 mass H2% based on sugar/water
slurry [7]. From sugar to electricity, biological fuel cells
mediated by microbes or synthetic enzymatic pathways
can convert sugar to electricity directly [10–12]. However,
there is a lack of energy-efficient biological or chemical
approaches that can convert hydrogen or electricity plus
CO2 to sugar. Biological conversion mediated by living
microorganisms has been reported for producing organic
matter from electricity or hydrogen [13,14], but they suffer
from low energy efficiencies due to cell duplication and low
product selectivity. Similarly, intensive research and devel-
opment efforts are being made to convert CO2 and water
plus solar energy to a variety of solar fuels, such as methanol
and hydrocarbons, through photochemical, electrochemical
and photoelectrochemical means, rather than sugar [15–
17]. Arguably, sugar could be a better energy carrier than
other liquid fuels for the transport sector in the future [18].
In this opinion paper, we propose novel, high-energy
efficiency, biological CO2 fixation pathways to fill the gaps
from electricity and hydrogen to sugar in the ECHo cycle
(Figure 1). Also, we discuss potential applications of the
ECHo cycle.
Artificial photosynthesis for biological CO2 fixation
CO2 can be biologically fixed by plants, microorganisms
and animals. All natural biological CO2 fixation pathways
require 12 mol of the reduced cofactors (e.g. NADPH) and/
or its equivalents plus 2–18 mol of ATP for the generation
of 1 mol of glucose from 6 mol of CO2, where ATP works as
an extra energy driving force for implementing thermody-
namically unfavorable reactions in nature [19]. For plants,
the synthesis of one glucose requires 12 NADPH and net 18
or 30 ATP for C3 or C4 plants, respectively, due to very low
CO2 concentration (e.g. 380 ppm) in the atmosphere. We
propose a hypothetical high-energy-efficiency CO2 fixation
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 Opinion Trends in Biotechnology June 2012, Vol. 30, No. 6

Non-renewable primary Renewable primary energy

energy
Geo- Tidal/
Coal thermal wave

Oil Solar

H2O CO2
CO2
Natural gas Wind +

Methane
Electricity
Hydro-
clathrate
CO2 H O H2O

O2
2
Nuclear 83% 102% + CO2 Biomass

O2 O2
121% 100%
122% 81% Sugar
H2
[CH2O]
CO2 H2O

ECHO cycle
TRENDS in Biotechnology

Figure 1. The ECHo cycle for the inter-conversions among the three major secondary energies along with primary energy sources. The dotted red lines present the
hypothetical biological CO2 fixation pathway. The percentage presented here reflects a theoretical energy efficiency from one to another element in the ECHo cycle, where
the reaction is assumed to occur with a 100% stoichiometric efficiency. The practical energy efficiencies are presented in Table 1.

process [Eq. 1] mediated by non-natural cascade enzymes energy forms [1]; (ii) it would utilize high-concentration CO2
from high concentration CO2 from power stations (Figure 2). from power stations rather than capture dilute CO2 from
This process could be scaled up easily because (i) it would not ambient air [20]; and (iii) carbohydrates are storable, trans-
be involved in costly conversions from nonpoint to point portable, stable chemical compounds with a combustion

36 e- 36 e-

Cathode Anode

C2H6O
9 ru5p #3 HPS 9 HCHO 9 H2O
+ CO2
Nafion membrane

+ H2O #8-11 9 NAD+

Medred

9 hu6p
#2 FADH
2ATP #4 PHI 9 O2
9 NADH
6 f6p 9 f6p 9 HCOOH
#12-18 9 NAD+
3 g3p
Medox

#5-7 2 f6p #1 FDH 18H2O

2ADP g3p 9 NADH
2ATP f6p
2ADP 9 CO2
Pi
H+
#19-21
(C6H10O5)n
Pi
(C6H10O5)n+1

TRENDS in Biotechnology

Figure 2. The in vitro synthetic enzymatic pathway for CO2 utilization powered by electricity. The enzymes are #1 formate dehydrogenase (FDH, EC 1.2.1.2); #2 formaldehyde
dehydrogenase (FADH, EC 1.2.1.46); #3 3-hexulose-6-phosphate synthase (HPS, EC 4.1.2.43); #4 hexulose phosphate isomerase (HPI, EC 5.3.1.27); #5 6-phosphofructokinase
(PFK, EC 2.7.1.11); #6 fructose-bisphophate aldolase (ALD, EC 4.1.2.13); #7 triosephosphate isomerase (TIM, EC 5.3.1.1); #8 transketolase (TK, EC 2.2.1.1); #9 transaldolase (TAL,
EC 2.2.1.2); #10, ribose 5-phosphate isomerase (RPI, EC 5.3.1.6); #11 ribulose-5-phosphate 3-epimerase (RuPE, EC 5.1.3.1); #12 glyceraldehyde-3-phosphate dehydrogenase
(G3PDH, EC 5.1.3.1); #13 phosphoglycerate kinase (PGK, EC 2.7.2.3); #14 phosphoglycerate mutase (PGCM, EC 5.4.2.1); #15 enolase (ENO, EC 4.2.1.11); #16, pyruvate kinase (PK,
EC 2.7.1.40); #17 pyruvate decarboxylase (PDC, EC 4.1.1.1); #18 alcohol dehydrogenase (ADH, EC 1.1.1.1); #19 phosphoglucose isomerase (PGI, EC 5.3.1.9); #20
phosphoglucomutase (PGM, EC 5.4.2.2); and #21 starch phosphorylase (aGP, EC 2.4.1.1). The listed compounds and metabolites are Medred, reduced mediator; Medox, oxidized
mediator; HCOOH, formate; HCHO, formaldehyde; ru5p, ribulose-5-phosphate; hu6p, 3-hexulose-6-phosphate; f6p, fructose-6-phosphate; g3p, glyceraldehydes-3-phosphate;
(C6H10O5)n+1 and (C6H10O5)n, linear polysaccharides (e.g., amylose or cellulose) with the degree of polymerization of n+1 and n, respectively; Pi, free inorganic phosphate; and
C2H6O, ethanol. Chemical compounds in the red and green boxes are substrates and products, respectively.

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Opinion Trends in Biotechnology June 2012, Vol. 30, No. 6

energy density of 17 MJ/kg, which can be distributed by
available infrastructure [18]. For electricity to sugar, the
overall stoichiometric reaction mediated by a synthetic
enzyme pathway is:
8CO2 ðgÞ þ 8H2 OðlÞðþelectricityÞ !
C6 H10 O5 ðsÞ þ C2 H6 OðlÞ þ 9O2 ðgÞ
where the inputs are CO2, water and electricity; the out-
puts are amylose (linear starch) or insoluble cellulose or
their equivalents, ethanol and oxygen. The whole pathway
contains six modules:
(1) electrochemical NADH regeneration (Eq. 2) for gener-
ation of 18 NADH in cathode and nine dioxygen in
anode [21],
(4) ribulose-5-phosphate regeneration by the eight
enzymes in the nonoxidative pentose phosphate and
glycolysis pathways (Eq. 5) [8],
8f 6p þ 2ATP ! 9ru5p þ g3p þ 2ADP [5]
(5) ethanol production from glyceraldehydes-3-phosphate
[1] (g3p) by the seven enzymes in the glycolysis and
ethanogenesis pathway (Eq. 6), and
g3pþPi þ 2ADP ! C2 H6 O þ CO2 þ H2 O þ 2ATP [6]
(6) starch (amylose, a linear a-1,4-glucosidic bond starch)
lengthening reaction mediated by starch phospho-
phorylase along with phosphoglucose isomerase and
phosphoglucomutase (Eq. 7),
f 6p þ ðC6 H10 O5 Þn ! ðC6 H10 O5 Þnþ1 þ Pi [7]

18NADþ þ18H2 O ! 18NADH þ 18Hþ þ9O2
(2) CO2 fixation to formaldehyde (CH2O) mediated by
formate dehydrogenase and formaldehyde dehydroge-
nase (Eq. 3) [22,23],
9CO2 þ18NADH þ 18Hþ ! 9CH2 O þ 9H2 O þ 18NADþ
(3) conversion of formaldehyde and ribulose-5-phosphate
(ru5p) to fructose-6-phosphate (f6p) by 3-hexulose-6-
phosphate synthase and hexulose phosphate isomer-
ase in the ribulose monophosphate pathway (Eq. 4)
[19,24],
9CH2 O þ 9ru5p ! 9f 6p
[2] The Gibbs free energy of Eq. 1 without electricity input
(i.e. a reverse starch and ethanol combustion) is
+4216.7 kJ/mol (Table 1), suggesting that this reaction
cannot happen. The combination of Eqs 3–7 results in a
stoichiometric reaction of 8CO2 + 18NADH + 18H+ !
(C6H10O5) + C2H5OH + 18NAD+ + 9H2O with a standard
Gibbs free energy of –460.4 kJ/mol (Table 1), suggesting
[3] that the above reaction powered by NADH is thermody-
namically feasible. The NADH can be regenerated from
NAD+ by electricity as in Eq. 2 [21]. Reaction 1 powered by
electricity could be technological feasible because (i) nearly
every reaction is reversible, except 6-phosphofructokinase
and pyruvate kinase, which control the overall reaction
direction toward the desired products; (ii) each of the
combined equations (2–7) is validated well; and (iii)
[4] there is a negative Gibbs free energy value for the overall

Table 1. Calculation of thermodynamics and energy efficiency for six unidirectional conversions in the ECHo cycle and natural
photosynthesis
Conversion (technology) Reaction DGo (kJ/mol) h theoretical a Ref. h practicala Ref.
Electricity ! H2 (electrolysis) H2O (l) ! H2 (g) + 1/2 O2 (g) +237.1 120.5% b [39] 60–85% [29]
H2 ! electricity (PEMFC) H2 (g) + 1/2 O2 (g) ! H2O (l) –237.1 83.0% c [39] 40–70% [39]
Carbohydrate ! H2 (reverse C6H10O5 (aq) + 7 H2O (g) ! –44.9 121.7% [7,8] 120% h [1]
artificial photosynthesis) 6 CO2 (g) + 12 H2 (g)
H2 ! carbohydrate + EtOH 8 CO2 (g) + 18 H2 (g) ! –54.5 81.4% calculated e 80% h estimated
(artificial photosynthesis, Eq 9) (C6H10O5) (s) + C2H6O (l) +
10 H2O (l)
Carbohydrate ! electricity C6H12O6 (aq) + 6 O2 (g) ! –2873.4 102.3% calculated f 10–83% i [11]
(biofuel cell) 6 CO2 (g) + 6 H2O (l)
Electricity ! carbohydrate + EtOH 8 CO2 (g) + 8 H2O (l) ! +4216.7 99.5% calculated g 68% [22]
(artificial photosynthesis, Eq 1) (C6H10O5) (s) + C2H6O (l) +
9 O2 (g) –460.4
8 CO2 + 18 NADH + 18H+ !
(C6H10O5) + C2H5OH +
18 NAD+ + 9 H2O
Solar energy ! carbohydrate 6 CO2 (g) + 6 H2O (l) ! +2873.4 4.6–6.0% d [40] 0.2–1.0% d [19]
(natural photosynthesis) glucose (aq) + 6 O2 (g)
a
Energy efficiency.
b
Electrolysis that happens at the ideal standard potential (1.23 V) [25].
c
Ideal hydrogen fuel cell that generates electricity at a standard potential (1.23 V) [25].
d
Relative to the whole wavelength range of solar radiation.
e
Based on the standard thermodynamics data [25].
f
Ideal open-circuit biofuel cell that generates electricity from carbohydrates at the standard potential [25].
g
Artificial photosynthesis process that consumes electricity to generate carbohydrates and ethanol at the ideal standard potential (1.24 V).
h
99% chemical conversion efficiency for cell-free synthetic enzyme biotransformation, where 1% energy losses are used for separation of the gas product hydrogen or
water-insoluble starch and for enzyme synthesis [1].
i
Coulombic efficiency.

303
Opinion
reaction (8CO2 + 18NADH + 18H+ ! (C6H10O5) + C2H5OH
+ 18NAD+ + 9H2O) [19]. To promote further the proceed-
ing of the reaction toward the desired products, this
process would be operated by: (i) using high-concentra-
tion and high-pressure CO2 plus carbonic anhydrase; (ii)
precipitating water-insoluble amylose in the presence of
ethanol; and (iii) in situ stripping of ethanol from the
aqueous phase, according to the principles of shifting
chemical equilibrium of reversible chemical reactions
[25]. It should be noted that many synthetic and natural
pathways can be designed to fix CO2 and convert it to
carbohydrates. However, the above pathway could have
the highest energy conversion efficiency, requiring 12
NADH only, whereas microorganisms and plants must
spend additional ATP plus 12 NADH or its equivalents
reducing power for the synthesis of 1 mol of glucose from
CO2 [26].
Similar to the above pathway design, hydrogen can re-
place electricity for NADH regeneration by using an NADP-
dependent hydrogenase, in the presence of transhydrogen-
ase or through redox enzyme engineering that can change
the coenzyme preference of redox enzymes (Eq. 8)
18NADþ þ18H2 ! 18NADH þ 18Hþ [8]
The combination of Eqs 3–8 leads to Eq. 9. The standard
Gibbs free energy of Eq 9 is –54.5 kJ/mol (Table 1), sug-
gesting that the reaction is thermodynamically feasible.
Increasing the gas pressure in bioreactors drives the reac-
tion forward to the desired products.
8CO2 ðgÞ þ 18H2 ðgÞ ! C6 H10 O5 ðsÞ þ C2 H6 OðlÞ þ 10H2 OðlÞ
[9]
The above pathways can be slightly modified for differ-
ent outputs, such as lactic acid, acetic acid, glucose-6-
phosphate, and sorbitol. For example, the co-product etha-
nol in Eqs. 1 and 9 can be consumed to regenerate NADPH
and its equivalents (Eq. 10) through the eight-enzyme
tricarboxylic acid cycle, along with another five enzymes
(i.e. aldehyde dehydrogenase, S-acetyl CoA synthetase,
nucleoside-diphosphate kinase, NAD transhydrogenase,
and flavin reductase) [27].
Applications
This ECHo cycle could supplement current and future
primary energy utilization systems and bridge between
primary and secondary energies because energy fluxes
among electricity, carbohydrate and hydrogen are smaller
than fluxes of primary energies utilized by human beings
[2]. Each element of this cycle can be converted to another
reversibly and efficiently, depending on resource avail-
ability, needs and costs. The two major roles of the ECHo
cycle are the storage of a fraction of difficult-to-store
electricity or hydrogen that is generated from various
primary energy sources in the form of carbohydrates
through new artificial photosynthesis (here) and the pro-
duction of high-purity hydrogen for hydrogen fuel cell
vehicles [1,7]. In addition, this cycle could have other
accessory functions: (i) fixing CO2 for partial mitigation
of greenhouse gas emissions; (ii) producing feed and food
from CO2 and water by artificial photosynthesis; (iii)
304
Trends in Biotechnology June 2012, Vol. 30, No. 6
conserving fresh water compared to natural plant photo-
synthesis; and (iv) constructing a sustainable ecosystem
for space travel or in emergency situations.
One of the most important conversions in this ECHo
cycle is the release of high-purity hydrogen from carbohy-
drates for powering hydrogen fuel cell vehicles (Figure 3a)
[1,7]. Another promising small-energy flux but high-value
market is powering portable electronics, such as cellular
phones and MP3 players, through enzymatic fuel cells
(Figure 3b) [10,28].
Carbon-neutral electricity generation is becoming in-
creasingly important, but most of it, such as wind and solar
electricity, suffers from large output variations [2–4].
Therefore, it is important to find high-efficiency, low-cost,
scalable electricity storage approaches [1,3,4]. Hydrogen
can be converted to electricity through high-efficiency
PEMFCs, and water electrolysis with practical efficiencies
of 60–85% has been suggested for storing electricity [29].
However, low-cost, high-density hydrogen storage
approaches are not available; compressing hydrogen con-
sumes too much energy; and reconstruction of mass gas-
eous hydrogen distribution infrastructure is more costly
than that needed for distributing carbohydrates [7]. To
solve the large-scale storage challenge of wind/solar elec-
tricity, especially off-peak electricity or surplus electricity,
we suggest the storage of low-cost or potentially free
electricity in the form of carbohydrates (Figure 3c), by
fixing CO2 mediated by the enzyme mixtures (Figure 2).
The overall efficiency of converting electricity to the chem-
ical energy is estimated to be 68% [85%, water electrol-
ysis [29] and 80%, biological CO2 fixation (Table 1)]. This
electricity-to-sugar efficiency could be higher than that of
methanol and hydrocarbons syntheses from H2 and CO2 or
syngas through chemical catalysis [30,31], because bioca-
talysis features modest reaction conditions, low energy
(a) (b)
E E
H H C
C
Transportation Portable electronics
(c) (d)
E E
H C H C
Electricity storage Space travel
CO2 fixation Emergency
Food production
Water conservtion
TRENDS in Biotechnology
Figure 3. Inter-conversions among the three secondary energy carriers (i.e., E,
electricity; C, carbohydrate; and H, hydrogen) in the ECHo cycle for different
applications.
Opinion
input, high energy efficiency, low-cost bioreactors, and
good chemical selectivity. In addition, the combined effi-
ciency of sugar-to-hydrogen, hydrogen-to-electricity, and
an electric motor (Figure 3a) could be much higher than
those of methanol and hydrocarbons through prime
movers, which can transform storable energy forms to
mechanical energy. High-energy efficiencies are mainly
due to (i) higher energy efficiencies for PEMFCs compared
to those of direct methanol fuel cells and internal combus-
tion engines; and (ii) 22% combustion energy gain in the
sugar-to-hydrogen biotransformation process [8,9,18].
Therefore, the storage of electricity in the form of carbohy-
drates may be better than methanol and hydrocarbons
based on energy efficiency analysis.
Currently it is not economically feasible to produce
carbohydrate from hydrogen because hydrogen (e.g.
$2.00–3.00/kg of hydrogen, $14.0–21.0/GJ) is usually more
costly than carbohydrates (e.g. $0.22–0.32/kg of sugar,
$12.9–18.8/GJ) (Figure 3c) [1]. However, in the case of food
shortages, it would become important to fix CO2 from
hydrogen or electricity for the production of feed and food,
regeneration of oxygen, and storage of hydrogen or elec-
tricity (Figure 3d).
Perspectives
Experimental validation of these hypothetical biological
CO2 fixation systems has not yet been achieved, but each
key component in these novel pathways is well-known and
tested [19]. The experimental setups are highly complicat-
ed and require close collaboration among biologists, elec-
trochemists, chemists and engineers. The construction of
cell-free cascade enzyme factories for implementing com-
plicated biological conversions, especially for the produc-
tion of low-value biofuels, remains at an early stage
[10,19,32]. However, cascade enzyme factories feature
many benefits, such as high product yield, fast reaction
rate, easy access and control for an open system, fast
assembly, tolerance of toxic compounds, and broad reaction
conditions, compared to microbial cell factories mediated
by living entities [10,19,32]. The major obstacles to the
large-scale implementation of cascade enzyme factories
are: (i) lack of stable enzymes and their complexes as
building blocks in the pathways; (ii) costly and labile
coenzymes; and (iii) efficient coenzyme regeneration by
electricity or hydrogen. However, such obstacles can be
addressed based on available biotechnological tools. With
regard to the first obstacle, many stable enzymes can be
obtained by: (i) the discovery and use of thermostable
enzymes from thermophiles; (ii) enzyme immobilization;
and (iii) enzyme engineering through rational design, di-
rected evolution, and their combination [1,10]. With regard
to the second obstacle, costly and labile coenzymes could be
replaced by low-cost stable biomimetic coenzymes associ-
ated with redox enzyme engineering [19,33–35]. With
regard to the third obstacle, more research is needed to
increase total turnover of in vitro coenzyme regeneration
[21,23,36,37].
Cascade enzyme factories could become a new low-cost
and high-yield biomanufacturing platform, especially for
white biotechnology [10,19,32,38]. With future break-
throughs in low-cost, carbon-free electricity or hydrogen
Trends in Biotechnology June 2012, Vol. 30, No. 6
generation from renewable primary energies, this ECHo
cycle could link air, water, food and energy for a sustain-
ability revolution.
Conflict of interest
YPZ has financial interests in the synthetic pathways pertaining to sugar-
to-hydrogen and biological CO2 fixation, both of which are covered under
provisional patent disclosures.
Acknowledgments
This work cannot be finished without support of the Biological Systems
Engineering Department of Virginia Tech. The author YPZ was partially
supported by VT CALS Bioprocessing and Biodesign Center. WH as a
visiting scholar was partially supported by the China Scholarship
Council.
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