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Perspective
http://pubs.acs.org/journal/aelccp

Photocatalysis versus Photosynthesis: A

Sensitivity Analysis of Devices for Solar Energy
Conversion and Chemical Transformations
Frank E. Osterloh*
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States

ABSTRACT: The chemical literature often does not dierentiate between

photocatalytic (PC) and photosynthetic (PS) processes (including articial
photosynthesis) even though these reactions dier in their thermodynamics.
Photocatalytic processes are thermodynamically downhill (G < 0) and are
merely accelerated by the catalyst, whereas photosynthetic processes are
thermodynamically unfavorable (G > 0) and require photochemical energy
input to occur. Here we apply this dierentiation to analyze the basic
functions of PC and PS devices and to formulate design criteria for improved
performance. As will be shown, the corresponding devices exhibit distinctly
dierent sensitivities to their functional parameters. For example, under
conditions of optimal light absorption, carrier lifetimes, and electrochemical
rates, the performance of PCs is limited only by their surface area, while type
1 PS devices are limited by their carrier mobility and mass transport, and
type 2 PS devices are limited by electrochemical charge-transfer selectivity. Strategies for the optimization of type 1 and 2
photosynthetic devices and photocatalysts are also discussed.

speeds up a slow reaction.15 This distinction was highlighted

T he last decades have seen increasing research activity in

photochemical processes for environmental remedia-
tion15 and for the generation of sustainable fuels from
sunlight.611 Light-driven systems that have excited states and
that promote a chemical reaction can be generally classied as
excitonic chemical conversion systems. In the literature, such
devices are more commonly referred to as photocatalysts, or
as photosynthetic or articial photosynthesis devices.
Interestingly, there appears to be no clear distinction between
the terms photosynthetic or photocatalytic. For example,
the International Union of Pure and Applied Chemistry
(IUPAC) denes a photocatalyst as a catalyst able to
produce, upon absorption of light, chemical transformations of
the reaction partners. The excited state of the photocatalyst
repeatedly interacts with the reaction partners forming reaction
intermediates and regenerates itself after each cycle of such
interactions.12 This denition refers to all excitonic chemical
conversion devices and includes photosynthetic ones. A rened
denition from Nozik13 and Bard14 dierentiates between
photosynthetic and photocatalytic process, based on the
thermodynamics of the coupled reaction: Photoelectrolytic
cells...can be classied as photosynthetic or photocatalytic. In
the former case, radiant energy provides a Gibbs energy to drive
a reaction such as H2O + H2 + 1/2O2, and electrical or thermal
energy may be later recovered by allowing the reverse,
spontaneous reaction to proceed. In a photocatalytic cell the
photon absorption promotes a reaction with G < 0 so there is
no net storage of chemical energy, but the radiant energy
recently by Rajeshwar as part of a historical perspective on
semiconductor photocatalysis.16 Here we apply this dier-
entiation to perform a detailed analysis of the functions and of
the design of photocatalytic (PC) and photosynthetic (PS)
devices. As we will show, all excitonic chemical conversion
devices can be classied as PC, type 1 PS, or type 2 PS devices,
depending on the energetics of the coupled reactions and
depending on the device design. It is shown that PC and PS
devices are separate technologies that show dierent
sensitivities to specic surface area, carrier mobility, and
charge-transfer kinetics. The relative importance of these
parameters and the inuence of reagent selectivity, mass
transport, optical absorption on performance will be discussed.
Two alternative approaches to improve photosynthetic systems
will also be described.
Classif ication of Photocatalysts and Photosynthetic Devices. As
excitonic chemical conversion systems, photosynthetic devices
and photocatalysts rely on the conversion of photons into
charge carriers and their reaction with redox species at the
solidliquid or solidgas interface (Figure 1A). Accordingly,
both types of devices must be able to 1 absorb light and
generate free photoelectrons and holes and 2 react charge
carriers with chemicals at the surface. The principal dierence
Received: December 7, 2016
Accepted: January 18, 2017

XXXX American Chemical Society 445 DOI: 10.1021/acsenergylett.6b00665

ACS Energy Lett. 2017, 2, 445453
ACS Energy Letters
Figure 1. (A) Elementary processes involved in photocatalysis and
articial photosynthesis. (B) Energetics of photocatalysis and
photosynthesis. (C) Spatial separation of half reactions (as in type
1 PS devices) versus (D) reaction selectivity (as in type 2 PS
devices).
between PS and PC systems lies in the thermodynamics of the
coupled chemical reactions (Figure 1B). While photocatalysts
use light to speed up chemical conversions that are
thermodynamically favorable (G < 0), PS systems drive
reactions that are thermodynamically forbidden (G > 0) and
that require the added photochemical energy input from the
light source to proceed. Because the products of PS have a
higher free energy than the reagents, the reverse photosynthetic
reaction is thermodynamically favored (G < 0). This means
that in addition to the basic functions 1 and 2, PS systems also
must be able to 3 suppress this reverse PS reaction.
Photocatalysts promote reactions with
G < 0 without storage of photo-
chemical energy. Photosynthetic devi-
ces use the energy of light to drive
reactions with G > 0. To achieve this,
photosynthetic systems must suppress
the reverse photosynthetic reaction.
This additional function distinguishes
them from photocatalysts and from
catalysts in general.
The reverse PS reaction can occur in a variety of ways, as
illustrated in the following. Let eq I be that of a general
photosynthetic reaction that converts oxidized and reduced
reagents into products.
R OX + R RED PRED + POX , G > 0 (I)
This endergonic reaction proceeds only in the presence of a
light absorber that produces electron hole pairs whose energy
exceeds G. The excitation process (eq II) itself is thermo-
neutral, because under steady-state conditions, the excited light
absorber is in equilibrium with its radiation eld.17
Cat + h e + h+ (II)
446
Perspective
These generated charge carriers then react according to the
half reactions III and IV to produce reduced and oxidized
products, PRED and POX.
R OX + e PRED (III)
R RED + h+ POX (IV)
Direct reaction of PRED and POX can potentially reverse the
photosynthetic reaction I, according to V.
PRED + POX R OX + R RED, G < 0 (V)
Alternatively, reversal of I can occur via reversal of III and IV,
respectively:
PRED + h+ R OX (VI)
POX + e R RED (VII)
This occurs, for example, when the photosynthetic products
come in contact with hole- and electron-donating sites at the
light absorber. In a photosynthetic device, processes V, VI, and
VII must be prevented in order to allow the photosynthetic
reaction I to move forward. This can be achieved in two
dierent ways. Either one separates the half reactions from each
other so that the products of reaction I cannot directly react
with each other or come in contact with the incorrect charge
donor sites on the light absorber. This type 1 approach requires
separate compartments for the half reactions III and IV and it
involves separating the electrons and holes and the reagents
and the products from each other (Figure 1C). The other
approach to prevent reversal of the PS reaction is demonstrated
in Figure 1D. In this type 2 approach, reagents, products, and
charge carriers are not separated from each other. Instead,
reactions VI and VII are suppressed by introducing charge-
transfer selectivity for the half reactions III and IV. This
selectivity can be accomplished, for example, by chemical
modication of the surface of the light absorber so that the
oxidized product POX is excluded from the reduction site, and
the reduced product PRED is excluded from the oxidation site.
Because the back reactions are suppressed, only the forward
reactions can occur, and both products P RED and P OX
accumulate in the same sample space. Because no product
separation takes place, the type 2 device design is applicable
only if the mixture of products and reagents is inert or
metastable with regard to the direct back reaction V. As will be
shown below, this applies to many compounds that are of
interest as alternative fuels.
Application to Excitonic Chemical Conversion Devices. In the
following we show that the classication into PC and type 1
and 2 PS schemes can be applied to the entire range of known
excitonic conversion devices (Table 1).
For example, several types of water photoelectrolysis devices
have been demonstrated for the light-driven conversion of
water into hydrogen and oxygen.18,19 This endergonic (G >
0) process can be accomplished with devices that contain
separate electrodes connected to photovoltaic cells,20,21
separate photoelectrodes in contact with an electrolyte,22 or
devices that are hybrids of these two, as shown in Figure 2A.
Because the anodic and cathodic processes are spatially
separated from each other, all of these devices belong to the
type 1 PS category.
In contrast, particle-based systems for overall water splitting
generally belong to the type 2 PS devices. For example,
illumination of a GaN:ZnO particle suspension in water
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Table 1. Excitonic Chemical Conversion Systems
reaction
water photoelectrolysis H2O H2 + 1/2 O2; G > 0
H2 evolution with sacricial reagent H2O + Red H2 + Ox; G < 0
O2 evolution with sacricial reagent H2O + Ox 1/2 O2 + Red; G < 0
natural photosynthesis 6 CO2 + 6 H2O C6H12O6 + O2; G > 0
CO2 reduction with sacricial reagent CO2 + Red + H2O CHxOy +
Ox; G < 0
molecular degradation with sacricial reagent dye + O2 Ox; G < 0
nitrogen xation N2 + 3 H2O 2 NH3 + 3/2 O2; G > 0
nitrogen xation with sacricial agent Red + N2 + H2O Ox + NH3; G
<0
CH activation
CC and CN coupling
generates H2 and O2 in the same sample space (Figure 2B).23
Alternatively, water splitting is accomplished by illumination of
BiVO4/Au/SrTiO3 particles immobilized on a gold substrate24
or of an InGaN/GaN nanorod array.25 In these cases, a type 2
PS architecture is possible because the H2/O2 product mixture
is metastable and reaction V is slow. However, some particle-
based water-splitting systems do not belong to the type 2
category. For example, a two-compartment reactor with
separately suspended SrTiO3:Rh and BiVO4 particles splits
water in the presence of cobalt complexes as redox shuttles.26,27
A membrane between compartments allows protons, hydrox-
ide, and redox reagents to transfer between compartments but
keeps H2 and O2 separate from each other. This is an example
of a type 1 PS device.
Type 1 photosynthetic devices spatially
separate cathodic and anodic half
reactions to prevent the reverse pho-
tosynthetic reaction (back reaction).
Type 2 photosynthetic devices employ
charge-transfer selectivity to prevent
the reverse reaction.
Many papers in the literature describe hydrogen or oxygen
evolution with sacricial reagents.28,29 Depending on the size of
the chemical bias, these devices can be photosynthetic or
photocatalytic. For example, hydrogen evolution (0 V RHE)
from a SrTiO3:Rh/Pt/ [Fe(CN)6]3/4 system (+0.36 V RHE)
is photosynthetic because there is a net gain of 0.36 eV per
transferred electron.30 On the other hand, water oxidation with
a BiVO4/sodium metaperiodate (E0 = +1.63 V) suspension31
and water reduction with a CdS/hydrosulde suspension32 (E
0.41 V RHE) are both photocatalytic, because there are
energy losses of 0.40 eV per electron. In photoelectrosyn-
thetic devices, the chemical bias is replaced by an applied
voltage bias, which needs to be considered in calculating the
photosynthetic eciency of the system.19
Natural photosynthesis is an interesting case because it has
attributes of both type 1 and type 2 PS devices.33 Clearly, the
overall reaction is thermodynamically uphill and the products of
Perspective
type 1 type 2
device PS PS PC
photovoltaic powered electrochemical cell or X
photoelectrochemical cell
suspension or lm of single absorber particles X
tandem absorber particles in two compartments X
tandem absorber particles in one compartment X
particle suspension or solution X
particle suspension or solution X
cyanobacteria, algae, plants X X
particle suspension or solution X
particle suspension or solution X
photovoltaic powered electrochemical cell or X
photoelectrochemical cell
particle suspension or solution X
particle suspension or solution X
particle suspension or solution X
natural photosynthesis (carbohydrates and O2) are metastable
under standard conditions. In plant cells, the carbon-reducing
half reaction (Calvin cycle) and the light-driven water oxidation
reaction are physically separated from each other (Figure 2C),
as is characteristic for a type 1 device. Coupling of the
subsystems is achieved by moving charge along the electron
transport chain and protons, ADP/ATP, and NADP/NADPH
across the cell. However, because of oxygen permeability of the
cell walls, oxygen can enter into the Calvin cycle to get reduced
preferentially over CO2. Essentially this is the back reaction of
photosynthesis. In a process known as photorespiration,34,35
enzymes are employed subsequently to remove these oxy-
genated carbon intermediates from the Calvin cycle. This
aspect of natural photosynthesis is reminiscent of a type 2 PS
device.
Recently, there has been increasing interest in the reduction
of CO2 using articial photosynthetic (AP) devices. Because of
the complexity of the electrochemical half reactions,3638 a type
2 PS system for CO2 reduction is very dicult to realize. Some
type 2 type particle absorber systems have been published, but
their eciency is extremely low.39,40 Most ecient AP devices
contain separate electrodes or photoelectrodes for water
oxidation and CO2 reduction and belong to the type 1 PS
device type.41,42 A notable exception was demonstrated by Arai
et al.43 Their IrOx/SiGe/RuL monolithic PV/electrolysis cell is
capable of reducing CO2 to formate at the RuL-coated cathode
with electrons from water oxidation by the IrOx photoanode.
Because it combines selective electrocatalysis features with
those or a conventional PV, it can operate in a single cell
compartment and should be classied as a type 1/2 hybrid PS
device.
Considerable research eort has been devoted to photo-
catalytic processes for environmental remediation and anti-
bacterial applications.1,4,44 Most of these devices rely on the
photochemical generation of highly reactive hydroxyl and
superoxide radicals when metal oxides are illuminated in the
presence of water, air, or hydrogen peroxide. The radicals then
abstract hydrogen atoms from hydrocarbons, causing various
follow-up reactions, and complete mineralization in some cases.
To date, this reaction has been shown to be eective for the
photodegradation of many organic compounds,45 including
halogenated hydrocarbons,1 dyes, alcohols, amines, and
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ACS Energy Letters
Figure 2. (A) Photoelectrochemical water-splitting cell (type 1 PS
device). (B) Water-splitting photocatalysis as an example of a type
2 photosynthetic device. (C) Natural photosynthesis as example of
a type 1/2 process with separate compartments for anodic and
cathodic reactions and cocatalysts for selective photochemical
charge transfer.
saturated hydrocarbons.4 Because the thermodynamics are
downhill, oxidative degradation processes belong to the class of
photocatalytic reactions. Lastly, some excitonic chemical
conversion systems have been found to promote nitrogen
xation and CC and CN bond activation.46 For example,
irradiation of Fe2Ti2O7 lms in the presence of ethanol or
hydrazine produced micromolar amounts of NH3 from N2 gas.
However, these reactions are very slow and proceed only in the
presence of a strong thermodynamic bias. Most of them show
substoichiometric reactivity and would require serious opti-
mization to make them photocatalytic. This suggests that
because of the complexity of the half reactions, PS 1 devices
with separate compartments for water oxidation and nitrogen
reduction are considered necessary for ecient ammonia
synthesis.
448
Perspective
Optimization of PS and PC Devices as Separate Technologies.
The classication of excitonic chemical conversion systems
allows a sensitivity analysis of the limiting functions of the
specic device types and their properties. As shown in Figure 3,
Figure 3. Limiting functions and parameters for PC and PS (1) and
PS (2) devices.
all excitonic chemical conversion devices have to generate
charge carriers from the absorption of light and react these
carriers with the reagents. These functions benet from (A)
large absorption coecients, (B) long excited state/carrier
lifetimes, and (C) fast electrochemical reaction kinetics (low
overpotentials). Indeed, the experimental correlation of each of
these properties with device activity is strong.47 For example, a
dependence of the conversion rate on the absorption coecient
is observed across the entire series of excitonic conversion
devices, including GaN:ZnO,48 molecular HER catalysts,49 and
Rh-doped SrTiO3 nanocrystals;30 for photoelectrodes50,51 and
photovoltaic devices;17,52 and for natural photosynthesis.34,53 In
addition, conversion rates are also found to scale with the
excited state/carrier lifetime. This is best established for
photovoltaic devices17 and photoelectrochemical cells,5456
but has also been conrmed experimentally for inorganic5760
and molecular photocatalysts6164 and for natural photosyn-
thesis.65,66 Lastly, the activity is strongly correlated with the
kinetics of the coupled reaction, as described by the
electrochemical reaction rate constant. This rate constant
depends on the reaction mechanism and on the thermody-
namics of the coupled redox reactions.36,6772 For example, the
simpler the reaction mechanism and the larger the thermody-
namic driving force, the larger the rate constant. Accordingly,
the replacement of slow redox couples (H+/H2, H2O/O2) with
fast ones (hydrosulde, methanol, H2O2, or AgNO3) is found
to raise the photocurrent of Fe2O3,73 BiVO4,74 and WO3
photoelectrodes75 and the conversion rate of suspended
photocatalysts.29,7678 Similarly, photocurrents for complex
reactions, including the two-electron proton reduction, the
four-electron water oxidation,79 or the four-electron CO2
reduction,38 are increased by cocatalysts.
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Besides light absorption, carrier lifetimes, and electro-
chemical reaction kinetics, the activity of photocatalysts
depends on only one additional parameter, the specic surface
area, A, of the catalyst. This is because the surface area
determines the quantity of chemical reagents in contact with
the light-absorbing system.67,80 This surface areaactivity
relationship, which is typical of conventional heterogeneous
catalysts,81,82 is well-supported by the experimental evidence.
For example, increasing the specic surface area boosts
photocatalytic hydrogen production with CdS,83 g-C3N4,9,84
KCa2Nb3O10, and TiO285 and photocatalytic oxygen produc-
tion with GaN:ZnO,76 Fe2O3,86,87 and WO3.88,89 Deviations
from this linear correlation are usually caused by secondary
eects, including surface-dependent electronhole recombina-
tion,60 quantum size eects,90 and surface potential changes of
the light absorber.91 On the basis of the surface area argument,
the largest photocatalytic activities are expected with molecular
light absorbers which have the best contact with their
surroundings. Indeed, quantum eciencies (QEs) for iodide
to tri-iodide oxidation in dye-sensitized solar cells have been
found to approach 100%.92 For more dicult reactions, the
eciency of molecular light absorbers drops. For example,
molecular iridium complexes photoreduce protons to hydrogen
with 16% QE.64,93 This is because for multielectron inner-
sphere charge-transfer reactions (like proton reduction and
water oxidation), the electrochemical kinetics of the conversion
reaction become the limiting factor.94,95
Photocatalytic (PC) and photosynthetic
(PS) devices are separate technologies.
Under optimized conditions (large
absorption coecients, long carrier
lifetimes, fast interfacial charge-transfer
kinetics), PCs are limited only by surface
area, while type 1 PS devices are limited
by charge mobility and mass transport
and type 2 PS devices are limited by
electrochemical selectivity.
In contrast to PCs, photosynthetic devices also must also be
able to suppress the reverse of the PS reaction, and this
additional function can become the limiting factor for the
device. Type 1 PS devices achieve this by separating and
transporting charge carriers over distances exceeding the optical
penetration depth of the absorber. This charge separation is
usually achieved with built-in electric elds from junctions96,97
and with engineered dipoles in the lattice98,99 or at the surface
of the absorber.100,101 Therefore, the performance of type 1 PS
device sensitivity depends on the value and spatial extension of
the electric elds and on the mobility of the charge
carriers.17,52,102 For example, the low photoelectrochemical
eciency of early transition-metal oxides, including Fe2O3, has
been attributed to the low mobility of their charge carriers.103
Main group element semiconductors have higher charge
mobility,104,105 which is why they are preferred for photovoltaic
cells. Because of the charge separation constraints, a linear
dependence of the conversion rate on the specic surface area,
as seen for many photocatalysts, is no longer observed in type 1
PS devices. For example, in SrTiO3/Ni nanocomposites, H2/O2
evolution rates rise with SrTiO3 particle size and decreasing
449
Perspective
surface area.106 Similarly, photoelectrochemical proton reduc-
tion on silicon nanowire arrays is less ecient than for planar
silicon lms.107 Additionally, because the anodic and cathodic
half reactions occur in dierent places, type 1 PS devices must
be able to eciently transport reagents and ions. That means
the activity can become mass transport limited, which is
experimentally observed for two-compartment water-splitting
cells, where it is found that electrolyte cycling increases
performance.108 Mass transport is also the limiting factor for
dual-compartment water-splitting tandem systems, where
protons and redox reagents have to diuse across a separating
membrane.27 Lastly, under light saturated conditions, natural
photosynthesis is found to be limited by electron and mass
transport in the Calvin cycle,35 or by external mass transport of
CO2.34,109
In type 2 photosynthetic devices, the mass and charge
transport functions are replaced by electrochemical selectivity.
This potentially allows the use of lower-grade semiconductors
as light absorbers. However, the surfaces of these need to be
engineered with suitable cocatalysts. For the water-splitting
reaction, the reduction of oxygen to superoxide is the main
back reaction and needs to be suppressed. In 2006, Maeda et al.
showed that this can be accomplished by encapsulating the
proton reduction sites with a Cr2O3 layer that acts as a
molecular sieve to prevent O2 access.110 Similarly, in 2007
Kudo and co-workers showed increased proton reduction
selectivity of Pt cocatalysts in the presence of [Fe(SO4)-
(H2O)5]+ and [Fe(OH)(H2O)5]2+ complexes,111 or in the
presence of carbonates112 and iodide.113 When these selective
proton reduction cocatalysts are used, type 2 PS devices are
able to promote the water-splitting reaction24,114117 with
coaccumulation of hydrogen and oxygen in the same sample
space. A similar strategy may be useable for type 2 PS device to
x CO2 and N2, although these reactions are more complex
than proton reduction. Additional energy may be required to
separate products in some cases, which can reduce the overall
activity further.26
In conclusion, it was shown that all excitonic chemical
conversion systems can be classied as photocatalytic or type 1
or type 2 photosynthetic devices. Because they jointly rely on
the generation and transfer of photochemical charge carriers,
the activity of all of these devices increases with the light
absorption coecient, the excited-state lifetime, and the
electrochemical reaction kinetics. In the absence of other
limiting factors, the activity of photocatalytic devices is most
sensitive to the surface area. This means that better
photocatalysts can be created by increasing the surface area
or by decreasing the size of the light absorber. Photosynthetic
systems must also be able to suppress the reverse,
thermodynamically favored PS reaction. This distinguishes
them from photocatalysts and catalysts in general. Type 1
photosynthetic devices accomplish this through spatially
separated reduction and oxidation half reactions. Therefore,
the activity of type 1 PS devices is a sensitive function of the
rate of charge and mass transfer across the system. That means
their activity can be improved by raising the eective electric
eld strength across the device, by increasing the charge carrier
mobility and mass-transfer rates of reagents and reaction
intermediates (protons and hydroxide, for example). These
charge- and mass-transfer limitations do not apply to type 2
photosynthetic devices which suppress the back reaction
through charge-transfer selectivity. Accordingly, the perform-
ance of type 2 PS devices is limited by the design of the
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ACS Energy Letters
interfaces and the choice of cocatalysts. For example, the
activity of type 2 water-splitting devices hinges on the quality of
cocatalysts for selective proton reduction and their ability to
suppress oxygen reduction. Natural photosynthesis combines
type 1 and 2 device principles (separation of cathodic and
anodic reactions and charge-transfer selectivity) to overcome
the functional limitations of its organic and inorganic building
blocks. A similar dual strategy may be useful for the next
generation of articial photosynthesis devices for solar fuel
production, carbon dioxide xation, and ammonia synthesis.
AUTHOR INFORMATION
Corresponding Author
*Phone: (+1)530 754 6242. Fax: (+1)530 752 8995. E-mail:
fosterloh@ucdavis.edu.
ORCID
Frank E. Osterloh: 0000-0002-9288-3407
Funding
This material is based upon work supported by the National
Science Foundation (CHE 1464938) and by the U.S.
Department of Energy, Oce of Science, Oce of Basic
Energy Sciences under Award Number DE-SC-0001234. The
opinions are those of the author and do not necessarily reect
the views of the funding agencies.
Notes
The author declares no competing nancial interest.
Biography
Frank Osterloh is an inorganic chemist working on devices for
articial photosynthesis (http://chemgroups.ucdavis.edu/~osterloh/
index.html). He has authored 90 scientic papers and is the recipient
of the ACS Inorganic Nanoscience award (2010) and the ACS Richard
A. Glenn Award (2014). In 2016, he was named Fellow of the Royal
Society of Chemistry.
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NOTE ADDED IN PROOF

Ammonia synthesis by a CdS:nitrogenase MoFe protein
biohybrid was reported by Brown et al.118 The system
employed an aminoethanol derivative as sacricial donor and
proceeded with 3.3% quantum eciency at 405 nm.

NOTE ADDED AFTER ASAP PUBLICATION

This paper was published ASAP on January 27, 2017 with an
error in column 2 of Table 1. The corrected paper reposted on
January 27, 2017.

453 DOI: 10.1021/acsenergylett.6b00665

ACS Energy Lett. 2017, 2, 445453