Letter

pubs.acs.org/NanoLett

Photocatalysis Deconstructed: Design of a New Selective Catalyst for

Artificial Photosynthesis
Vivek Singh,† Ignacio J. Castellanos Beltran,† Josep Casamada Ribot,† and Prashant Nagpal*,†,‡,§
†
Department of Chemical and Biological Engineering, ‡Materials Science and Engineering, and §Renewable and Sustainable Energy
Institute (RASEI), University of Colorado Boulder, Boulder, Colorado 80303, United States
*
S Supporting Information

ABSTRACT: A rapid increase in anthropogenic emission of greenhouse gases, mainly carbon dioxide, has been a growing cause
for concern. While photocatalytic reduction of carbon dioxide (CO2) into solar fuels can provide a solution, lack of insight into
energetic pathways governing photocatalysis has impeded study. Here, we utilize measurements of electronic density of states
(DOS), using scanning tunneling microscopy/spectroscopy (STM/STS), to identify energy levels responsible for photocatalytic
reduction of CO2−water in an artificial photosynthetic process. We introduce desired states in titanium dioxide (TiO2)
nanoparticles, using metal dopants or semiconductor nanocrystals, and the designed catalysts were used for selective reduction of
CO2 into hydrocarbons, alcohols, and aldehydes. Using a simple model, we provide insights into the photophysics governing this
multielectron reduction and design a new composite photocatalyst based on overlapping energy states of TiO2 and copper
indium sulfide (CIS) nanocrystals. These nanoparticles demonstrate the highest selectivity for ethane (>70%) and a higher
efficiency of converting ultraviolet radiation into fuels (4.3%) using concentrated sunlight (>4 Sun illumination), compared with
platinum-doped TiO2 nanoparticles (2.1%), and utilize hot electrons to tune the solar fuel from alkanes to aldehydes. These
results can have important implications for the development of new inexpensive photocatalysts with tuned activity and selectivity.
KEYWORDS: Artificial photosynthesis, hot electrons, quantum dots, selective catalysis

T he simultaneous reduction of CO2 and water using

sunlight has been an important step in the life cycle on
earth.1 This single reaction performed by plants in an
energetically frugal, albeit inefficient process,2 allows simulta-
neous balance of CO2 gas and energy harvesting from primary
source of energy on earth, the Sun. Several strategies are being
investigated currently for converting sunlight into viable
renewable source of energy,3 to address the growing emission
of greenhouse gases4−6 and depleting sources of cheap energy
for burgeoning human population. Developing an efficient
artificial photocatalyst to carry out a simultaneous reduction of
CO2 and water can address this issue of rising level of
greenhouse gas emission and provide an alternative source of
renewable energy (Figure 1a). While several studies have
recently addressed developing modified TiO2-based photo-
catalysts for water splitting or CO2−water reduction,7−13 the
effect of chemical modification on the electronic structure of
the TiO2 semiconductor has been largely unexplored. More-
over, lack of insight into photophysics governing recombination
pathways, defect mediated photocatalytic reduction, and
energetic levels participating in electronic reduction of CO2
following photogeneration of the electron−hole pair, has also
prevented rational design of new photocatalysts with higher
efficiency and/or selectivity.
Titanium dioxide (TiO2) has been extensively studied for
several photocatalysis, photoelectrochemical, and catalytic
reactions.7−13 There have been several experimental and
theoretical investigations into modified TiO2 semiconductors
for enhancing light absorption or improving the adsorption of
reactant species.7−13 While most of the studies focused on
enhancing the catalytic rates on TiO2, improving the selectivity
of the products obtained can play a crucial role in their viable
application, especially due to the high costs of separation
processes. The difference in reduction potentials of solar fuels
(alkanes, alcohols, aldehydes, Figure 1a,d) provides an
opportunity to carefully align these respective products with
“molecule-like” energy-levels (instead of bulk-like energy
bands) of quantum-confined semiconductors nanocrystal states,
Received: October 10, 2013
Revised: January 4, 2014
Published: January 20, 2014

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Figure 1. Energy levels responsible for photocatalysis in unmodified TiO2 nanoparticles. (a) Schematic of the proposed artificial photosynthesis in
TiO2-QD based catalysts for selectively producing alkanes, alcohols, and aldehydes. (b) CO2−water photocatalytic reduction data, for unmodified
TiO2 nanoparticles, under different intensities of simulated solar irradiation (AM1.5 spectrum = 1 Sun). The chemical composition of different
catalytic products (hydrogen H2, methane CH4, ethane C2H6, acetaldehyde CH3CHO, and higher hydrocarbons including propane, butane, and
paraffins CxHy) is indicated using color coded bar graphs, on a per electron mole basis. The colored asterisk sign indicates the highest yields for
respective products obtained in our measurements. (c) Internal quantum efficiency and selectivity of solar fuels (for ethane production) under
different intensities of solar irradiance. The internal quantum efficiency (QE, percent) is computed based on the fraction of sunlight above the energy
bandgap of TiO2 nanoparticles and the total catalytic yield of different products obtained, per electron mole basis (since different products require
different number of electrons in the multielectron reduction process). Unmodified TiO2 exhibits low activity and selectivity for CO2−water
reduction. The symbols represent the average internal QE over several experiments, and the lines represent the highest and lowest yields measured.
(d) STS data showing defect levels (∼0.5−1 eV below conduction band) in TiO2 nanoparticles, likely responsible for photocatalytic activity (see
discussion on advantages of ambient measurements in the Supporting Information). The solid line shows the first derivative of current with voltage
(dI/dV) or the density of electronic states, the dashed line represents the current−voltage spectrum, and levels indicated on the right represent the
relative reduction potential values for different fuel products formed from CO2−water reduction.15 The work function of the Pt−Ir tip and the
electron affinity of TiO2 semiconductor were used to represent the data on an absolute energy level, with respect to vacuum. Standard hydrogen
electrode potential was used to represent NHE and energetic levels (w.r.t. vacuum) on the same scale. (e) Cross-section and 3D map of STS data
collected on 15 nm unmodified TiO2 nanoparticles. The current−voltage spectrum (I−V) shown here is used to obtain the density of electronic
states (dI/dV) based on tunneling probability (or current) from the Pt−Ir tip. The work function of the tip and the electron affinity of TiO2
semiconductor were used to obtain energy values with respect to vacuum level (0 eV).

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Figure 2. Effect of platinum metal doping on TiO2 energy levels and photocatalytic rates. (a) CO2−water photocatalytic reduction products obtained
using doped TiO2−Pt (1 wt %, see Methods in the Supporting Information) catalyst illuminated with different intensities of AM1.5 simulated solar
irradiation. The solar irradiance was increased from half up to 4.6 times the incident radiation. The increase in sunlight illumination results in change
in product yields due to filling up of lower energy levels and likely slower cooling of hot carriers, resulting in products with higher reduction
potentials. (b) Internal quantum efficiency (percent) and selectivity (for ethane hydrocarbon fuel) obtained using TiO2−Pt (1 wt %) photocatalyst.
(c) STS spectrum collected with 0.5 wt % Pt metal dopant in TiO2 nanoparticles and (d) 1 wt % Pt doped TiO2 semiconductor nanoparticle. While
the 0.5 wt % Pt metal dopant does not cause significant changes in the electronic DOS of the TiO2 semiconductor (compared to Figure S1 in
Supporting Information), 1 wt % platinum clearly shows increased DOS between the bandgap, extending all of the way through the bandgap. This
caused likely trapping, and eventually recombination, of the photogenerated electron and hole excited in the doped semiconductor (as shown by
arrows in d). This enhanced recombination on platinum sites is likely responsible for reduced photocatalytic yields on increasing the light intensity
(as shown in b).

for the selective generation of solar fuels. Therefore, these
semiconductor photocatalysts with different band alignments
and/or bandgap energies can yield selective products on
illumination with band-edge photons. Moreover, careful tuning
of energy states can help in utilizing hot electrons (especially
with solar concentrators) to change the selective solar fuel from
low reduction potential alkane to aldehyde (which requires
higher energy electrons for reduction). Therefore, we can
utilize modifications on TiO2 semiconductors, including the
attachment of semiconductor quantum dots, to tune the
energetic alignment of band-edge states. Since chemical
modification of the Fermi level (FL) in semiconductor
nanoparticles can have important consequences on recombi-
nation dynamics of photogenerated charges14 and density of
electronic states which participate in charge transfer for
photoreduction of adsorbed species, we carried out careful
photophysical studies on unmodified (Figure 1b,c) and
modified TiO2 semiconductor nanoparticles (Figures 2−5).
The energetic position of these states can affect the reduction
potential (Figure 1d) and hence likely product of simultaneous
reduction of CO2−water (because simultaneous or synergistic
reduction of CO2−water does not require a large overpotential
599
∼1.5−1.7 eV, when compared to CO2 reduction without
proton (H+) assistance):15
H 2O + h+ → H+ + ·OH
CO2 + 8H+ + 8e− → CH4 + 2H 2O
CO2 + 6H+ + 6e− → CH3OH + H 2O
CO2 + 4H+ + 4e− → HCHO + H 2O
where e− and h+ represents photogenerated electrons and
holes, respectively. Moreover, since different solar fuels
(alkanes, alcohols, and aldehydes) require a different number
of photogenerated electrons, their respective efficiencies are
normalized to the number of electron moles of fuel produced
(see Methods in the Supporting Information).
We used correlated STM and scanning tunneling spectros-
copy (STS)16,17 for measurement of single nanoparticle
electronic density of states (see Methods in Supporting
Information). Unmodified TiO2 nanoparticles demonstrated
low catalytic rates for reducing CO2−water under simulated
AM1.5 illumination (represented as 1 Sun) and very low
selectivity toward specific solar fuels resulting in a mixture of
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Figure 3. TiO2−Cu2−xO composite photocatalyst. (a) Chemical analysis of photocatalytic products obtained using TiO2−Cu2−xO (0 < x < 1)
composite catalyst (see Methods in Supporting Information), for CO2−water reduction, on illuminating with simulated solar radiation. (b) TiO2−
Cu2−xO photocatalyst shows higher yields (internal QE) for CO2−water reduction than unmodified TiO2, but variation in oxidation state of copper
results in change in semiconductor bandgap (Figure S2 in the Supporting Information) and traps on the surface, leading to enhanced recombination,
lower yields, and unselective product formation. Due to the large number of defect states present on the surface, the highest catalytic yields are
obtained under low light intensities (here 0.5 Sun illumination). On increasing the photogeneration rate (or solar irradiance), while the yield
decreases (explained using our photophysical model, Figure 5c), the filling of low energy electron states (c) leads to more products with a higher
reduction potential (acetaldehyde and higher hydrocarbons CxHy), thereby increasing the observed selectivity. (c) STS data of the composite
photocatalyst showing the overlapping energy levels of Cu2−xO and the TiO2 semiconductor.

alkanes, aldehydes, and alcohols (Figure 1b,c). However, the
presence of some defect states in TiO2 nanoparticles ∼0.5−1
eV below the conduction band (Figure 1d) accelerated the
yield of CO2−water reduction reaction (Figure 1b,c). The role
of these defect states has also been studied by other
groups,7,9−12 and nominally unmodified TiO2 nanoparticles
with a larger number of defect states showed higher catalytic
activity (see Figure S1 in the Supporting Information). These
defect states are likely electron traps14 since they are
energetically closer to the conduction band (∼0.5−1 eV)
than the valence band (∼2.2−2.7 eV, Figure 1d). Therefore,
multiphonon emission leading to relaxation of photogenerated
charges in these sub-bandgap states18 supports their role as
electron traps. While adsorption of oxygen (or CO2 here) is the
rate-limiting step in photocatalytic reactions and oxygen
vacancies with similar energies (∼0.5−1 eV below conduction
band) have been predicted to catalyze the reaction,7 our
measurements suggest that photogenerated electron trapping
can also lead to similar adsorption of reactant species. Similar
findings also reported by other groups7−13 can likely explain the
improved photocatalytic activity due to TiO2 modifications,
leading to visible light absorption and improved catalytic
activity in TiO2 nanostructures.7,9,13 Therefore, three-dimen-
sional mapping of electronic-DOS in TiO2 nanoparticles (using
individual current−voltage scans as shown in Figure 1e) helped
us in spatially correlating these electronic states responsible for
accelerated photocatalytic yields for CO2−water reduction.
600
Chemical doping of nanoparticle can be used to selectively
tune the FL and introduce energetic states with-in the bandgap
of a semiconductor.17,19 To utilize this, we introduced some
well-studied metal dopants in the TiO2 semiconductor to
understand their role in photocatalysis. We first introduced
varying amounts of platinum (Pt) dopant in TiO2 to optimize
the Pt loading and obtain highest catalytic rates for solar fuel
production. While there has been variability in literature on the
amount of Pt metal doping to obtain the highest photocatalytic
rates,7,12,20 we obtained the highest yield (23.1%, Figure 2a,b)
for 1 wt % (percentage by weight) Pt under 1 Sun (AM1.5)
simulated irradiation. On studying the effect of metal doping on
energetic states, we did not observe any additional states in the
electronic DOS of 0.5 wt % Pt-doped TiO2 nanoparticles, when
compared to unmodified TiO2 (Figure 2c compared to Figure
1d,S1). However, the analysis of STS data on 1 wt % Pt-doped
TiO2 clearly revealed bandtail states within the TiO2 semi-
conductor bandgap (Figure 2d). Since the photocatalytic
activity of CO2−water reduction was enhanced several fold
due to the introduction of Pt metal (Figure 2a), it is likely
caused due to an increase in adsorption of oxygen atom on the
Pt interface.12 But as we increased the photogeneration rate by
increasing the light intensity to enhance the photocatalytic
conversion, we saw a decrease in catalytic yields (Figure 2b).
This observation can be explained since the bandtail states
extended throughout the entire Pt-doped TiO2 bandgap, likely
facilitating the trapping and recombination of both photo-
generated electron and holes (Figure 2d). Therefore, while the
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Figure 4. Characterization of our new photocatalyst TiO2−CIS. (a) Chemical composition and (b) photocatalytic yields and selectivity for CO2−
water reduction obtained using our designed TiO2−CIS photocatalyst. The new TiO2−CIS catalyst (see Methods in Supporting Information)
combines high selectivity (>70% selectivity for ethane production) with high yield (>5% for 5 Sun illumination) and represents an important step
toward rational design of new catalyst using energy level tuning, as shown in this photocatalysis data. (c) Electronic DOS tuning can be easily
achieved by tuning the energy levels of the quantum confined CIS nanoparticle, as shown in STS data of the composite nanoparticle. 1.7 eV bandgap
CIS nanocrystals (∼3.8 nm in size) were attached to TiO2 nanoparticles resulting in desired energy levels below the conduction band of TiO2
semiconductor and possible tuning the products formed from photocatalytic reduction of CO2−water.

Pt dopant may increase the adsorption of reactant molecules,12
enhancing the photocatalysis rates (Figure 2a), it also increases
the recombination of photogenerated electrons and holes,
leading to an overall reduction in observed photogenerated
hydrogen yields. This kind of metal-mediated enhanced
recombination is not uncommon in semiconductor−metal
interfaces.21
To prevent metal dopants from acting as recombination sites,
we incorporated other inexpensive copper-based nanoparticles,
with staggered energy levels (Figure 3c, Figure 4c), to add the
desired electronic energy states in TiO2 composite photo-
catalyst. This can also tune the energetic pathway and hence the
likely products formed from CO2−water reduction. To develop
a robust and stable photocatalyst (see stability measurements in
Supporting Information), we utilized copper-oxide nano-
particles grown on surface of TiO2 as “dopants”. The new
composite nanoparticle has combined energetic states from the
TiO2 nanoparticle and the Cu2−xO (0 < x < 1) semiconductor
(Figure 3c). On illumination with AM1.5 light spectrum, there
is a rapid increase in CO2−water reduction, as compared to
unmodified TiO2 photocatalyst (Figure 3a,b compared to
Figure 1b,c). However, the overall incident photon to fuel
conversion efficiency (Figure 3c) is low because of variable
oxidation state of copper-oxide nanoparticles. Since Cu2O
(bandgap 2.1 eV) nanoparticles can be oxidized to CuO
(bandgap 1.2 eV) nanoparticles, we have observed Cu2−xO
nanoparticles with bandgap ranging from 1.87 to 1.37 eV
(Supplementary Figure S2). This change in oxidation state of
the Cu2−xO semiconductor can give rise to a charged defect or
601
trap which is likely responsible for an enhancement in
recombination rate of photogenerated electron and results in
lower photocatalytic yields at higher photogeneration rates
(Figure 3c). To develop a more stable catalyst (see stability
measurements in Supporting Information) which can produce a
specific product by using the energetic alignment of states, we
synthesized copper−indium sulfide (CIS) nanocrystals22
attached to TiO2 nanoparticles.
We studied the electronic DOS of our new composite
nanoparticle photocatalyst (TiO2−CIS, using single nano-
particle scanning tunneling spectroscopy (Figure 4c). The
Fermi level in the TiO2−CIS quantum dots was expected to
favor multielectron reduction to alkane hydrocarbon fuels
(Figure 4c). When we conducted photocatalytic reduction of
CO2−water, we observed evolution of hydrocarbon gases like
ethane, propane, and so forth, as shown in Figure 4a. However,
the most striking result was that CIS nanoparticles with a
bandgap ∼1.7 eV demonstrated very high selectivity (>70%)
for the formation of ethane gas (Figure 4a,b), as predicted by
our study (Figure 4c). Moreover, when we increased the
photon flux and the lower energy states get filled up, hot
electrons favor formation of acetaldehyde, and the predominant
product switches from alkanes to aldehyde (Figure 4a,b). With
high selectivity, hot-electron tunability of the reaction product,
combined with yield of ∼5% for this multielectron reduction
process using a small concentrator (∼5 Sun illumination, Figure
4b), this new inexpensive photocatalyst shows a lot of promise
for improved catalytic reduction of CO2−water into selective
solar fuels (see stability measurements in the Supporting
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Figure 5. Photophysics in TiO2−CIS nanoparticle catalyst. (a) Current sensing atomic force microscope (CS-AFM) spectrum of a single TiO2−CIS
nanoparticle in two regions marked “1” (red curve, TiO2 showing electron injection) and “2” (black curve, CIS showing presence of holes). The inset
shows comparable current spectrum of unmodified TiO2 nanoparticle using gold coated current sensing AFM tip. (b) CS-AFM image of a single
photocatalyst nanoparticle. The image is acquired by applying a small bias between the gold coated AFM tip, and the nanoparticles dispersed on
conductive indium−tin−oxide (ITO) substrate. Cross-section slices of the 3D spectrum obtained clearly shows spatial separation of injected
electrons and holes in the composite TiO2−CIS photocatalyst. (c) Schematic of the proposed model explaining the photophysics of the
multielectron reduction on photocatalyst. n and p represent photogenerated electron and hole concentration per nanoparticle, on illumination with
photons above the TiO2 bandgap. Nd represents the total number of defects/dopants per nanoparticle, and the dashed line represents recombination
pathways for photogenerated (with rate constant α) and trapped electrons (with rate constant α) with bandedge photogenerated holes in the
photocatalyst. (d) Relationship between photocatalytic rate of solar fuel produced by CO2−water reduction and the rate of photogeneration
(expressed as comparable solar irradiance). The decrease in photocatalytic rate of TiO2−Pt doped nanoparticles and the superlinear increase in
TiO2−CIS solar fuel production rate is explained well using our simple model.

Information). Moreover, this new class of quantum dot (QD-
TiO2) based composite photocatalysts developed here allows
careful tuning of electronic DOS in the composite photo-
catalyst, by utilizing quantum confinement effect and hot-
electron states.23−25
To improve our insights into the mechanism governing high
efficiency of photocatalytic yields in the new TiO2−CIS
nanoparticle, we utilized current sensing atomic force
microscopy (CS-AFM) (Figure 5a,b,S3 see Methods in
Supporting Information). We observed a clear spatial
separation of electron and hole, as shown in Figure 5a and b.
This spatial separation of photogenerated charges can lead to
longer lifetimes (due smaller overlap of electron and hole wave
functions) and therefore likely higher photocatalytic yields. We
developed a simple model (Figure 5c) to explain the
photophysics governing the photogeneration, recombination,
charge trapping, and the multielectron photocatalytic reduction
of adsorbed species in these dopant/defect centers on TiO2
nanoparticles. Upon irradiation with light above the TiO2
nanoparticle bandgap (photogeneration rate g), photogener-
ated electrons (n) and holes (p) are excited in the conduction
and valence “band” of the nanoparticle. A fraction of
photogenerated electrons is transferred/trapped (nd) in differ-
ent dopant/defect centers (total number Nd) in these
nanoparticles. Different photophysical events like recombina-
tion between photogenerated electrons and holes (rate
constant α), transfer/trapping of photogenerated electrons
602
(rate rt) in dopant/defect centers and back to conduction band
(rate rdt), and recombination between electrons in dopant/
defect centers and photogenerated holes (rate constant β)
change the steady state concentration of electrons and hence
rate of photocatalytic reduction (R = r × n, since reduction is
the rate determining step). Using charge neutrality (p = n + nd)
and charge balance for electrons (dp/dt = g − αpn − rtn(1 −
nd/Nd) + rdtnd − rn = 0 at steady state) and holes (dp/dt = g −
αpn − βpnd − rn)), we get a relationship between the
photogeneration rate (g) and the rate of photocatalysis (R).
Since the photocatalysis rate depends on rate of recombination
(α,β), trapping (rt,rdt), and fraction of electrons in defects (nd,
compared to n), we identified four regimes for change in
photocatalysis rate (r × n) with rate of photogeneration (g =
αn(n + nd) + βnd(n + nd) + rn). In the first regime, we identified
when α ≫ β (recombination between photogenerated electron
and hole) and n ≫ nd, g ∝ n2, and R(= r × n) ∝ g0.5
(bimolecular recombination) or expected square root depend-
ence between rate of photocatalysis and photogeneration rate.
In photocatalysis mediated by TiO2 nanoparticles, since traps
and defects play an important role, we also modeled (β ≫ α, g
≈ βnd(n + nd)) trap mediated recombination. The second class
of results predict when n > nd (Nd is small and/or rt is slow), a
linear relationship exists between photocatalytic rate (R = r ×
n) and incident photon rate (g ≈ βndn, nd is constant,
unimolecular recombination, Figure 1c observed in TiO2
nanoparticles). In cases when Nd is large (compared to n,p)
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and trapping rate (rtn(1 − nd/Nd)) of photogenerated electrons
is significant, we observed inverse relationship between
bandedge photogenerated electrons (n) and trapped electrons
(nd ∝ n−x, 0 < x < 1) depending on trapping rates (rt, rdt), total
available defects/dopants per nanoparticle (Nd), and the rates
of recombination (α,β). In this third regime, we expect to
observe superlinear relationship between photocatalytic rate (r
× n) and rate of photogeneration (g ∝ n1−x or n ∝ g1/(1−x)).
This superlinear dependence (Figure 4b and 5d observed in our
TiO2−CIS photocatalyst) implies the rate of multielectron
photocatalytic reduction (R) to obtain solar fuels can be
enhanced by increasing the photon flux or concentrating
sunlight. This can have important implications for design of
inexpensive photocatalysts by using solar concentrators, than
employing precious metal dopants in new photocatalyst design.
However, this increase cannot occur indefinitely (Figure 4b
observed in TiO2−CIS), and as the defect states get filled on
increasing the rate of photogeneration (rtn(1 − nd/Nd)), our
model predicts the slope turns to linear or unimolecular
recombination regime. The fourth regime of results obtained
from our model include cases when nd > n and hence a possible
decrease in multielectron photocatalytic reduction of CO2−
water can occur (g ≈ βnd2 ≈ βn−2x) on increasing the rate of
photogeneration (Figure 2b and 3b observed in TiO2−Cu2−xO
and TiO2−Pt).
The experimental results on photocatalysis and the measure-
ments of electronic DOS can explain the observed dependence
of catalytic yields and selectivity in different TiO2-based
photocatalysts. The insights obtained into the energetic states
involved in photocatalysis led a rational design of a new
composite TiO2−CIS catalyst, with high selectivity and yields
for CO2−water reduction. These results, combined with our
model for photocatalytic reduction, explain the photophysics
behind this important multielectron reduction reaction. The
model also clearly explains the observed relationship between
photocatalytic rate and solar concentration for different
unmodified (Figure 1c) and modified (Figure 2b, 3b, and 4b)
TiO2 photocatalysts. Therefore, this new class of QD-TiO2
photocatalysts developed here, and the photophysics governing
multielectron reduction of CO2-water, can lead to development
of new inexpensive and selective photocatalysts.
■
ASSOCIATED CONTENT
*
S Supporting Information
General methods, measuring photocatalytic activity, X-ray
diffraction, X-ray photoelectron spectroscopy, STM and STS,
CSAFM, TEM and optical characterization for copper indium
sulfide nanoparticles, advantage of STM/CSAFM character-
ization in air, photocorrosion studies of our TiO2−CIS catalyst,
and supplementary figures. This material is available free of
charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: pnagpal@colorado.edu.
Author Contributions
V.S. and I.J.C.B. contributed equally.
Notes
The authors declare no competing financial interest.
603
■
Letter
ACKNOWLEDGMENTS
This work was supported by start-up funds from University of
Colorado and NSF CAREER Award CBET-1351281. The
authors would like to thank Prof. John Falconer and Hans
Funke for help with photocatalysis measurements.
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