Volume 15

Number 2

Energy &
February 2022
Pages 401–868

Environmental
Science
rsc.li/ees

ISSN 1754-5706

PAPER
Hyungjun Kim, Su-Il In, Taeghwan Hyeon et al.
Electronic interaction between transition metal single-atoms
and anatase TiO2 boosts CO2 photoreduction with H 2 O
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Electronic interaction between transition metal

single-atoms and anatase TiO2 boosts CO2
Cite this: Energy Environ. Sci.,
2022, 15, 601 photoreduction with H2O†
Byoung-Hoon Lee, ‡ab Eunhee Gong, ‡c Minho Kim, ‡de Sunghak Park, f

Hye Rim Kim,c Junho Lee,c Euiyeon Jung, ab Chan Woo Lee,ab Jinsol Bok,ab
Yoon Jung,ab Young Seong Kim,a Kug-Seung Lee, g Sung-Pyo Cho,h
Jin-Woo Jung,i Chang-Hee Cho, i Sébastien Lebègue, d Ki Tae Nam, f
Hyungjun Kim,*j Su-Il In *c and Taeghwan Hyeon *ab

Single-atom catalysts are playing a pivotal-role in understanding atomic-level photocatalytic processes.

Received 24th May 2021,
Accepted 20th September 2021
DOI: 10.1039/d1ee01574e
rsc.li/ees
However, single-atoms are typically non-uniformly distributed on photocatalyst surfaces, hindering the
systematic investigation of structure–property correlation at atomic precision. Herein, by combining
material design, spectroscopic analyses, and theoretical studies, we investigate the atomic-level CO2
photoreduction process on TiO2 photocatalysts with uniformly stabilized transition metal single-atoms.
First, the electronic interaction between single Cu atoms and the surrounding TiO2 affects the
reducibility of the TiO2 surface, leading to spontaneous O vacancy formation near Cu atoms. The
coexistence of Cu atoms and O vacancies cooperatively stabilizes CO2 intermediates on the TiO2
surface. Second, our approach allows us to control the spatial distribution of uniform single Cu atoms
on TiO2, and demonstrate that neighboring Cu atoms simultaneously engage in the interaction with CO2
intermediates by controlling the charge localization. Optimized Cu1/TiO2 photocatalysts exhibit 66-fold
enhancement in CO2 photoreduction performance compared to the pristine TiO2.

Broader context
Heterogeneous photocatalysis represents an attractive platform for the storage of renewable energy and production of solar-chemicals. TiO2 is the most
important photocatalyst that occupies 490% of the entire photocatalyst industry due to its environmental benignity, high photocatalytic activity and cost-
effectiveness. Although various important advances have been effective in tailoring macroscopic photocatalytic properties of TiO2, atomic-level strategies to
enhance the photocatalytic performance of TiO2 have been scarce because the position and valence of cocatalysts are difficult to control on an atomic scale.
Reversible electron transfer from metal cofactors to surrounding redox-mediating ligands controls catalytic processes in homogeneous catalysts and
metalloenzymes. Similarly, redox-active reducible oxides (e.g. TiO2 and CeO2) stabilize a single atom in an extended system, and function as an electron
reservoir, which can influence the degree of charge transfer at the interface. To this end, we investigate how electronic interaction of a single atom and
surrounding TiO2 regulates photocatalytic CO2 reduction. In the current work, we demonstrate that single Cu atoms, which are site-specifically stabilized in the
Ti vacancies of TiO2, interact with surrounding TiO2 and control the overall electronic properties (e.g. reducibility, defect formation) of TiO2. We also found that
the electronic interaction is significantly dependent upon the presence of nearby single atoms.

a
Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul 08826, Republic of Korea
b
School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul 08826, Republic of Korea. E-mail: thyeon@snu.ac.kr
c
Department of Energy Science & Engineering, Daegu Gyeongbuk Institute of Science and Technology (DGIST), Daegu, 42988, Republic of Korea. E-mail: insuil@dgist.ac.kr
d
Université de Lorraine and CNRS, LPCT, UMR 7019, Vandœuvre-lès-Nancy 54506, France
e
Department of Applied Chemistry, Kyung Hee University, Yongin, Gyeonggi 17104, Republic of Korea
f
Department of Materials Science and Engineering, Seoul National University, Seoul 08826, Republic of Korea
g
Pohang Accelerator Laboratory (PAL), Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea
h
National Center for Inter-University Research Facilities, Seoul National University, Seoul 08826, Republic of Korea
i
Department of Emerging Materials Science, DGIST, Daegu 42988, South Korea
j
Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea. E-mail: linus16@kaist.ac.kr
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d1ee01574e
‡ These authors contributed equally to this work.

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Introduction
Among numerous photocatalytic materials,1–5 TiO2 is the most
intensively studied photocatalyst due to its environmental
benignity and cost-effectiveness along with intrinsically high
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photocatalytic activity.6–8 Various strategies including facet
engineering,9 vacancy formation,10 structural disorder,11,12 ele-
mental doping,13,14 band engineering15 and cocatalyst
design16–19 have been applied to improve the photocatalytic
properties of TiO2 including light absorption, charge separa-
tion and surface catalytic property. However, atomic-level stra-
tegies to enhance the photocatalytic performance of TiO2 have
been scarce and deposition of a noble metal cocatalyst (Pt, Pd,
Rh and Ir) is generally required to improve the intrinsically low
surface catalytic activity of TiO2, which has limited broader
photocatalytic applications of TiO2.1–3,16–18
Earth-abundant first-row transition metal atoms (Fe, Co, Ni,
Mn and Cu), which are highly effective as active catalytic
species for the conversion of small molecules such as H2O,
O2, CO2 and N2, have attracted significant research interest in
designing high-performance single-atom catalysts (SACs) com-
prising earth-abundant elements.20–33 Likewise, a number of
atomically dispersed metals on a photocatalyst surface have
emerged as effective platforms for various photochemical reac-
tions. These include H2 evolution,24–30 CH4 conversion,19 N2
reduction,31 and CO2 reduction,16,34–37 demonstrating the ver-
satility of a single atom as an effective cocatalyst system.
However, the single-atom photocatalyst is still in its infancy
and the determining factor that influences the photocatalytic
performance is not well understood. Considering the impor-
tance of TiO2 in photocatalytic applications, it is significant to
establish the structure–activity correlation that regulates the
photocatalytic performance of single-atom cocatalysts on TiO2.
Very recently, it was identified that the catalytic performance
of SACs can be controlled by tuning the local atomic
configuration.21,25,38–44 Especially, significant differences have
been observed in the catalytic performance of single atom/
reducible oxide systems (e.g. TiO2 and CeO2), depending on the
local environment of single atoms.25,41–44 Redox-active reduci-
ble oxides stabilize a single atom in an extended system and
function as an electron reservoir, which can influence the
degree of charge transfer at the interface.45,46 Considering that
the charge transfer between a metal cofactor and redox-
mediating ligands regulates the entire catalytic process in
biological enzymes, the surrounding support in a heteroge-
neous system is equally important to that of supported metal
atoms. Only recently, dynamic processes such as structural
distortion and electronic structure relaxation on a single atom
catalyst have been correlated with the coordinating support,
which significantly affected entire catalytic characteristics
including molecular interaction and charge transfer
property.47,48 Therefore, understanding the influence of elec-
tronic interaction between an atomic catalyst and surrounding
support toward catalytic reactivity is very important to accu-
rately establish structure–activity correlation in a single atom
catalyst system.
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Herein, combining material design, photocatalytic experi-
ments and theoretical analyses, we investigate how electronic
interaction between redox-active TiO2 and single Cu atoms
affects atomic-level photocatalytic CO2 reduction. The site-
specific stabilization of a metal atom in a Ti vacancy eliminates
the possible coexistence of other atomic configuration or sub-
nanometric clusters, enabling investigation of the photocataly-
tic CO2 reduction on a TiO2 surface with atomic precision. We
first identify the electronic properties (e.g. reducibility, defect
formation) of TiO2 through interacting with stabilized single
atoms, which arise from electronic metal–support interaction.
Interestingly, spontaneous O vacancy formation is favoured
near Cu atoms in Ti vacancies, and the coexistence of Cu atoms
and O vacancies synergistically boosts photocatalytic CO2
reduction by eliminating the CO2 activation barrier, enabling
66-fold enhancement in CO2 reduction activity compared to
that of pristine TiO2. Our synthetic approach further enables
the control of the spatial distribution of uniform single
Cu atoms on TiO2 and demonstrates that the presence of
multiple adjacent single Cu atoms leads to different structural
relaxation processes through cooperative molecular CO2 inter-
action by controlling the charge localization.
Results and discussion
Electronic interaction between a single atom and support
The redox-mediating property of a support can directly affect
the electronic interactions at a metal–support interface. To
investigate, we first considered the influence of electronic
interaction on both a single Cu atom and the surrounding
TiO2. The d states of an active metal atom in ML6 coordination
(that is, an MO6 octahedron in TiO2) experience octahedral
splitting to eg and t2g states, which individually interact with
symmetrically matched p states of O valence states (ps and pp),
leaving the rest of the p states nonbonded (pNB) (Fig. 1a).
Accordingly, charge transfer at the metal/support interface
determines the relative alignments of metal/support electronic
states and thus can affect the electronic properties of the
support material as well as the reactivity of the active metal
center. Interestingly, for a single Cu atom on anatase TiO2
(Fig. 1b), the coordination environment of a single metal atom
influences the valence states and lability of a metal and support
material. A Cu atom in a Ti vacancy induces an oxidizing
(O-rich) condition that partially oxidizes an oxide anion (O2 )
to stabilize the metal–support interface. As a result, the mid-
gap O states of Cu1/TiO2 are exposed above the Fermi level and
increase surface reducibility. This contrasts to pristine TiO2
where the O states are below the Fermi level in the absence of
mid-gap states. Due to the upshift in the O state, TiO2 becomes
vulnerable to hydrogenation and consequently, favours O
vacancy formation near the Cu atom in ambient conditions.
This is supported by the thermodynamic preference to
O vacancy formation as shown in I - IV of Fig. 1c and d,
where Cu1/TiO2 results in 0.75 eV downhill in contrast with
pristine TiO2 of +4.41 eV uphill. Critically, our theoretical result
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Fig. 1 Enhanced surface reducibility of a single-atom catalyst by electronic metal–support interfacial hybridization. (a) Schematic alignments of the
d orbital splitting of a metal atom in a coordinate complex (green on the left), the energy levels of the support material (middle) and their metal–support
hybrid states based on ligand field theory (black in the middle). The resulting states of a single-atom catalyst are shown on the right. (b) Structure and
schematic illustration of the density of states of Cu1/TiO2 (left) and pristine TiO2. For Cu1/TiO2, the spin density of the Cu(dz2)–O state near the Fermi level
is shown in yellow. (c) DFT energetics of oxygen vacancy formation (Cu1/TiO2 in red and pristine TiO2 in black), where the chemical potential of oxygen
was considered as m(O) = 1/2 E(O2) and the corresponding structural change of Cu–O4 (in green) in Cu1/TiO2 where Cu is in blue, O is in red, and
Ti is in cyan.

indicates that the intimate electronic interaction between a
metal atom catalyst and the surrounding support material
cooperatively changes their electronic properties (e.g., the elec-
tronic states of a single atom and the reducibility and defect
formation of the support material).
CO2 photoreduction mechanism on Cu1/TiO2 with an O
vacancy
Considering that the presence of an O vacancy on a photo-
catalyst surface has been shown to influence photocatalytic
performance substantially,10,45,49 the identification of sponta-
neous O vacancy formation near the Cu atom is significant. We
can understand the photocatalytic CO2 reduction mechanism
on Cu1/TiO2 with an O vacancy (denoted as Cu1/TiO2 x) based
on the fast-hydrogenation pathway (Fig. 2).10 A photoexcited
state of Cu1/TiO2 x can be described with a proton that
balances the surface charge with a photoexcited electron loca-
lized to the dx2 y2 state of the Cu atom resulting in a Cu+ state
(Bader spin population, ms = 0.00 for Cu+ in the photoexcited
Cu1/TiO2 x state vs. 0.72 for Cu2+ in the resting Cu1/TiO2 x
state) (Fig. S1, ESI†). Based on DFT energetics, all the elemen-
tary steps of CO2 reduction in Cu1/TiO2 x become energetically
favourable (Fig. 2b). CO2 can be first chemically adsorbed
favourably at the O vacancy site near the Cu atom (1 - 2 in
Fig. 2a, 0.30 eV) where the square planar Cu–O4 (1) is
distorted into seesaw Cu–O4 (2) to form a Cu–C bond. The
following proton–electron transfer reduces terminal O into
water and forms a favourable metal–CO bond (4 in Fig. 2a) that
efficiently removes the potential barrier for the deoxygenation
of CO2 to CO (3 - 4 in Fig. 2a, 0.59 eV, red in Fig. 2b), which
is the energetically most unfavourable step in perfect TiO2
(+1.35 eV, blue in Fig. S2, ESI†) and one of the unfavourable
steps in defective TiO2 x (+0.37 eV, black in Fig. 2b). The
following reduction step selectively hydrogenates the carbon
(4 - 5 in Fig. 2a, 0.02 eV) compared with either copper
(+0.72 eV) or terminal oxygen (+2.02 eV) (Fig. S3, ESI†), since it
can simultaneously form favourable C–H and Ti–O bonds,
leading to a successive reduction of carbon to methane
(5 - 8 in Fig. 2a). The oxygen vacancy can be readily replenished
by favourable vacancy formation (9 - 1 in Fig. 2a, 1.56 eV) as

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Fig. 2 Photocatalytic CO2 reduction at Cu1/TiO2 with an oxygen vacancy. (a) CO2 reduction mechanism at Cu1/TiO2 x and (b) DFT energetics of CO2
reduction at Cu1/TiO2 x (red) and TiO2 x (black). During the reduction process, the photoexcited electron is assumed to be transferred from the
conduction band minimum of TiO2 (–0.25 VRHE).
shown in Fig. 1c, where the defective TiO2 x suffers from a
thermodynamic barrier (+0.14 eV). Considering that the regenera-
tion of the oxygen vacancy is the bottleneck for the CO2 reduction
reaction at TiO2,10 the promoted O vacancy formation near the
single Cu atom effectively enhances catalytic efficiency.
Material synthesis and characterization
Various site-uniform single metal atom TiO2 photocatalysts
have been synthesized through template confined thermody-
namic redistribution of single atoms (Fig. S4, ESI†).25 The site-
uniform single atoms in the Ti vacancies of TiO2 eliminate the
coexistence of multiple atomic sites and sub-nanometric clus-
ters, which enables us to correlate the photocatalytic CO2
reduction performance directly to the single atoms in the
Ti vacancies. Structural characterization was performed on
Cu1/TiO2 samples (Fig. 3 and Fig. S5–S14, ESI†). Inductively
coupled plasma-atomic emission spectroscopy (ICP-AES) was
performed to determine the loading amount of the Cu atoms
(Table S1, ESI†). Hereafter, we denote Cu1/TiO2 (x), where x is
the Cu atom concentration in at%. The scanning transmission
electron microscopy (STEM) and the transmission electron
microscopy (TEM) images reveal the absence of observable Cu
nanoparticles in the prepared Cu1/TiO2 (Fig. 3a, Fig. S5 and S9,
ESI†). Energy-dispersive X-ray spectroscopy (EDS) analysis with
STEM shows that Cu atoms are uniformly dispersed on the TiO2
surface even at a high Cu atom concentration (0.70 at%)
(Fig. 3b). The results are consistent with the X-ray diffraction
(XRD) patterns, which show no additional peaks other than
anatase TiO2 in all the Cu1/TiO2 with various Cu at% (Fig. S7,
ESI†). From our theoretical results, stabilizing Cu atoms causes
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spontaneous O vacancy formation adjacent to Cu atoms. There-
fore, Cu1/TiO2 would possess both Ti3+ (near Cu atoms) and
Ti4+ (far from Cu atoms) on the surface. To investigate the
electronic structure change of TiO2 upon stabilizing Cu atoms,
electron energy-loss spectroscopy (EELS) was performed (Fig. 3e
and f). The L2,3 edge of 3d transition metals provides informa-
tion of the coordination structure, symmetry and oxidation
state of central atoms. The Ti L2 and L3 edges are further split
into two characteristic peaks (eg and t2g) that develop through
octahedral crystal field splitting. Therefore, crystalline anatase
TiO2 possesses four characteristic peaks, as shown in Fig. 3f.
When Ti4+ is reduced to Ti3+, the octahedral crystal field
splitting is disturbed and eg and t2g are not well distinguished,
exhibiting two peaks at slightly lower energy loss. Interestingly,
the EELS spectra of our Cu1/TiO2 (0.21) possess features of both
four peaks (site 2) and two peaks (site 1) when taken upon
different sites, indicating that both Ti3+ and Ti4+ coexist on the
surface. Note that the peak occurs at slightly lower energy loss
even in the case of the Ti4+ site due to the presence of abundant
Ti3+ nearby. The electronic structure of TiO2 upon stabilizing
Cu atoms was further studied by X-ray photoelectron spectro-
scopy (XPS). The Ti 2p peak of pristine TiO2 is located at
458.4 eV, which is a typical Ti4+ peak of anatase TiO2.51
Interestingly, the Ti 2p peak of Cu1/TiO2 shows a downshift
along with increasing Cu concentration (0.2 eV at 1.42 at%),
consistent with the EELS spectra, indicating that TiO2 is
partially reduced upon stabilizing single Cu atoms (Fig. S8,
ESI†). Then, the atomic structure of Cu1/TiO2 with different Cu
concentrations was analysed using X-ray absorption spectro-
scopy (XAS) (Fig. 3g and h and Fig. S11–S14, ESI†). From the
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Fig. 3 Material characterization of Cu1/TiO2 samples. (a) Low-resolution STEM and (b) STEM-EDS elemental mapping image of Cu1/TiO2. High-
resolution STEM Z-contrast image of (c) Cu1/TiO2 (0.70) and (d) Cu1/TiO2 (0.21). (e) STEM image and (f) corresponding EELS spectra of Cu1/TiO2 (0.21) at
different sites. Cu K edge (g) XANES, and (h) FT-EXAFS spectra of Cu1/TiO2 samples.
Cu K edge X-ray absorption near-edge structure (XANES)
spectroscopy, we found that the oxidation state of the Cu atoms
is the Cu2+ state in all the Cu1/TiO2 samples exhibiting the
absorption edge at 8996.3 eV and peak at 8997.3 eV, regardless
of the Cu loading amount (Fig. 3g). The absence of the peaks at
8981.4 eV (Cu1+) and 8980.8 eV (Cu0) indicates that oxidation
states other than Cu2+ are absent. XANES spectra of CuO, Cu2O,
and Cu foil were measured as the references, confirming the
Cu2+ oxidation state in all the Cu1/TiO2 samples. The Cu K edge
extended X-ray absorption-fine-structure (EXAFS) analysis
reveals that the absence of the Cu-based nanoparticle for-
mation is consistent with the XRD, EDS, and TEM results,
and the identical local coordination structure of Cu atoms in
all the Cu1/TiO2 samples. The two characteristic peaks of Cu–O
and Cu–O–Ti are observed in all the samples, indicating that
the Cu atoms are present in the Ti vacancies of anatase TiO2.
Profile fitting on the EXAFS spectra was performed, confirming
that the Cu atoms are stabilized in the Ti vacancies. The
coordination number (CN) of the Cu–O bonds in all Cu1/TiO2
samples was similar (4.6–4.8), showing that negligible differ-
ences exist in the local coordination structure of Cu atoms at
different concentrations (Fig. 3h, Fig. S14 and Table S2, ESI†).
Note that the CN of Cu–O bonding is smaller than that of Ti–O
bonding in typical anatase TiO2, indicating that Cu atoms are
undercoordinated. Considering the downshift of Ti 2p spectra
in the XPS analysis of Cu1/TiO2, undercoordinated Cu atoms
indicate that partial reduction of the TiO2 surface is associated
with favorable O vacancy formation near Cu atoms, which is
consistent with our theoretical prediction.
Considering the negligible differences observed in the STEM,
XRD, XANES and EXAFS analyses, we could exclude the influence of
the difference in the local coordination structure of single Cu atoms
upon increasing Cu concentration. To gain further insights, we
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directly imaged the local structure of Cu atoms on TiO2 using Cs-
corrected STEM analysis (Fig. 3c and d and Fig. S9 and S10, ESI†).
From the low-resolution STEM and TEM images, agglomeration of
Cu was not observed, which is consistent with the XRD and XAS
results. Because the atomic mass of Cu is greater than that of Ti, we
could observe that bright dots (indicating Cu atoms) are uniformly
distributed on the TiO2 surface. The bright dots are exclusively
located on the Ti position, suggesting that the thermodynamic
redistribution process leads Cu atoms to be stabilized in the
Ti vacancies. EELS experiment was performed to verify that the
bright dots are single Cu atoms (Fig. S10, ESI†). In single Pt atom
catalysts on metal oxide supports that were synthesized via a typical
wet-impregnation method, inevitably sub-nanometer-sized Pt oxide
clusters are generated above 0.04–0.08 Pt at% (or 0.1–0.2 wt%),
complicating the precise interpretation of catalyst properties at high
Pt concentrations.43 In contrast, our thermodynamic redistribution
of single atoms in a nano-confined space at a high temperature
(1223 K) ensured stabilization of single atoms exclusively in the
Ti vacancies even at a high concentration. Interestingly, upon
imaging Cu1/TiO2 with high Cu concentration (0.70 at%), we found
that the spatial distance between multiple Cu atoms becomes very
close (Fig. 3c). From these material characterization results, we
could find two distinctive characteristics regarding Cu1/TiO2. Firstly,
Cu atom stabilization in the Ti vacancy influences the reducibility of
the TiO2 surface. Secondly, upon increasing the Cu content, the
spatial distance between adjacent Cu atoms becomes very close in
that multiple Cu atoms can simultaneously interact with one CO2
molecule.
Photocatalytic CO2 reduction experiment
The photocatalytic CO2 reduction experiments were performed
in a gas–solid reaction setup (1000 ppm CO2 feed, He balance)
under simulated solar irradiation without any sacrificial
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reagent or photosensitizer (Fig. S15, ESI†). All the prepared
single-atom TiO2 photocatalysts incorporated with Cu, Co, Ni,
and Rh atoms (metal loading of 0.21 at%) exhibited enhanced
photocatalytic CO2 reduction compared to pristine TiO2
(Fig. 4a). Whereas the pristine TiO2 exhibited a CH4 production
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Isolated Cu atoms in an MO6 octahedron in TiO2 possess
d orbitals inside the bandgap of TiO2 and photogenerated
electrons transfer from the conduction band of TiO2 to the
d orbitals of the isolated copper atoms.25 The TRPL analysis
confirms that isolated Cu atoms facilitate charge transfer,

rate of 21.6 ppm g 1 h 1, the CH4 production rates of various
single-atom incorporated TiO2 were at least doubled, exhibiting
44.6 (Rh1/TiO2), 97.3 (Ni1/TiO2), 123.5 (Co1/TiO2), and 1416.9
(Cu1/TiO2) ppm g 1 h 1, indicating that the incorporation of
single atoms in TiO2 can improve the surface catalytic activity
of TiO2 to favour photocatalytic CO2 reduction. Specifically, the
CH4 production rate of Cu1/TiO2 was significantly increased,
with a 66-fold enhancement, even with the low loading amount
of Cu atom (0.21 at% or 0.17 wt%). Time-resolved photolumi-
nescence (TRPL) spectroscopy was performed to investigate the
influence of Cu atoms on the charge carrier dynamics (Fig. S16
and Table S3, ESI†). TRPL decay was fitted using a bi-
exponential fitting model (eqn (1)) where t1 and t2 are the
decay times, and A1 and A2 are the corresponding magnitudes.
I(t) = A1
exp( t/t1) + A2
exp( t/t2)
The signal decays when the material undergoes electron–
hole recombination (longer lifetime, t1) and charge transfer/
trapping (shorter lifetime, t2).52,53 Cu1/TiO2 (0.21) has a smaller
average lifetime (0.477 ns) than pure TiO2 (0.711 ns), suggesting
that an electron is transferred from TiO2 to Cu (Fig. S16, ESI†).
promoting the CO2 reduction reaction.
Previously, copper nanoparticle-based cocatalysts (e.g. CuO,
Cu2O, Cu(OH)2 and Cu) on TiO2 were shown to be effective for
photocatalytic CO2 reduction with H2O.17,56,57 It is noteworthy
that the CH4 production rate of Cu1/TiO2 is also 30 times higher
than the reported copper oxide nanoparticle-cocatalyst system
on TiO2, demonstrating that the atomically dispersed
Cu exhibits a superior photocatalytic performance compared
to copper oxide nanoparticles.56 We modified our synthetic
methods and synthesized a Cu nanoparticle (CuNP)/TiO2 photo-
catalyst with various concentrations and compared the
photocatalytic activity with Cu1/TiO2. All the CuNP/TiO2 photo-
catalysts with different Cu concentrations exhibited a much
lower CO2 reduction performance compared to optimized
Cu1/TiO2 (0.21) (Fig. S17, ESI†). Specifically, the best
(1)
CuNP/TiO2 exhibited 240.0 ppm g 1 h 1 for CO2 to CH4 conver-
sion while Cu1/TiO2 (0.21) exhibited 1416.9 ppm g 1 h 1. The
photocatalytic performance remained stable upon 5 cycles
without noticeable performance decrease (Fig. 4b). We per-
formed various material characterizations including EELS,
STEM-EDS and Cs-STEM analysis on Cu1/TiO2 (0.21) to inves-
tigate the recyclability and material stability of Cu1/TiO2 after

Fig. 4 Comparison of the photocatalytic CO2 reduction activity. (a) Photocatalytic CO2 reduction performance of various M1/TiO2 (M = Cu, Co, Ni, Rh,
and pristine TiO2). (b) Cyclic stability of CO2 reduction on Cu1/TiO2. (c) Cu concentration-dependent CO2 reduction performance on Cu1/TiO2. The DFT
optimized structure of (d) Cu1/TiO2 x and (e) Cu2/TiO2 x after photoexcitation and CO2 adsorption where the binding pocket at the single Cu atom is
highlighted by an orange dotted circle. The charge density difference between CO2 adsorption [Dr = r(CO2–Cun/TiO2 x) r(Cun/TiO2 x) r(CO2)] is
shown in yellow and cyan for charge accumulation and depletion, respectively, with the isosurface level being 5  10 3 e Å 3.

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5 cycles of CO2 photoreduction. As can be seen from the STEM
images (Fig. S20a and b, ESI†), Cu1/TiO2 (0.21) maintains its
initial morphology after a sequential CO2 photoreduction.
STEM-EDS analysis shows that the Cu atoms maintain their
homogeneous dispersion in the spent Cu1/TiO2 (0.21) (Fig. S21,
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ESI†). Atomic level imaging using Cs-STEM directly visualizes
single Cu atoms on the surface of Cu1/TiO2 (0.21) (Fig. S20c,
ESI†). These results are mutually consistent, demonstrating
that the Cu atoms stably maintain their initial atomic disper-
sion after the CO2 photoreduction. EELS analysis was per-
formed on the spent Cu1/TiO2, featuring both four peaks
(Ti4+, site 2) and two peaks (Ti3+, site 1) (Fig. S22, ESI†),
indicating that Cu atoms favourably regenerate the O vacancy,
as predicted by the theoretical calculation. Isotopic 13CO2
experiments and control experiments confirm CO2 as the
hydrocarbon source (Fig. S18 and S19, ESI†). Cu1/TiO2 also
exhibited notable C2H6 production (64.2 ppm g 1 h 1). Recent
studies reported that oxidative CH4 coupling to C2H6 can occur
on the TiO2 surface upon light irradiation.18,58 Considering that
C2H6 production is only observed on Cu1/TiO2, a high CH4
production rate is essential for C2H6 formation through further
coupling of CH4. We then investigated the effect of the loading
amount of Cu atoms on the photocatalytic CO2 reduction
performance (Fig. 4c). The photocatalytic performance was
heavily dependent on the concentration of Cu atoms. Interest-
ingly, the photocatalytic CO2 reduction performance was max-
imized with a very low Cu atom amount (0.21 at%) and
gradually decreased with increasing Cu atom concentration.
Specifically, a significant decrease in CH4 production rate was
observed for the catalyst with a Cu atom concentration of
1.42 at%, which is approximately 16 times lower than that with
0.21 at%. In general, for nanoparticle-based cocatalysts,
enhancement in photocatalytic performance is observed upon
increasing the cocatalyst amount (typically up to 1–3 wt%),
which is known to originate from the increase in the number of
active sites.1,2 In contrast, Cu1/TiO2 exhibited the highest CO2
reduction performance at very low concentrations (0.21 at% or
0.17 wt%). Considering that all the Cu1/TiO2 samples with
different concentrations are composed of single Cu atoms as
cocatalysts, the observed phenomenon is apparently different
from the previous understanding. This indicates that factors
other than the number of active sites should be taken into
account to determine what significantly affects the photocata-
lytic performance of single-atom photocatalysts.
Electronic effect of adjacent Cu atoms on CO2 photoreduction
Very recently, charge transfer between the support and single
atom has been shown to modify the d state of stabilized metal
atoms through structural relaxation. This result indicates that
the catalytic behaviour of SACs can be predicted by analogy to
coordination chemistry.48 Structural relaxation heavily depends
on neighbouring metal cofactors in coordination complexes
where single or multiple metal atoms can lead to different
relaxation processes. We hypothesized that if catalytic inter-
action on SACs resembles that of coordination complexes, the
presence of an adjacent single atom can also lead to different
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relaxation processes. Although cooperative catalytic interaction
of multiple adjacent active sites is not often considered in
heterogeneous photocatalysts, it has been demonstrated that
cooperation of adjacent active sites in homogeneous catalysts
or metal–organic-frameworks leads to different molecular inter-
actions with CO2.54,55 The electronic effect of adjacent
Cu atoms on the active Cu site was investigated through
theoretical calculation by locating an additional copper atom
in Cu1/TiO2 x, denoted as Cu2/TiO2 x henceforth. While the Cu
atom in Cu1/TiO2 x preferably binds CO2 with d(Cu–C) = 2.02 Å
(Fig. 4d) by the aforementioned Cu–O4 distortion, evidenced by
the axial Cu–O bond elongation from 1.86 to 2.17 Å and vertical
ascent of Cu atom by Dz(Cu) = +0.68 Å, Cu2/TiO2 x does not
allow chemisorption of CO2 at the O vacancy site with
d(Cu–C) = 3.05 Å and vertical descent of Cu atom by
Dz(Cu) = 0.20 Å (Fig. 4e). As shown in the molecular orbital
density (Fig. S23, ESI†), the Cu–O4 active centre has well
localized electrons in its low symmetry of the seesaw (C2v)
structure, leading to strong Lewis basicity of the Cu atom.
Therefore, the Cu atom can efficiently transfer electrons to
the oxygen p state (1a2) of CO2 and break the symmetry of CO2
into two p states of each terminal oxygen atom (Fig. S23a and b,
ESI†) and bend the C–O–C bond angle (1801 - 1471). Then, the
single Cu site and the nearby O vacancy offer an active binding
pocket (highlighted by an orange dotted circle in Fig. 4d), at
which the bent CO2 can be favourably accommodated through
a bidentate interaction,50 while the terminal O p states are
respectively interacting with the Cu–C bond and Ti–O bond as
shown in the structure and charge density difference in Fig. 4d.
On the other hand, Cu2/TiO2 x can stabilize d electrons by a
strong charge delocalization with the nearby Cu atom through
symmetrically matched d orbitals, which results in the distor-
tion of the Cu–O4 complex into a more symmetrical square
planar (D4h) structure, as shown in Fig. S23c and S24 (ESI†). As
a result, the structure relaxation of Cu–O4 induced by charge
delocalization prevents (1) the charge localization to the
Cu atom for strong basicity of a Cu atom and (2) the conserva-
tion of a binding pocket structure, both of which are electro-
nically and sterically required for chemical bond formation
between CO2 and Cu (Fig. 4d).
Conclusions
In summary, we have investigated the atomic-level photocata-
lytic process on the TiO2 surface using uniformly stabilized
single Cu atoms on TiO2. Most importantly, our experimental
and theoretical results are mutually consistent, highlighting
that the redox-mediating property of the support can directly
affect electronic interaction at the metal atom–support inter-
face. In the case of Cu1/TiO2, the presence of a single Cu atom
partially oxidizes an adjacent surface O atom to stabilize the
metal–support interface, and thereby spontaneously generates
an O vacancy near the single Cu atom. CO2 is chemically
adsorbed on the O vacancy site by strong charge transfer of
the localized electron in the single Cu atom. Consequently, an
Energy Environ. Sci., 2022, 15, 601–609 | 607

Paper
isolated Cu atom on the TiO2 surface plays two important roles
in the photocatalytic CO2 reduction. Firstly, it promotes the
O vacancy formation and replenishment by enhancing the
surface reducibility of the surrounding TiO2. Secondly, it
induces electron localization to the active Cu centre that can
Published on 20 September 2021. Downloaded by CHONNAM NATIONAL UNIVERSITY on 2/10/2023 5:32:35 AM.
offer a binding pocket for favourable chemisorption of a CO2
molecule. The charge localization to the Cu atoms is disturbed
when additional Cu atoms are closely located, which directly
affects the CO2 photoreduction performance. Optimized
Cu1/TiO2 photocatalysts exhibit 66-fold enhancement in CO2
photoreduction performance compared to the pristine TiO2.
Author contributions
B. H. L., E. G., M. K., S. P., K. T. N., H. K., S. I. I. and T. H.
conceived the research. B. H. L., E. G. and M. K. designed the
experiments. B. H. L., E. J., C. W. L., Y. S. K. and Y. J. performed
and analysed the material synthesis. E. G., J. L. and H. R. K.
performed photochemical measurements. M. K., S. L. and H. K.
performed computational analysis. S. P. C. conducted the
HAADF-STEM analysis. K. S. L. conducted the XAFS analysis.
J. W. J. and C. H. C. performed TRPL analysis. B. H. L., E. G.,
M. K., Y. S. K., S. P., K. T. N., H. K., S. I. I. and T. H. wrote the
manuscript. H. K., S. I. I. and T. H. supervised the project. All
the authors commented on the manuscript.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Synthesis and physicochemical property analysis of the nano-
material samples was supported by the Research Center Pro-
gram of the IBS (IBS-R006-D1) in Korea (T.H.). X-ray absorption
spectra characterization at Pohang Accelerator Laboratory (PAL)
8C beamline was supported by a National Research Foundation
of Korea (NRF) grant funded by the Korean government (No.
2019M3D1A1079309) (K.S.L.). Photochemical property analysis
of the materials was supported by the Ministry of Science and
ICT in Korea (2021R1A2C2009459) (S.I.I.), and theoretical ana-
lysis was supported by the Creative Materials Discovery Pro-
gram (Grant 2017M3D1A1039378) (M. K. S. L. and H. K.).
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