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Accepted Article

Title: Engineering atomic interface by single Pt atoms for enhanced

photocatalytic hydrogen production

Authors: Yuanjun Chen, Shufang Ji, Wenming Sun, Yongpeng Lei,

Qichen Wang, Ang Li, Wenxing Chen, Gang Zhou, Zedong
Zhang, Yu Wang, Lirong Zheng, Qinghua Zhang, Lin Gu,
Xiaodong Han, Dingsheng Wang, and Yadong Li

This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
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the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.

To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201912439

Angew. Chem. 10.1002/ange.201912439

Link to VoR: http://dx.doi.org/10.1002/anie.201912439

http://dx.doi.org/10.1002/ange.201912439
Angewandte Chemie International Edition
RESEARCH ARTICLE
Engineering atomic interface by single Pt atoms for enhanced
photocatalytic hydrogen production
Yuanjun Chen, Shufang Ji, Wenming Sun, Yongpeng Lei*, Qichen Wang, Ang Li, Wenxing Chen,
Gang Zhou*, Zedong Zhang, Yu Wang, Lirong Zheng, Qinghua Zhang, Lin Gu, Xiaodong Han,
Dingsheng Wang*, Yadong Li*
Abstract: It is highly desirable to optimize the structure of
photocatalysts at the atomic scale to facilitate the separation of
electron-hole pairs for enhanced performance, but it still remains
challenging. Here, we report a highly efficient photocatalyst by
assembling single Pt atoms on defective TiO2 support (Pt1/def-TiO2).
Except as proton reduction sites, single Pt atoms promote the
neighboring TiO2 units to generate surface oxygen vacancies and
form Pt-O-Ti3+ atomic interface. Experimental results and density
functional theory calculations demonstrate that Pt-O-Ti3+ atomic
interface effectively facilitates photogenerated electrons to transfer
from Ti3+ defective sites to single Pt atoms, thereby enhancing the
separation of electron-hole pairs. This unique structure makes
Pt1/def-TiO2 exhibit a recorded-level photocatalytic hydrogen
production performance with an unexpectedly high turnover
frequency of 51423 h-1, exceeding the Pt nanoparticles supported
TiO2 catalyst by a factor of 591.
Introduction
[*] Y. Chen[+], Dr. S. Ji[+], Z. Zhang, Prof. D. Wang, Prof. Y. Li
Department of Chemistry, Tsinghua University, Beijing 100084
China
E-mail: wangdingsheng@mail.tsinghua.edu.cn
ydli@mail.tsinghua.edu.cn
Dr. W. Sun[+]
College of Science, China Agricultural University, Beijing 100193,
China
Prof. Y. Lei, Q. Wang
State Key Laboratory of Powder Metallurgy & Hunan Provincial Key
Laboratory of Chemical Power Sources, College of Chemistry and
Chemical Engineering, Central South University, Changsha,
410083, China
E-mail: lypkd@163.com
Dr. A. Li, Prof. X. Han
Beijing Key Laboratory of Microstructure and Property of Advanced
Materials, Beijing University of Technology, Beijing 100024, China
Dr. W. Chen
Materials and Green Applications, School of Materials Science and
Engineering, Beijing Institute of Technology, Beijing 100081, China
Prof. G. Zhou
School of Science, Hubei University of Technology, Wuhan 430068,
China
E-mail: gzhou@mail.buct.edu.cn
Dr. Y. Wang
Shanghai Synchrotron Radiation Facilities, Shanghai Institute of
Applied Physics, Chinese Academy of Sciences, Shanghai 201204,
China
Dr. L. Zheng.
Beijing Synchrotron Radiation Facility, Institute of High Energy
Physics, Chinese Academy of Sciences, Beijing, China
Dr. Q Zhang, Prof. L. Gu
Beijing National Laboratory for Condensed Matter Physics, Institute
of Physics, Chinese Academy of Sciences, Beijing 100190, China.
[+] These authors contributed equally to this work.
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.
10.1002/anie.201912439
Photocatalytic water splitting into hydrogen fuel holds promise
as a clean and sustainable energy-conversion approach to solve
the increasing energy crisis and environment challenges. [1]
Since the discovery of photocatalytic water splitting in 1972, TiO 2
Accepted Manuscript
materials have been regarded as the benchmark catalysts and
have attracted existence research interests. [2] However, limited
by the low light utilization and rapid photogenerated electron-
hole recombination, the catalytic performance of TiO 2-based
photocatalysts remains far from satisfactory. [3] Engineering
defects can efficiently tune the optical property and energy band
structure to enhance intrinsic photocatalytic properties of TiO 2
and improve the light absorption capacity. [4] However, on the
other hand, the induced defects unavoidably lead to new
trapping and recombination centers of photogenerated charge
carrier, which might result in a decrease of photocatalytic
activity.[5] Apparently, it is important and highly desirable to
optimize the defects distribution and structure to promote
intrinsic properties of photocatalysts and inhibit charge carrier
recombination.[6]
Tremendous efforts have been devoted to facilitating the
separation of electron-hole pairs for enhanced photocatalytic
performance.[5a,7] Particularly, one popular strategy is
assembling metal nanoparticles as co-catalysts on
semiconductors to form hetero-structured photocatalysts. The
metal nanoparticles can not only accept photogenerated
electrons to facilitate the interfacial charge separation and
transfer, but also offer proton reduction sites. [8] Among various
metals, Pt is deemed as the best co-catalyst owing to a suitable
Fermi level for trapping electrons and a low potential for H 2
evolution. Within this hetero-structured photocatalysts, the
rational construction of phase interfaces plays an essential role
in determining the charge transfer efficiency and consequent
reaction activity.[9] However, limited fraction of interfacial sites of
current hetero-structured photocatalysts restricts the further
improvement of photocatalytic performance. Additionally, the low
atom-utilization efficiency as well as the high cost and scarcity of
Pt hinder the application of these hetero-structured
photocatalysts. Recently, single-atomic sites catalysts (SACs)
have emerged as a new frontier in catalysis because of
maximum atom-utilization efficiency and outstanding catalytic
performance.[10] And, downsizing metal nanoparticles into single
atoms can fully expose phase interfaces. Moreover, the
structural specificity of SACs featured with spatial atomic
isolation and unique electronic structure may endow SACs with
unexpected properties that nanometer-sized co-catalysts do not
possess.
Here, we report a highly efficient and robust photocatalyst
with isolated Pt atoms anchored on defective TiO 2 support
(Pt1/def-TiO2). We discover that single Pt atoms can not only
serve as proton reduction sites, but promote the neighboring
Angewandte Chemie International Edition 10.1002/anie.201912439

RESEARCH ARTICLE

TiO2 units to generate the surface oxygen vacancies via a atoms. Meanwhile, the darker regions around Pt atoms, marked
hydrogen spillover effect,[11] leading to the formation of atomic by a blue arrow, are clearly observed in Figure 1f, implying the
interface between isolated Pt atom and Ti 3+ defect with the defective structure of TiO2 support. As shown in intensity profiles
atomically dispersed Pt-O-Ti3+ active center. A series of photo- from two different regions (region 1 and 2) in Figure 1f, only one
electrochemical characterizations and density functional theory maximum peak is observed, consistent with the individual Pt
(DFT) calculations reveal that the existence of Pt-O-Ti3+ atomic atoms (Figure 1g).
interface contributes to the enhanced transfer efficiency of the
photogenerated electrons from Ti3+ defective sites to single Pt
atoms, which facilitates the separation of electron-hole pairs and
inhibits their subsequent recombination. The unique construction
of Pt-O-Ti3+ atomic interface endows the Pt1/def-TiO2 catalyst
with excellent photo-electrochemical properties and a record-
level photocatalytic hydrogen production performance. The

Accepted Manuscript
remarkably high turnover frequency (TOF) of 51423 h-1 is
observed on the Pt1/def-TiO2 catalyst, which is 591 times higher
than that of Pt nanoparticle supported TiO2 catalyst (Pt NPs/f-
TiO2) and surpasses most of known photocatalysts.

Results and Discussion

The synthesis procedures are illustrated in Figure 1a, and

the experimental details are described in the Methods. The
sodium titanate was firstly prepared. The transmission electron
microscopy (TEM) image of sodium titanate displays a
multilayered tubular morphology (Figure S1). Then, the
H2PtCl6·6H2O in 0.1 M HCl aqueous solution was injected into
Figure 1. (a) Schematic diagram of preparation process of the Pt1/def-TiO2
the suspension that containing sodium titanate nanotubes under
catalyst. (b-d) TEM image (b), HRTEM image (c), and EDS mappings of Pt
a vigorous stirring. Subsequently, the mixture was collected and (blue), Ti (green), O (red), respectively (d) of Pt1/def-TiO2. (e, f) AC HAADF-
dried, followed by calcination in air at 400℃ to transform titanate STEM image (e) and the corresponding enlarged image (f) of Pt1/def-TiO2
into anatase TiO2 support. The final catalyst consisted of single catalyst. The Pt atoms are marked by the yellow circles. (g)The intensity
profiles obtained in regions 1 and 2 in (f). Scale bars are 100 nm, 5 nm, 10 nm,
Pt atoms supported on defective TiO2 (Pt1/def-TiO2) was
10 nm and 2 nm in b, c, d, e and f, respectively.
obtained after a low-temperature reduction treatment under 5%
H2/Ar atmosphere at 160 ℃ . TEM and high-resolution
transmission electron microscopy (HRTEM) images reveal that
To further determine the local coordination structure of
the morphology of Pt1/def-TiO2 catalyst is a multilayered tubular
Pt1/def-TiO2, element-selective X-ray absorption fine structure
structure with the rough surface (Figures 1b and 1c). As shown
(XAFS) measurement was employed. From the normalized X-
in Figure 1c, the disordered layers on the surface of Pt1/def-
ray absorption near edge structure (XANES) curves of Pt L3-
TiO2 are clearly observed and marked with blue dashed lines.
edge, the white line intensity of the Pt1/def-TiO2 is higher than
The X-ray diffraction (XRD) patterns of Pt1/def-TiO2
that of Pt foil reference and lower than that of PtO 2 (Figure 2a).
demonstrates the characteristic peaks indexed to anatase TiO 2
This finding reveals that single Pt atoms in the Pt 1/def-TiO2 carry
phase, and no corresponding signals associated with crystalline
partially positive charge, suggesting the charge transfer between
Pt species are detected, indicating a high dispersion of Pt
single Pt atoms and the surrounding O atoms via enhanced
species (Figure S2). This result is further confirmed by high-
metal-support interaction. As shown in Figure 2b, the Fourier
angle annular dark-field scanning transmission electron
transferred extended X-ray absorption fine structure (FT-
microscopy (HAADF-STEM) image, where no obvious Pt
EXAFS) plot of the Pt1/def-TiO2 displays only a major peak at
nanoparticles are observed (Figure S3). The energy-dispersive
1.6 Å, attributed to Pt-O coordination. In addition, no FT-EXAFS
X-ray spectroscopy (EDS) mappings reveal the uniform
peaks associated with Pt-Pt coordination are detected, indicating
dispersion of Pt, Ti, O elements (Figure 1d). The Pt loading
the sole existence of single Pt atoms. Quantitative least-squares
content of Pt1/def-TiO2 is measured by inductively coupled
EXAFS best-fitting analysis was performed to investigate the
plasma optical emission spectroscopy (ICP-OES) as 0.02 wt%.
coordination configurations of Pt1/def-TiO2 and references. The
To directly observe the dispersion of Pt species in Pt1/def-TiO2
structural parameters of Pt1/def-TiO2 and Pt foil are summarized
at the atomic scale, the aberration-corrected high-angle annular
in Table S1. The EXAFS fitting curves of Pt1/def-TiO2, PtO2 and
dark-field scanning transmission electron microscopy (AC
Pt foil are shown in Figure 2c, 2d and Figures S4 to S7,
HAADF-STEM) was performed, where clearly demonstrates that
respectively. Compared with PtO2 and Pt foil references, the
several isolated bright dots labeled by yellow circles are
fitting results of Pt1/def-TiO2 demonstrate the first shell
distinguished from surrounding light atoms of TiO 2 support
coordination number of the Pt atoms coordinated by O atoms is
(Figures 1e and 1f), suggesting the existence of individual Pt
about 5, and the corresponding bond length is about 1.98 Å.

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Angewandte Chemie International Edition
RESEARCH ARTICLE
Based on the best-fitting EXAFS results, DFT calculations were
performed to establish and optimize the atomic structure model
of Pt1/def-TiO2 that displays in the inset of Figure 2c.
Figure 2. (a) XANES spectra of Pt L3-edge over Pt1/def-TiO2 catalyst, Pt foil
and PtO2. The area marked by rectangle frame highlights the white line
intensity of Pt1/def-TiO2 catalyst, Pt foil and PtO2. (b) FT-EXAFS spectra of
Pt1/def-TiO2 catalyst, Pt foil and PtO2. (c) EXAFS R space fitting curve (blue
line) and the experimental one (circle) of Pt1/def-TiO2 catalyst. (d) EXAFS k
space fitting curve (blue line) and the experimental one (circle) of Pt1/def-TiO2
catalyst.
Moreover, we discover that single Pt atoms can facilitate the
neighboring TiO2 units to generate the surface oxygen vacancies
and Ti3+ defects during the low-temperature reduction treatment
in the synthesis of Pt1/def-TiO2 catalyst via a hydrogen spillover
effect. To reveal this novel phenomenon, we utilized in situ
environmental transmission electron microscopy (ETEM) to
directly observe and record the process of single Pt atoms-
driven defect engineering. The evolution trajectory of defects
was tracked in the temperature window from room temperature
to 200 oC under the H2 atmosphere. The captured video (Movie
S1) and the corresponding representative images obtained at
different temperatures (Figure 3a) demonstrate that TiO2
support maintains tubular shape with smooth surface below 160
o
C. As the operation time is prolonged at 160 oC, the outside
surface of TiO2 becomes rough and highly disorder surface
layers gradually emerge, indicating the formation of surface
defects on the outside surface of TiO2. When the temperature is
elevated to 180 oC and 200 oC, the degree of disorder on the
outside surface of TiO2 is obviously strengthened. And more
crystalline TiO2 layers in the outside surface transform into
disorder layers. As highlighted by yellow dot lines, the thickness
of crystalline TiO2 layers gradually decreases along with
increasing surface roughness on outside TiO2 surface,
suggesting crystalline TiO2 layers in the outside surface
gradually transform into disorder and defective layers. However,
negligible variations on inner surface of TiO 2 are observed. The
obvious structural difference between the outside surface and
inner surface of TiO2 well confirm that the formation of surface
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10.1002/anie.201912439
defects is promoted by single Pt atoms, because single Pt atoms
are located on the outside surface of TiO2 support. To further
verify it, the Pt-free TiO2 (f-TiO2) was prepared with the same
synthesis procedure of Pt1/def-TiO2 except that H2PtCl6·6H2O
was not added. For comparison, the f-TiO2 sample was also
tested and observed by ETEM measurement under the identical
condition. The ETEM images show that no obvious changes in
the surface of f-TiO2 are detected even at the high operating
temperature of 200 oC (Figure S8). The in situ observation of
ETEM offers direct and solid evidences to demonstrate the
evolution of single Pt atoms-driven surface defect engineering.
We further conducted DFT calculations to investigate the
formation mechanism of single Pt atoms-driven surface defect
Accepted Manuscript
engineering (Figure 3b and Figure S9). Firstly, hydrogen
molecule adsorbed on the Pt site of Pt1/def-TiO2 with a side-on
adsorption mode. The distances between hydrogen atoms and
Pt are 2.003 and 2.045 Å. The small adsorption energy (-1.48
kcal mol-1) indicates hydrogen molecules undergoes a
physisorption. The H-H bond of active H2* is larger than that in
free molecule (0.781 vs 0.746 Å). One hydrogen atom can
transfer to its neighboring O2c atom on the surface with only a
small barrier (18.9 kcal mol-1). Next, the other hydrogen atom on
Pt site transfers to the O2c-H specie to form one water molecule.
The barrier in this step is 29.3 kcal mol -1. The new formed water
molecule is not able to desorb from Pt site easily because of a
desorption energy about 33.0 kcal mol -1. According to the
previous study, the oxygen vacancies on anatase TiO 2 (101)
surface are less stable than them in bulk. Hence, the oxygen
diffusion from subsurface to surface will fill the surface
vacancies, and this process in this model is accompanied by the
diffusion of water molecule from O2c to Ti5c.[12] According to our
calculation results, the oxygen diffusion from subsurface to
surface needs to overcome a barrier of 27.2 kcal mol -1. After that,
the following oxygen diffusion is believed to conduct from bulk to
subsurface to maintain the five-coordinated Pt to trigger the next
round of reaction (Figure S10). It should be noted that on the
top of Ti5c, the desorption energy of water decease to 16.1 kcal
mol-1, indicating water is easy to desorb.
Angewandte Chemie International Edition
RESEARCH ARTICLE
Figure 3. (a) Representative movie images acquired at different temperatures
of Pt1/def-TiO2. Frames from Movie S1 acquired at various temperatures of the
heat-treatment of Pt1/def-TiO2 with ETEM under an H2 atmosphere from room
temperature to 200 °C. Scale bar, 10 nm. (b) The optimized structures of
intermediate states and transition states on Pt1/def-TiO2 surfaces during the
single Pt atoms-driven surface defect engineering.
To confirm this unique phenomenon, a series of photo-
electrochemical experiments are carried out. [13] Firstly, electron-
paramagnetic resonance (EPR) measurement was conducted to
detect the oxygen vacancies, which demonstrates a signal of
oxygen vacancy at the g values of 2.003. As shown in Figure
S11, the signal intensity of oxygen vacancies of Pt 1/def-TiO2 is
obviously higher than that of f-TiO2, suggesting the existence of
single Pt atoms promotes the generation of oxygen vacancies.
Secondly, Raman spectra were performed to investigate the
surface information. As shown in Figure S12, the peaks of
Raman spectra of Pt1/def-TiO2 and f-TiO2 at 145, 197, 396 and
515 cm-1 are ascribed to anatase TiO2 phase.[13a] Compared with
the commercial P25, the peak intensities of Pt1/def-TiO2 and f-
TiO2 are obviously decreased (Figure S12a). And the shift and
broadening of the Eg peaks at ~144 cm-1 in enlarged Raman
spectra of Pt1/def-TiO2 are more obvious than that of f-TiO2
(Figure S12b), indicating Pt1/def-TiO2 possesses more
disordered phase on the surface and higher oxygen vacancies
concentration. Furthermore, X-ray photoelectron spectroscopy
(XPS) analysis was carried out to study the chemical states of
Pt1/def-TiO2 and f-TiO2. The O 1s spectra of Pt1/def-TiO2 exhibits
two peaks at 530 eV and 532.1 eV, which are attributed to lattice
oxygen (deemed as the oxygen band of Ti-O-Ti) and the oxygen
atoms near oxygen vacancies, respectively. The peak area at
532.1 eV in Pt1/def-TiO2 is much larger than that of f-TiO2
(Figure S13), suggesting the content of oxygen vacancies in
Pt1/def-TiO2 is obviously higher than that of f-TiO2. In Ti 2p
spectra, the XPS peaks at 458.7 eV and 457.9 eV are ascribed
This article is protected by copyright. All rights reserved.
10.1002/anie.201912439
to Ti4+ and Ti3+ defect, respectively31. As is well known, the
formation of Ti3+ defect is directly related to the presence of
oxygen vacancies. The signal intensity of Ti 3+ of Pt1/def-TiO2 is
much stronger than that of f-TiO2 (Figure S14), revealing the
obviously increased concentration of oxygen vacancies of
Pt1/def-TiO2 owing to the existence of single Pt atoms. Taken
together, it is well confirmed that single Pt atoms favor the
surrounding TiO2 units to generate the surface oxygen
vacancies and Ti3+ defects, leading to forming the atomic
interface of single Pt atoms and Ti3+ defects in form of Pt-O-Ti3+
structure. The unique Pt-O-Ti3+ atomic interface enhances the
photo-electrochemical properties of Pt1/def-TiO2. Figure S15
shows UV-vis spectra of Pt1/def-TiO2 and f-TiO2. Although
Accepted Manuscript
Pt1/def-TiO2 and f-TiO2 have the similarly strong absorption in
the UV region, their visible light absorption has a large difference.
The f-TiO2 shows a very weak absorption in the range of 400-
430 nm, while the Pt1/def-TiO2 exhibits a much stronger
absorption in the visible light region of 400-800 nm, which is
associated with the abundant surface oxygen vacancies and Ti 3+
defects of the Pt1/def-TiO2. And, the color of the Pt1/def-TiO2
sample is light yellow, while f-TiO2 displays white, which is
consistent with the light absorption property. Furthermore,
photocurrent response measurements were conducted to
investigate the charge-separation efficiency. As shown in Figure
S16, the photocathode of the Pt 1/def-TiO2 demonstrates a higher
photocurrent density compared with f-TiO2, indicating that the
unique Pt-O-Ti3+ atomic interface endows Pt1/def-TiO2 with
better performance on generating photogenerated electron-hole
pairs and suppressing their subsequent recombination. All
above results confirm that the single Pt atoms can promote the
neighboring TiO2 units to generate the surface oxygen vacancies,
leading to the formation of atomic interface between isolated Pt
atom and Ti3+ defect with the atomically dispersed Pt-O-Ti3+
active center.
Given the excellent photo-electrochemical properties, the
Pt1/def-TiO2 was applied in photocatalytic hydrogen production
reaction. As shown in Figure 4a and 4b, the f-TiO2 catalyst
exhibits a poor photocatalytic performance with 672 μmol g-1 h-1,
which may result from the fast electron-hole recombination. As
expected, the as-obtained Pt1/def-TiO2 catalyst exhibits a
remarkably enhanced photocatalytic performance even at a low
Pt content of 0.02 wt%. The photocatalytic H2 production rate of
Pt1/def-TiO2 catalyst reaches up to 52720 μmol g-1 h-1. For
comparison, the Pt nanoparticles as co-catalysts supported on
TiO2, marked with Pt NPs/f-TiO2 catalyst, was prepared and
characterized (Figure S17). And the photocatalytic activity with
a H2 production rate of 4458 μmol g-1 h-1 is observed on this Pt
NPs/f-TiO2 catalyst. The photocatalytic H2 production rate of
Pt1/def-TiO2 is about 78.5 and 11.8 times than those of pure f-
TiO2 and Pt NPs/f-TiO2 (Figure 4b). Moreover, the Pt1/def-TiO2
catalyst achieves an unexpectedly great turnover frequency
(TOF) of 51423 h-1, which is a significant enhancement by a
factor of 591 in comparison with Pt NPs/f-TiO2 (TOF, 87 h-1)
catalyst (Figure 4c). To our best knowledge, the Pt1/def-TiO2
catalyst exhibits a recorded-level photocatalytic H2 production
activity, which outperforms most of previously reported
photocatalysts (Table S2). These results reveal that maintaining
Pt species as isolated atomic sites to form Pt-O-Ti3+ atomic
Angewandte Chemie International Edition 10.1002/anie.201912439

RESEARCH ARTICLE

interface plays a crucial role in boosting the photocatalytic processes are highly complex as determined by the previously
performance. reported literatures [12,15], therefore, in the HER calculations, the
oxygen vacancies were not introduced.

As shown in Figure 5a, single Pt atom at either hollow2

adsorption site or Pt5c substitution site does not show a good
catalytic activity. More precisely, we can see that the single Pt
atom at the Pt6c substitution position (∆GH*=-0.06 eV) exhibits
better catalytic activity than the Pt catalyst (based on Pt(111)
slab model [16] (|∆GH*| = 0.10 eV) (Figure 5b and Figure S25),
because it is closer to the optimization values (i.e., |∆GH*|  0)
[16a]
, using a simple kinetic model combining with statistical
analysis on a DFT database of hydrogen chemisorption energies
on materials.[17] As shown in Figure 5c, the configurations of

Accepted Manuscript
reactant initial states, intermediate states, and final states for
Volmer step, Tafel step and Heyrosky step were inset together
with their reaction pathways. In neutral media, water molecules
are the reacting species. Water molecules are inert, therefore,
water activation and dissociation kinetic in Volmer step (water
Figure 4. (a) Hydrogen production monitored over 2h in the presence of dissociation and H* formation) is usually crucial for the entire
CH3OH as sacrificial electron donors. (b,c) The photocatalytic H2 production process [17]. For the considered model, the energy barrier in
activities (b) and TOFs (c) of Pt1/def-TiO2 and references. (d) Cyclic tests of Volmer step is 33.6 kcal/mol. Then both Heyrovsky step and
Pt1/def-TiO2 under UV-visible light. Tafel step were considered and the corresponding energy
barriers were calculated. Obviously, the favorable hydrogen
desorption process is the Tafel step with an energy barrier of
The cyclic tests were performed to assess the photocatalytic 28.2 kcal/mol, being much lower than that of Heyrovsky step
durability. As revealed in Figure 4d, the Pt1/def-TiO2 catalyst (96.4 kcal/mol). Furthermore, the barrier of Tafel step is also
shows a negligible decline in continuous H 2 production during lower than that of Volmer step, indicating that the water
the subsequent cyclic runs. Furthermore, we characterized the dissociation is indeed the rate-determining-step.
spent Pt1/def-TiO2 catalyst after cyclic durability tests. The
corresponding XRD pattern matches well with the fresh Pt 1/def-
TiO2 catalyst, suggesting its crystallinity and structure are well
retained (Figure S18). Also, TEM images, HRTEM images, EDS
mapping as well as AC HAADF-STEM images together confirm
that no nanoparticles aggregation is detected and Pt species are
existed as isolated atoms (Figures S19 and S20). Furthermore,
the Pt-L3-edge XANES and EXAFS spectra of the spent Pt 1/def-
TiO2 are similar to those of the fresh Pt1/def-TiO2, indicating
atomic dispersion and structural properties of Pt species are still
preserved after cyclic durability tests (Figures S21 and S22).
The above results demonstrate the excellent stability of Pt 1/def-
TiO2.

We further conducted DFT calculations to gain insight into

the mechanism of the process. Several sites on TiO2 (101)
surface such as two hollow sites, and top site of O 2c (Figures
S23 and S24) were considered as the adsorption sites for single
Pt atom. Among them, hollow1 was the most stable adsorption
sites. Furthermore, the substitution configuration Pt 5c, where Pt
atom replaces the topmost Ti5c atom was also chosen as a
substrate for HER process since in this configuration, the
EXAFS measurement determined the existence of 5-coordinated
Pt atom. It should be noted that oxygen vacancies are common Figure 5. (a) DFT calculation of free energy ∆GH* of H adsorption on Hollow2
on anatase TiO2(101) surface [14]. Hence the substitution (purple), Pt5c (green), Pt6c (blue) positions in Pt1/def-TiO2 and Pt NPs (orange)
configuration Pt6c, where Pt atom replaces the topmost Ti6c atom at a potential U = 0 relative to the RHE at pH =7. (b) The detailed geometrical
was also chosen as an alternative substrate for HER process structures of Pt1/def-TiO2 at Hollow2 (purple), Pt5c (green), Pt6c (blue) positions
since it will convert into Pt5c once an oxygen vacancy is formed. and Pt NPs (orange). (c) Mechanism study for hydrogen evolution of Pt1/def-
The corresponding binding and substitution energies were listed TiO2.
in Table S3. For oxygen vacancies, their formation and diffusion

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Angewandte Chemie International Edition
RESEARCH ARTICLE
Conclusion
In summary, we fabricate a high-performance photocatalyst
by assembling isolated Pt atoms on the defective TiO 2. We
discover that the presence of single Pt atoms promotes the
construction of Pt-O-Ti3+ atomic interface. The control
experiments and various photo-electrochemical characterization
as well as DFT calculations together well confirm that the
transfer efficiency of photogenerated electron from Ti3+ defective
sites to single Pt atoms is facilitated via the Pt-O-Ti3+ atomic
interface, which favors the separation of electron-hole pairs and
suppresses the subsequent recombination. Owing to this unique
atomic interface, the Pt1/def-TiO2 catalyst achieves a recorded-
level photocatalytic H2 production performance, exceeding
almost all of known photocatalysts. This work presents an
effective approach to boost catalytic performance via the
construction of atomic interface. We believe this design concept
will be widely applied to develop other highly efficient catalysts.
Acknowledgements
This work was supported by the National Key R&D Program of
China (2018YFA0702003, 2018YFB0704100), the National
Natural Science Foundation of China (21671117, 21871159,
21890383, 21703219, 51872008), the National Postdoctoral
Program for Innovative Talents (BX20180160), the China
Postdoctoral Science Foundation (2018M640113), and the
Beijing Natural Science Foundation (No. 1182005). We thank
the BL14W1 station in Shanghai Synchrotron Radiation Facility
(SSRF) and the 1W1B station in Beijing Synchrotron Radiation
Facility (BSRF) for XAFS measurements.
Keywords: single Pt atoms • surface defect engineering •
atomic interface • photocatalytic hydrogen production
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Angewandte Chemie International Edition 10.1002/anie.201912439

RESEARCH ARTICLE

RESEARCH ARTICLE
Yuanjun Chen, Shufang Ji, Wenming
Sun, Yongpeng Lei*, Qichen Wang, Ang
Li, Wenxing Chen, Gang Zhou*, Zedong
Zhang, Yu Wang, Lirong Zheng,
Qinghua Zhang, Lin Gu, Xiaodong Han,
Dingsheng Wang*, Yadong Li*

Single Pt atoms assembled on defective TiO2 support (Pt1/def-TiO2) as a highly Page No. – Page No.
efficient photocatalyst not only serve as proton reduction sites, but promote the
Engineering atomic interface by single
neighboring TiO2 units to generate surface oxygen vacancies, leading to the
Pt atoms for enhanced photocatalytic
formation of atomic interface between isolated Pt atom and Ti 3+ defect with the

Accepted Manuscript
hydrogen production
atomically dispersed Pt-O-Ti3+ active center. This unique structure endows Pt1/def-
TiO2 with excellent photocatalytic hydrogen production performance.

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