Electrochimica Acta 412 (2022) 140129

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Electrochimica Acta
journal homepage: www.journals.elsevier.com/electrochimica-acta

A facile “dark”-deposition approach for Pt single-atom trapping on facetted

anatase TiO2 nanoflakes and use in photocatalytic H2 generation
Gihoon Cha a, 1, Anca Mazare a, b, Imgon Hwang a, Nikita Denisov a, Johannes Will c,
Tadahiro Yokosawa c, Zdeněk Badura d, Giorgio Zoppellaro d, Alexander B. Tesler a,
Erdmann Spiecker c, Patrik Schmuki a, d, e, *
a
Department of Materials Science WW4-LKO, Institute for Surface Science and Corrosion (LKO), Friedrich-Alexander-University of Erlangen-Nuremberg, Martensstrasse
7, D-91058, Erlangen 91058, Germany
b
Advanced Institute for Materials Research (AIMR), National University Corporation Tohoku University (TU), Sendai 980-8577, Japan
c
Institute of Micro- and Nanostructure Research (IMN) and Center for Nanoanalysis and Electron Microscopy (CENEM), Friedrich-Alexander-Universität Erlangen-
Nürnberg (FAU), IZNF, Cauerstraße 3, Erlangen 91058, Germany
d
Regional Center of Advanced Technologies and Materials, Šlechtitelů 27, Olomouc 78371, Czech Republic
e
Department of Chemistry, Faculty of Science, King Abdulaziz University, P.O. Box 80203, Jeddah 21569, Saudi Arabia

A R T I C L E I N F O A B S T R A C T

Keywords: In recent years, single-atom (SA) catalysts have become strongly investigated in electrocatalysis and increasingly
Platinum single-atom also in photocatalysis. Here we demonstrate that single-crystalline anatase TiO2 nanoflake (NF) layers after a
Photocatalysis facile thermal air annealing process provide suitable anchoring sites for Pt SAs. Remarkably, such air annealed
Hydrogen generation
(001) faceted single-crystalline TiO2 nanoflakes can trap and stabilize Pt SAs and assemblies when immersed into
Single-crystal anatase TiO2
a Pt precursor solution for sufficient time in absence of any illumination, i.e., under "dark deposition” conditions.
Single-atom catalysis
“Dark”-deposition These decorated species act as more efficient co-catalysts for the H2 evolution reaction, compared to the classical
Pt nanoparticles (NPs). Here we show that such single-crystal-based TiO2 photocatalyst, decorated with Pt SAs,
can display a 4-fold increase in photocatalytic H2 production at a lower Pt loading than observed for a classical Pt
nanoparticle Pt/TiO2 arrangement.

1. Introduction
Over the past few years, single atom (SA) catalysts have not only
been of high interest in thermal heterogeneous catalysis but also entered
strongly into the field of electrocatalysis where it is used for organic
electrosynthesis, fuel cells, batteries, electrolyzers, and particularly
focusing on oxygen reduction or evolution, hydrogen evolution or
oxidation, carbon dioxide reduction or nitrogen reduction reactions) [1,
2]. The reason to utilize SAs is mainly due to the maximized
surface-to-volume ratio of such catalysts and novel reaction pathways
that become available at the SA level [3-11]. Most recently, SAs became
also attractive as co-catalysts in photocatalytic reactions [3,6,12-16]. In
photocatalysis, the mobile charge carriers (electron-hole pairs) that are
generated by illuminating a semiconductor, experience charge transfer
reactions with the environment. To enhance the kinetics of the slow
transfer reactions, typically noble metal co-catalysts are required for
photocatalytic reactions and, in particular, for the photocatalytic H2
evolution reaction (HER). Noble metals such as Au, Pt, Pd, etc. are
usually used in the form of nanoparticles (NPs) [15,17-21].
In contrary to the common methods, used to deposit noble metal co-
catalyst as NPs, SA co-catalysts have several substantial advantages such
as a minimal noble metal loading, i.e., reduced costs, and, at the same
time, a maximal surface-to-volume ratio. One of the most crucial issues
for using SA co-catalyst is its surface immobilization on the desired
substrate. Typical approaches for SA loading include methods based on
chemical trapping or molecular-beam-soft-landing [22-24].In general
SA traps are based on specific electronic or geometric features of the
substrates [25].
In the current state of research of the application of SA in photo­
catalysis, two semiconductors are primarily investigated, i.e.,

* Corresponding author at: Department of Materials Science WW4-LKO, Institute for Surface Science and Corrosion (LKO), Friedrich-Alexander-University of
Erlangen-Nuremberg, Martensstrasse 7, D-91058, Erlangen 91058, Germany.
E-mail address: schmuki@ww.uni-erlangen.de (P. Schmuki).
1
Present address: Bavarian Center for Battery Technology (BayBatt), University of Bayreuth, 95447 Bayreuth, Germany.

https://doi.org/10.1016/j.electacta.2022.140129
Received 3 December 2021; Received in revised form 25 February 2022; Accepted 27 February 2022
Available online 1 March 2022
0013-4686/© 2022 Elsevier Ltd. All rights reserved.
G. Cha et al.
nanostructured C3N4 and anatase TiO2 [6]. The former has good visible
light absorption characteristics. On the other hand, nanostructured
anatase TiO2 is a benchmark photocatalytic material owing to its
excellent photocorrosion stability and wide range of applications that
rely on photocatalytic reactions [19,26]. It is worth pointing out that
among the polymorphs of TiO2, anatase shows a higher reactivity to the
red-ox potential of water and thus has more optimized energetics than
rutile [26-29].
In the field of electrochemistry and photoelectrochemistry, the for­
mation of the anchoring points on the support materials’ surface, which
can set up and sustain single atom (SA) states, is vital. Thus, the for­
mation of suitable trapping sites is indispensable for granting stability to
the SAs. So far, many approaches were investigated for the SA deposition
including methods such as coprecipitation, atomic layer deposition,
photochemical reduction, etc., which are based on metal-containing
precursors that are placed, reduced, and anchored on the support by
defects or vacancies [11]. Two points are further of significant impor­
tance for SACs in electrocatalysis, i.e., selectivity (since alternative re­
action pathways compared to classic nanoparticles might be involved),
and activity/stability (the strong interaction between SA and the sup­
port can significantly influence their electrochemical activity and sta­
bility) [11,30]. Yang et al. reported on a series of impregnation and
annealing approaches to decorate TiO2 nanoparticles with Pt-O units
that provide a remarkable reactivity [31].
In contrast to these approaches, concerning TiO2 and single-atom co-
catalysts, we showed recently that surface defects (Ti3+-Ov) induced by
reducing in Ar/H2 atmosphere (e.g., Pt SA deposition on anatase TiO2
sputtered layers [25], or Pd, Pt or Au on (001) TiO2 nanosheets [32]) or
native defects in anodic TiO2 nanotubes (e.g., Ir or Pt SA deposition on
anatase TiO2 nanotubes [33]), or on TiO2 nanoflakes (e.g. Pt SA [34])
allow a direct, simple immersion reaction of the TiO2 surface with a Pt4+
precursor to form Pt SAs with a nominal charge (d) of ≈2.
In view of single-crystalline (SC) anatase, facetted SC layers have
attracted wide attention. The preferential faceting of anatase was shown
to significantly influence the electron and hole transfer in various pho­
tocatalytic reactions. In the case of single-crystalline anatase with (101)
and (001) faceting, the different surface energy of these two facets leads
to the formation of an intrinsic electron junction, which under illumi­
nation (in an aqueous environment) results in electrons exiting from the
(101) and holes from the (001) planes [25,26]. Yang et al [35]. reported
the hydrothermal formation of single-crystal anatase TiO2 nanosheets
(NSs) with a high percentage of (001) facets. The key parameter that was
identified in this process was the presence of fluoride ions, acting as a
capping agent that enables the preferential growth of (001) faceted
crystals (the surface energy of the (001) facets is reduced via the fluoride
termination) [35-38].
To note is that such (001) faceted powder nanosheets have recently
gained attention in photocatalytic and also in other TiO2 applications
[39-41]. However, the application of such crystallite powder nanosheets
in photoelectrochemistry requires their further coating on a conductive
substrate, thus making the production process more complicated and
less efficient. In this sense, direct growth of faceted nanosheets on an
FTO substrate by hydrothermal synthesis is a straightforward approach,
leading to nanoflake photoanodes [42-44].
Here, we explore such single-crystalline (001) faceted TiO2 nano­
sheets (or nanoflakes), grown directly on FTO substrates by a hydro­
thermal method, that we further use for Pt single-atom decoration and
photocatalytic H2 evolution considering the feasibility to anchor Pt
single-atoms. We show that a simple air annealing treatment is sufficient
to create suitable trapping sites on the single crystal surface. These traps
then react in an immersion treatment of the TiO2 nanosheets in a
chloroplatinic acid solution without further UV illumination – we denote
this process thus as “dark-deposition”. We then explore the SA decorated
TiO2 nanoflakes for photocatalytic H2 evolution and find a remarkable
reactivity compared to the classic anatase/Pt NP system. Such SAs
decorated TiO2 nanoflakes were then also characterized by
2
Electrochimica Acta 412 (2022) 140129
photoelectrochemistry in order to gain additional information on rele­
vant charge transfer processes.
2. Experimental
2.1. TiO2 nanoflakes fabrication
Before the TiO2 nanoflakes fabrication on FTO substrates (7 Ω•m− 2,
Pilkington, UK), the FTO glasses were cleaned by ultrasonication in
acetone, ethanol, and DI water for 15 min each followed by drying under
a N2 stream. To fabricate TiO2 nanoflakes (NFs) with preferential (001)
faceting directly on the FTO substrates, a hydrothermal synthesis was
carried out at 150 ◦ C for 15 h using a Teflon-lined stainless steel auto­
clave (capacity 250 mL). The aqueous hydrogen chloride (HCl) solution
was prepared by adding 30 mL HCl (37 %) (Sigma-Aldrich, Germany)
into 30 mL DI water in a Teflon cell, followed by stirring for 15 min.
Afterward, 1.5 mL titanium isopropoxide (Sigma-Aldrich, Germany) was
added into the diluted HCl solution and vigorously stirred for 15 min at
room temperature. As a F− precursor that influences the surface energy
and fundamental structure unit in the TiO2 crystal, 0.5 g ammonium
hexafluorotitanate ((NH4)2TiF6, Sigma-Aldrich, Germany) was added to
the prepared solution, and then stirred at room temperature until
completely dissolved (for 15 min). The cleaned FTO substrates were
then fixed on the ceramic holder obliquely (the fluorine-doped Tin oxide
surface was facing downwards). Subsequently, the hydrothermal syn­
thesis was carried out followed by cooling down to room temperature in
the oven naturally. FTO/TiO2 NF samples were then cleaned with DI
water and dried under a N2 stream. Before the Pt deposition, the TiO2
NFs were annealed at different temperatures for 1 h in air, to remove the
F-terminated remnant contamination layer from the deposition process
[44].
2.2. Pt deposition on TiO2 samples (dark / photodeposition)
The Pt “dark”- (or photo-) deposition on the prepared TiO2 NFs was
performed by the facile dip-coating method with common Pt precursor
as H2PtCl6 (Metakem GmbH, Germany) in aqueous methanol solution
(50 vol %). Normally, a Pt stock solution was prepared initially with a
certain concentration of H2PtCl6 in DI water according to specifications
before the “dark”- (or photo-) deposition. For instance, 2 × 10− 4 M, 1 ×
10− 3 M, and 5 × 10− 3 M of H2PtCl6 stock solutions were prepared for the
concentrations of 1 × 10− 6 M and 5 × 10− 6 M, and 5 × 10− 5 M,
respectively. The annealed TiO2 nanoflakes samples were immersed into
10 mL of aqueous methanol solution in a quartz finger cell (reactor)
followed by the addition of 50 μL of the stock solution into it per each
concentration. Afterward, Ar purging (15 min) was performed to remove
the oxygen present in the solution. (і) “Dark”-deposition - to build up the
dark conditions, the quartz finger cell was wrapped with aluminum foil
after Ar purging, and then kept under stirring at 500 RPM for 24 h
(alternatively for 10 min or 1 h). After the “dark”-deposition, the sam­
ples were rinsed with DI water and then dried under a N2 stream. (ii)
Pre-photodeposition - after Ar purging, the quartz finger cell that con­
taining 50 μL of 1 × 10− 3 M H2PtCl6 stock solution was exposed to the
light source of λ = 365 nm LED (100 mW) for 3 h leading to the for­
mation of Pt nanoparticles (NPs) on the surface of TiO2 NFs and,
simultaneously, accompanying by H2 evolution reaction. The illumi­
nated samples were then rinsed with DI water followed by drying under
a N2 stream.
2.3. Characterization methods
A field-emission scanning electron microscope (FE-SEM, Hitachi,
S4800) equipped with an Energy Dispersive X-Ray (EDAX Genesis, fitted
to SEM chamber) were used for characterization of the morphology and
chemical composition of the samples. HAADF-STEM (High-angle
annular dark-field scanning transmission electron microscopy) and EDS
G. Cha et al. Electrochimica Acta 412 (2022) 140129

(Energy-dispersive X-ray spectroscopy) mapping were performed with a
double-corrected FEI Titan Themis3 300 using an acceleration voltage of
300 kV. The microscope is further equipped with a monochromator and
a Super-X detector system for STEM-EDS analysis. High-resolution
STEM-HAADF (HRSTEM-HAADF) images were taken with a collection
angle from 61 to 200 mrad, a beam current of 120 pA, and a dwell time
of 50 µs. The crystal phase structure of the samples was obtained by X-
ray diffraction (XRD, X’pert Philips PMD diffractometer) operating with
graphite monochromatized Cu irradiation (wavelength: λ = 1.54056
Å.). The chemical composition of the samples was evaluated by X-ray
Photoelectron Spectroscopy (XPS, PHI5600), and spectra were cali­
brated to the Ti 2p peak to 458.0 eV. Fitting of the peaks was performed
in Multipak software, using an asymmetric peak shape for the metallic
platinum and a Gaussian-Lorentzian peak shape for the platinum peaks
attributed to Ptδ+ or Pt4+. EPR spectra were recorded on JEOL-X-320
spectrometer with a variable He temperature set-up ES-CT470 appa­
ratus. All the samples were measured with similar weight (≈15 mg). In
all measurements, EPR tubes were kept at the same position in the cavity
for comparison. Spectra were collected at T = 80 K with following
experimental parameters: modulation amplitude 0.7 mT, modulation
frequency 100 kHz, time constant 0.03 s, microwave power 1 mW and
sweep time 2 min with 3 accumulations to improve signal to noise ratio.
Diffusive reflectance spectra were measured by a fiber-based UV-vis-
IR spectrophotometer (Avantes, ULS2048) equipped with an integrating
sphere AvaSphere-30 using AvaLight-DH-S-BAL balanced power light
source. The optical bandgap of the TiO2 films was obtained by Kubelka-
Munk equation using UV-Vis diffuse reflectance spectra for the indirect
allowed transitions.
2.4. Photocatalytic H2 evolution measurements
The H2 evolution measurements, “dark”- or photo- deposited TiO2
NF samples, were performed by immersion the samples into 10 mL of
aqueous methanol solution followed by Ar purging for 15 min. After­
ward, the samples were exposed to the LED light source of λ = 365 nm
(100 mW). The illuminated area was approximately 1 cm2. For the
“normal” photodeposition, the annealed TiO2 nanoflakes were placed in
a quartz reactor containing 5 × 10− 6 M Pt precursor with 10 mL aqueous
methanol solution and were subjected to illumination with the same LED
light source, while at the same time, measuring the H2 evolution ac­
tivity. The photocatalytic H2 evolution was determined by a gas chro­
matograph (GCMS-QO2010SE, SHIMADZU) with a thermal
conductivity detector (TCD).

Fig. 1. (a) SEM image of the as-formed NFs (low magnification), (b) schematic representation of the NF facets, (c,d) high-resolution SEM images of as-formed and
anatase TiO2 NFs (annealed at 450 ◦ C in air). (e) H2 evolution rate at λ = 365 nm of the “dark”-deposited (D-D) as-formed and annealed TiO2 NFs. (f) XPS F 1s high-
resolution peak for the “dark”-deposition as-formed and anatase NFs (F/Ti atomic ratio).

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2.5. Photoelectrochemical characterization
Incident photon-to-electron conversion efficiency (IPCE) measure­
ments were carried out in the 300–600 nm range with a setup
comprising an Oriel 6356 150 W Xe arc lamp as the light source and an
Oriel cornerstone 7400 1/8 monochromator as described previously
[45,46]. The measurements were carried out in aqueous 0.1 M Na2SO4
solutions, and at an applied potential of +500 mV, in an electrochemical
cell equipped with a quartz window and operated in a three-electrode
configuration with the nanoflake photoanode as a working electrode,
an Ag/AgClSat electrode as the reference electrode, and a Pt foil as the
counter electrode. To measure J-V spectra, the photoelectrode was
irradiated using a 365 nm wavelength LED light source providing an
intensity of 20 mW•cm− 2 and in 0.1 M Na2SO4 electrolyte. The exper­
iment was carried out in a three-electrode electrochemical cell with Pt
foil as a counter electrode and Ag/AgClSat as a reference electrode.
3. Results and discussion
Fig. 1a, c shows high-resolution SEM images of as-formed (001)
facetted TiO2 nanoflakes (NFs) at various magnifications, together with
a schematic representation of the different NF facets (Fig. 1b). The TiO2
NF layers were formed by hydrothermal synthesis on fluorine-doped tin
oxide (FTO) substrates as described in the experimental section. The
TiO2 NF surface, as synthesized, is very smooth and the sheets show F-
termination [43,47] resulting from the used growth process. Previously
we demonstrated that annealing in air reduces the F-termination on the
TiO2 nanostructures [44]. We annealed the as-formed NFs for 1 h at 150,
300, 450, 600, and 800 ◦ C in air (Figs. 2 and S1,2), and the NFs annealed
at 450 ◦ C were shown to be optimal for H2 evolution after SA decoration,
as will be further discussed. The SEM of the surface after partial
F-removal (Fig. 1d) shows clearly roughness – i.e. the presence of surface
defects after this annealing process. After annealing, the samples display
a similar faceted structure but show a reduction in the F-termination by
approx. 50%, as evident from XPS measurements (see F1s peak in
Fig. 1f).
This is in line with literature reporting that the defluorination in­
troduces Ti3+ surface defects [48,49]. To test the feasibility of using
these surface defects as anchoring points for a Pt co-catalyst on the single
crystal surface, we immersed the annealed surface in an H2PtCl6 solution
for up to 24 h. For reference, we also immersed a non-annealed sample.
In neither case in SEM, any surface modification after the H2PtCl6
exposure can be seen. Then we tested the samples (non-annealed and
air-annealed after exposure to H2PtCl6) and compared them to the ac­
tivity of a sample not exposed to H2PtCl6 (as shown in Fig. 1e). As seen,
the anatase (001) faceted TiO2 NFs result in a negligible H2 generation

Fig. 2. (a) High-resolution SEM images of the as-formed and annealed TiO2 NFs at 300, 450, and 800 ◦ C for 1h showing the (101) and (001) facets. (b) High-
resolution XPS spectra of the as-formed and annealed NFs for Ti 2p, O 1s, and F 1s with (c) corresponding F/Ti ratio obtained from the atomic percentage. (d)
XRD spectra of the as-formed and annealed TiO2 NFs with a comparison of (e) anatase peak (101) and (f) anatase (105) and (211) peaks.

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rate at λ = 365 nm (Fig. 1e, black line). When “dark”-deposited, i.e., with
a Pt SA co-catalyst decoration, the annealed TiO2 NFs display superior
H2 evolution rate as well as stability over the experimental duration, i.e.,
24 h (Fig. 1e, blue line), compared to the “dark”-deposited as-formed
faceted TiO2 NFs (Fig. 1e, red line).
We evaluated in more detail the surface morphology, chemistry, and
crystallinity of the as-formed and the NFs annealed at 150, 300, 450,
600, and 800 ◦ C in air – see Fig. 2 and the high-resolution SEM images of
the different facets in Figs. S1,2, and additional XPS and XRD data in
Fig. S3 and Table S1. The formation of holes on the (001) surface and a
roughening (surface defects) on the (101) surface is observed with
increasing annealing temperature, the latter disappears when annealed
at 800 ◦ C (Figs. 2a and S1,2). With increasing the annealing temperature
there is no significant difference in the Ti 2p XPS peaks, whereas, in the
case of F 1s, there is a substantial decrease, which leads to a F/Ti ratio of
almost zero for temperatures higher than 600 ◦ C. There is however a
difference in the O1s peak for NFs annealed at 800 ◦ C where a pro­
nounced shoulder is clearly visible at ≈532–536 eV – this is due to the
presence of SnO2 due to the diffusion of Sn4+ ions into the lattice of TiO2
from the substrate (the fluorine-doped tin oxide glass). This is clearly
visible in the XPS survey spectra where typical Sn peaks appear only
after annealing at 800 ◦ C (Fig. S4).
The XRD patterns are shown in Fig. 2c, and the overlaid anatase
(105) and (211) peaks in Fig. 2d,e, together with the peak profile fitting
in Table S1. The latter yields a preferred alignment of (101) and (200)
lattice planes as compared to (004). This texture is stable upon both Pt
loading and annealing at elevated temperatures. In addition, XRD
analysis yields an initially tensile strained crystal structure of the as-
formed NFs, which relaxes towards anatase bulk equilibrium after
annealing at 450 ◦ C for 1 h. Interestingly, this lattice strain relaxation is
accompanied by hole formation at the surface of the NFs as revealed by Fig. 3. X-band CW EPR spectra of as-formed TiO2 NFs powder (red line) and
after thermal annealing at different temperatures: 1 h at 300 ◦ C (green line),
HR-SEM imaging (see further Figs. 2a and S1,2) and could, thus, be
450 ◦ C (blue line) or 800 ◦ C (magenta line). The EPR spectra were recorded on
related to the out-diffusion of vacant lattice sites. Whereas Pt loading
powder samples, at T = 80 K and with 1.0 mW of applied microwave power.
does not affect the average measured lattice parameters, annealing at
800 ◦ C for 1 h leads again to a tensile strain of the anatase lattice, which
becomes highly dominant, in comparison to the g⊥=1.999 signal (a),
indicates defect formation in the anatase NF bulk at 800 ◦ C.
and an additional contribution from another type of Ti3+ sites can be
Additional information on the defect structure of the NFs (collected
observed, which is characterized by lower g-values (g⊥=1.967 and g||=
from scraped-off powder) was obtained by electron paramagnetic
1.936, marked as c in Fig. 3). It is speculated that these Ti3+ centers (c)
resonance (EPR) spectroscopy Fig. 3. shows the EPR signals for as-
are subjected to smaller orthorhombic distortions compared to the other
formed NFs and annealed NFs at different temperatures. The as-
lattice embedded Ti3+ sites in anatase, and thus such resonances are
prepared NFs (Fig. 3, red trace), characterized by the highest content
similar to those found in lattice embedded Ti3+ centers observed in rutile
of fluorine within the series, shows very weak signals, just above
polymorphs (g⊥=1.97 and g||= 1.94). The presence of surface exposed
background noise, with g⊥=1.999 (marked as a) and at g⊥=1.984
Ti3+ centers that usually express broad and unresolved signals around
(marked as b). These g-values values are consistent with Ti3+ sites, lat­
g~1.93 [53] is not evident in the sample treated at 450 ◦ C, but a minor
tice embedded, located in anatase phase that are experiencing small
fraction of such sites can be seen in the sample annealed at 800 ◦ C, from
differences in lattice distortions [50]. The parallel g-components of the
the uneven background line (zero level signal) at magnetic field higher
Ti3+ fingerprints are known to be much weaker, and especially in
than 337 mT.
as-prepared NFs, remain unresolved. In addition, hyperfine interactions
Another type of defects usually encountered in literature for TiO2
with fluorine nuclei (19F, I=1/2) do not emerge in the EPR spectrum.
nanotubes subjected to air annealing conditions, is voids, that originate
Thermal annealing of NFs leads to an increase of the recorded EPR signal
from protonated titanium vacancies present in the amorphous material
intensities. In the thermally treated samples (Fig. 3, green spectrum is
[54] (a strongly containing hydroxyl material), but are not directly
the sample annealed at 300 ◦ C; blue spectrum corresponds to annealed
evident in our single crystalline material.
at 450 ◦ C and magenta spectrum to annealed at 800 ◦ C), a very weak
Evaluating the photocatalytic H2 evolution efficiency for “dark”-
cluster of resonances develops at low magnetic fields, < 323 mT (with
deposited TiO2 NFs, i.e., Pt SA decorated, for as-formed and NFs
g>ge), which corresponds to resonances addressable to oxygen-based
annealed at a different temperature, we observed that annealing treat­
spin containing sites (e.g. Ti-O•). Significant enhancements of the sig­
ments at 450 ◦ C and 600 ◦ C led to similar H2 evolution rates (Fig. S5).
nals associated to the lattice embedded Ti3+ species are especially
From these, we selected the partially defluorinated samples at 450 ◦ C for
observed after thermal annealing at 450 ◦ C and 800 ◦ C. Similarly to the
further investigations – this considering that previous photo­
as-prepared NFs and in agreement with their XRD analysis, in the
electrochemical investigations showed 450 ◦ C annealed NFs to have
thermally treated NFs become well observable the diverse impacts of
better electron transport time than those annealed at 600 ◦ C [45], and
lattice distortions acting onto the reduced Ti3+ sites, which express two
that annealing at 800 ◦ C had the disadvantage of Sn diffusion. A key
sets of g⊥ values, at g⊥=1.999 (a), g⊥=1.984 (b) and g||= 1.956 in both
parameter for the activity of the samples is the exposure time in the
450 ◦ C and 800 ◦ C samples, and these results are in agreement with
H2PtCl6 solution, which was varied from 10 min to 24 h (see Fig. 4).
previous observations from literature reports [51,52]. However, in the
Results from high-resolution SEM and TEM images demonstrating the
EPR spectrum associated to the sample annealed at the highest tem­
morphology of either “dark”-deposited by immersion in 5 × 10− 6 M
perature (Fig. 3, 800 ◦ C, magenta line), the g⊥=1.984 (b) component

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Fig. 4. (a) Photocatalytic H2 evolution rate (μL h− 1) for pre- or normal photodeposition of Pt NPs (NO.6 and NO.7), and different Pt SAs decoration – 5 × 10− 6 M
precursor for 10 min, 1 h and 24 h (NO.1, NO.2 and NO.3, respectively), and 24 h “dark”-deposition using different precursor concentration of 1 × 10− 6 mM (NO.4)
and 5 × 10− 5 mM (NO.5). (b) HR-SEM images of the annealed nanoflakes (NFs) (c–f) various “dark”-deposited treatments leading to Pt SAs and (g) pre-
photodeposited treatment leading to Pt NPs (NO.6). (h) HR-STEM image of the 24 h “dark”-deposited Pt NFs (NO.3) and (i,l) corresponding HAADF-STEM im­
ages of the O/Ti and Pt distribution.

PtCl62− solution for 10 min, 1 h, and 24 h are shown in Fig. 4c–d or for
pre-photodeposited Pt NPs in Fig. 4h. For the “dark”-deposition, SEM
characterization does not reveal the presence of any NPs on the surface
of the TiO2 NFs. Evidently, with times up to 24, the photocatalytic H2
evolution increases and the SEM does not show any trace of particle
formation. Therefore, in all further experiments, this optimal “dark”-­
deposition immersion time was used to produce SA-loaded NFs. In
contrast, conventional Pt deposition, i.e., samples that were prepared
using the pre-photodeposited approach, as expected, show the
formation of 2–5 nm in diameter Pt NPs (Fig. 4h).
Regarding the influence of the concentration, we found that among
the tested precursor concentrations, i.e., 1 × 10− 6 M, 5 × 10− 6 M, and 5
× 10− 5 M, the highest H2 evolution rate was achieved for the 5 × 10− 6 M
concentration. For the lowest precursor concentration (1 × 10− 6 M) no
Pt NPs were observable. Interestingly, for the highest concentration, i.e.,
5 × 10− 5 M, distinct Pt NPs with a diameter of 4–8 nm were obtained in
much higher numbers than attained for the pre-photodeposited sample
(Fig. 4f,g). In addition, both photodeposition and “dark”-deposition with

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higher concentration lead to preferential deposition of NPs on the (101)
facets.
The presence of Pt SAs and agglomerates of a few SAs on the “dark”-
deposited samples is evident from HR-STEM-HAADF, considering also
the usual SA literature [3,6,12-16,55] (Fig. 4i), and STEM-EDX images
as taken for a sample deposited for 24 h (Fig. 4j–l), see also the FTT
analysis in Fig. S6 confirming the Pt SAs deposition on the (101) facet of
the NF. The results distinctly point out that facetted anatase layers after
annealing can effectively trap Pt SAs directly by “dark-deposition” (a
simple 24 h immersion in the dark in a H2PtCl6 solution) (Fig. 4h,
marked area). TEM-EDX images further demonstrate the uniformity of
the Pt SAs trapping on the TiO2 NF surface (Fig. 4j–l). Interestingly, SAs
and their agglomerates locate preferably on (101) facets of the NFs
(Fig. S6).
The chemical composition and the coordination states of the anatase
and Pt decorated NFs, i.e., Pt NPs obtained by pre-photodeposition and
Pt SAs formed by the 24 h “dark”-deposition, were further evaluated by
the survey and high-resolution XPS analysis (Figs. 5b–f and S7). As
shown, a clear shift to 72.06 eV is observed in the Pt 4f7/2 peak (Fig. S7a)
for the “dark”-deposited Pt SAs, compared to 70.18 eV for the Pt NPs

Fig. 5. (a) XRD spectra of the pre-photodeposited, “dark”-deposited, as-formed, and annealed TiO2 NFs. (b) XPS survey spectra of the annealed, pre-photodeposited,
and “dark”-deposited NFs. High-resolution XPS spectra and peak fitting of the Pt 4f of (c) the pre-photodeposited (Pt NPs) and (d) “dark”-deposited (Pt SAs) on TiO2
NFs. (e) High-resolution XPS spectra of Cl 2p of the samples shown in (b). (f) The atomic percentage (at.%) was obtained from XPS measurements.

7
G. Cha et al. Electrochimica Acta 412 (2022) 140129

decorated NFs. Further fitting of the Pt 4f peaks results as follows. (i) For
the pre-photodeposited Pt NPs (NO.6), the typical asymmetric metallic
Pt peaks, i.e., Pt0 4f7/2 and 4f5/2 peaks appear at 70.18 eV and 73.51 eV,
respectively. (ii) For the “dark”-deposited NFs (NO.3) Pt is present in a
SA state, i.e., Ptδ+ 4f7/2 and 4f5/2 peaks appear at 72.06 eV and 75.43 eV,
respectively, having also a small contribution of 11.3 % from Pt2+ at
74.0 and 77.4 eV. The Ptδ+ peak locations of the Pt SA state (δ ≈ 2+) are
in line with literature on Pt SA [25,32,56]. A very low amount of
chlorine is also detected by XPS after the “dark”-deposition (Fig. 5e), and
considering the Pt/Cl ratio of 1:0.67, the surface attached Pt SAs are only
mildly coordinated with chloride. The presence of Cl in low amounts and
the δ ≈ 2+ suggests that the surface trapping of the Pt SAs takes place via
2+
a galvanic displacement reaction Ti3+ →Ti4+ ; Pt 4+ →Ptsurface trapped [25],
as reported for after defective material [2,4,6].
The Pt SAs prepared by “dark”-deposition on TiO2 NFs demonstrate a
photocatalytic H2 evolution efficiency much higher than that obtained
by the conventional crystalline Pt NPs decoration, even though the pre-
photodeposited sample demonstrates either 3-fold higher Pt loading as
measured by XPS (Fig. 5f) or 1.5-fold higher loading as measured by EDX
(Table S2). It should be noted that the higher amount of Pt loading
obtained by the XPS analysis is due to the high surface sensitivity of the
analytical technique. The presence of Pt SAs on the surface of the NFs
cannot be detected by XRD (Fig. 5a), while only the anatase crystalline
structure together with the SnO2 from the FTO was evident (with no
change in the measured lattice parameters, compared to the NFs
annealed at 450 ◦ C for 1 h, see Table S1).
Finally, we performed a long-term UV illumination experiment for
the annealed, “dark”-deposited Pt SAs (NO.3), and pre-photodeposited
Pt NPs (NO.6) for the estimation of photogenerated H2 evaluation
rates. It is noteworthy that almost a 4-fold increase of photogenerated H2
was measured for these optimized Pt SA “dark”-deposited NFs (NO.3) for
illumination times of up to 24 h, as compared to the pre-photodeposited
Pt NPs on TiO2 NFs (NO.6) (Fig. 6a). The photocatalytic H2 evolution
rate of the Pt SAs decorated NFs was measured as ~44 µL h− 1 and by
longer illumination times from 2 h up to 24 h, it demonstrates only a
slight decrease to 41.3 µL h− 1, which is about 6 % (Fig. 6b, blue line). At
the same time, the pre-photodeposited Pt NPs on the NFs demonstrate a
more pronounced reduction in the photogenerated H2 production rate
by prolonging illumination from 25.27 µL h− 1 to 12.14 µL h− 1, which is
52 % (Fig. 6b, red line). To note that this difference in H2 production rate
occurs despite the higher Pt at.% loading as calculated from EDX mea­
surements (0.1 at.% for pre-photodeposited and 0.07 at.% for “dark”-
deposited decorated NFs (Table S2). Moreover, while destabilization of
the SA occurs for the “dark”-deposited NFs (as evident from the SEM

Fig. 6. (a) Amount of H2 evolution photogenerated over 24 h of irradiation at λ = 365 nm for the annealed, the “dark”-deposited (NO.3), and the pre-photodeposited
(NO.6) TiO2 NFs. (b) Photocatalytic H2 evolution rate over 24 h illumination for the samples shown in (a) with additional data at 4, 8, 16, and 20 h of irradiation for
the dark”-deposited NTs (NO.3). (c) Photoelectrochemical J-V curves measured under irradiation at λ = 365 nm for the annealed, the “dark”-deposited (NO.3), and
the pre-photodeposited (NO.6) TiO2 NFs. (d) IPCE and corresponding bandgap (inset plot) spectra of the annealed, the “dark”-deposited (NO.3), and the pre-
photodeposited (NO.6) TiO2 NFs.

8
G. Cha et al.
images in Fig. S8, Pt particles in the 1–4 nm diameter range), it does not
have a significant influence on the H2 evolution rate. Hence, the reac­
tivity of the entire photocatalyst is virtually maintained throughout the
illumination time (on average 41.3 µL h− 1).
In order to elucidate more on the effect of Pt on the charge transfer
reaction, we acquired the photocurrent-voltage characteristics of the
TiO2 NFs with and without Pt loading, this for SA and NP decorated
substrates (Fig. 6c). In general, the voltage dependance of the photo­
current can be described by the Gärtner-Butler-Johnson approach as
outlined in Eqs. (1) and (2) [57-59],
( [ ( )1/2 ]( )− 1 )
Jph = qφ0 1 − − exp − αdsc U − − Ufb 1 + αLp (1)
α = A(hν − Eg)n/2 (hν)− 1
(2)
where φ0 (s− 1 cm− 2) is the photon flux, q (C) is the charge transferred
per ion, α (m− 1) is the optical absorption coefficient, dsc (nm) is the
depletion layer width for a potential of 1 V across it, e0 (1.6 × 10− 19 C) is
the electron charge, ε is the dielectric constant of TiO2, ε0 (8.85 × 10− 12
F m− 1) is the permittivity of vacuum, U (V) is the applied potential, Ufb
(V) is the flat-band potential, Lp (nm) is the hole diffusion length, A is a
constant, hν (1240 eVnm− 1) is the photon energy of the incident light,
Eg is the bandgap, and n equals 1 (for direct transitions) or 4 (indirect
transitions).[60]
In line with Eq. (1), photocurrent growth is observed essentially with
(U-Ufb)1/2 for all three samples and reaches a comparable magnitude. In
other words the presence of Pt does not affect the anodic photocurrent
(hole transfer reaction) over the entire investigated range, neither in the
form of SAs nor as NPs. This means the beneficial effect of SAs (and NPs)
in photocatalysis must entirely be ascribed to a facilitated electron
transfer reaction.
Various literature ascribes to Pt SAs an effect on the optical band-gap
[6]. Diffuse reflectance measurements of the same samples demonstrate
identical reflectance in the UV spectral range due to light absorption via
a band-to-band electron excitation in anatase TiO2 (Fig. S9a) [46]. On
the other hand, both plain and Pt-SA decorated TiO2 NF samples
demonstrate identical reflectance spectra in the visible spectral range,
while the Pt-NP TiO2 NF sample shows slightly lower reflectance. The
latter is attributed to the photon absorption by Pt NPs under visible light
irradiation due to the plasmonic effect, i.e., the collective oscillation of
free electrons confined to the metallic NP [61,62], while in the case of
Pt-SA decoration this phenomenon does not occur [63]. Correspond­
ingly, comparable optical bandgap energies of 3.27 eV were obtained,
estimated from the Kubelka-Munk transformations (see Fig. S9b).
To investigate in more detail Pt effects on the electronic properties,
we acquired IPCE measurements and evaluated the bandgap according
to Eq. (2) (Fig. 6d). An. The data for the bandgap evaluation are a replot
of the IPCE spectra (according to an indirect transition) yield for all
samples a bandgap value of 3.19 eV – this is well in line with the re­
ported bandgap energies of anatase TiO2 (Fig. 6d, inset) [64]. This
clearly shows that in the present case any sort of light absorption effect
by Pt SAs can be excluded as a reason for the enhancement of photo­
catalytic H2 generation.
4. Conclusions
In conclusion, the current work introduces a strategy to use (001)
faceted TiO2 nanosheets/nanoflakes as a substrate to "dark”-deposit Pt
single-atoms (SAs). Traps are achieved by annealing of the nanoflakes
and defluorination, whereas usually SA trapping on TiO2 is established
on (Ti3+-Ov) TiO2 states (by annealing in Ar/H2 atmosphere) or native
defects formed in anodic TiO2 nanotubes. Here we introduce single-
crystalline TiO2 NF surfaces with enough defect sites to effectively
reduce Pt precursor and trap it as a SA layer. Such an optimal Pt SAs
decoration of the NFs provides a 4-fold higher reactivity for photo­
catalytic H2 production compared to conventional Pt NPs decoration on
9
Electrochimica Acta 412 (2022) 140129
the same NFs. The “dark”-deposition process is facile, low-cost, and does
not require special instrumentation, yet forms an efficient single-atom
layer on TiO2 NFs. We have optimized the deposition procedure to
obtain maximal H2 generation rates by adjacent deposition time and Pt
precursor concentration. An optimal “dark”-deposition timeframe is 24
h, and using a minimal Pt precursor concentration of 5 × 10− 6 M out­
performs the classical Pt photodeposited or pre-photodeposited nano­
particles decoration, showing a stable rate over extended illumination
times. We believe that this work introduces a fundamentally new tool in
SAs co-catalyst engineering using the surface defects and the (001)
facets of anatase NFs, that show potential in their further use, and may
inspire the alternative green energy generation community to investi­
gate further the SA catalysis phenomenon.
CRediT authorship contribution statement
Gihoon Cha: Investigation, Writing – original draft, Data curation,
Formal analysis. Anca Mazare: Formal analysis, Visualization, Writing –
original draft, Writing – review & editing. Imgon Hwang: Investigation,
Data curation, Formal analysis. Nikita Denisov: Investigation, Data
curation, Formal analysis. Johannes Will: Investigation, Formal anal­
ysis. Tadahiro Yokosawa: Investigation, Data curation, Formal anal­
ysis, Writing – review & editing. Zdeněk Badura: Formal analysis,
Writing – review & editing. Giorgio Zoppellaro: Resources, Writing –
review & editing. Alexander B. Tesler: Formal analysis, Writing –
original draft, Writing – review & editing. Erdmann Spiecker: Re­
sources, Visualization. Patrik Schmuki: Resources, Conceptualization,
Writing – original draft, Writing – review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The authors would like to acknowledge the DFG and the Operational
research program, Development and Education (European Regional
Development Fund, Project No. CZ.02.1.01/0.0/0.0/15_003/0000416
of the Ministry of Education, Youth and Sports of the Czech Republic) for
financial support. Fahimeh Shahvardanfard is acknowledged for her
contribution to this work. J.W. and E.S. acknowledge the research
training group GRK 1896 “In Situ Microscopy with Electrons, X-rays,
and Scanning Probes”. A.B.T. acknowledges the DFG (grant number
442826449; SCHM 1597/38-1 and FA 336/13-1) for financial support.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.electacta.2022.140129.
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