RESEARCH ARTICLE

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Spontaneous Dewetting of Au-Thin Layers on Oxide- and

Fluorine-Terminated Single Crystalline Anatase and Efficient
Use in Photocatalytic H2 Production
Xin Zhou, Si-Ming Wu, and Patrik Schmuki*

react with suitable red-ox species in

In the present work, the spontaneous dewetting of thin Au layers on single water.[2–4] Excited electrons from the con-
crystalline anatase nanosheets into narrow-disperse Au nanoparticles is duction band of TiO2 are able to reduce
investigated. Patterns of the Au particles can be formed on the main facets of H2 O in aqueous environment to H2 , while
anatase that provide a high co-catalytic activity for photocatalytic generation the holes oxidize –H2 O to O2 or H2 O2 (or
react with sacrificial agents to correspond-
of H2 . Dewetting is distinctly influenced by the respective facets (001) and
ing oxidation products).[5,6] The principle is
(101), the deposit thickness, and secondary thermal dewetting, but most a most striking direct path to H2 ; and thus,
strongly by the surface termination of the nanosheets. Fluoride termination directly to a clean energy source.[7–9] TiO2 is
not only leads to an enhanced Au-phobic behavior but strongly affects the widely utilized in photocatalytic hydrogen
co-catalytic activity for photocatalytic generation of H2 . While fluoride synthesis because it combines some unique
features: Not only are the energies of the
termination with or without Au decoration is detrimental for hole transfer, the
conduction and valence band edge suitable
interplay of the Au co-catalyst and surface fluoride yields highly beneficial for the bias-free reduction and oxidation
effect for electron transfer. This results in a three-times higher photocatalytic of water but also TiO2 is easily accessible,
H2 production for the F-terminated surface. The findings suggest that non-toxic, and foremost, provides excellent
dewetting of Au on surface fluorinated TiO2 is an effective way to modulate chemical and photochemical stability.[10–12]
surface dewetting and achieve a strongly enhanced photocatalytic activity. In order to reach a reasonable efficiency
of photocatalytic processes, commonly,
several measures are required to maxi-
mize reaction rates. First, nanostructured
1. Introduction photocatalysts are employed, which are usually nanoparticles
or nanoparticle aggregates that, on the one hand, provide a
Photocatalytic hydrogen(H2 ) production using titanium dioxide large specific surface area, and, on the other hand, provide
(TiO2 ) as a solar light absorbing semiconductor has attracted minimized charge carrier diffusion paths to reach the solid–
wide interest ever since the pioneering report of Fujishima and liquid interface where they can react in a desired way.[11,13]
Honda in 1972.[1] In this process, light irradiation leads to pho- Many advanced approaches are based on 1D morphologies such
toexcitation in the semiconductor, producing mobile electrons as nanotubes, nanowires, nanofibers, nanorods, or anchored
and holes in the conduction band and valence band, respectively. nanosheets. While nanotubes and wires can provide better con-
The excited charge carriers diffuse or migrate on their respec- trolled charge separation, nanosheets provide defined reactive
tive band until they reach the semiconductor surface, where they facets with a facet dependent charge transfer.[12,14–17]
However, in spite of nano-structure optimization, on plain ox-
ide surfaces, the transfer of conduction band electrons, and as
X. Zhou, S.-M. Wu, P. Schmuki
Department of Materials Science WW4-LKO a consequence, the hydrogen evolution reaction are kinetically
University of Erlangen-Nuremberg strongly hampered. Therefore, to accelerate the reaction rate,
Martensstrasse 7, 91058 Erlangen, Germany co-catalysts are typically placed on the TiO2 surfaces. Most of-
E-mail: schmuki@ww.uni-erlangen.de ten, these co-catalysts are noble metals such as Pt, Pd, or Au
P. Schmuki that mediate the electron transfer to the electrolyte.[18–23] Co-
Regional Centre of Advanced Technologies and Materials
catalysts, among other effects, provide a Schottky junction that
Palacký University Olomouc
Šlechtitelů 241/27, Olomouc 77900, Czech Republic aids a fast charge transfer away from the conduction band onto
the metal.[24,25] A variety of techniques exists, such as photode-
The ORCID identification number(s) for the author(s) of this article position, electrodeposition, colloidal chemistry, or impregnation,
can be found under https://doi.org/10.1002/smll.202303306 to decorate TiO2 with noble metal co-catalysts.[26–31] An alterna-
© 2023 The Authors. Small published by Wiley-VCH GmbH. This is an tive approach was extensively investigated by Nguyen and Al-
open access article under the terms of the Creative Commons Attribution tomare et al., that was “thermal dewetting” of sputter deposited
License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited. thin noble-metal layers that were examined particularly on TiO2
nanotube layers.[13,32–35] Dewetting was shown to be a simple
DOI: 10.1002/smll.202303306

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straightforward method to form and use dewetted noble metals
as co-catalysts in photocatalytic H2 generation. When deposited
on polycrystalline substrates, noble metal nanoparticles were ob-
tained with a broad particle size distribution ranging from some
to several tens of nanometers.
Other TiO2 nanostructures that recently attracted attention are
preferentially facetted TiO2 nanosheets; this not only dispersed as
powders in solution but also grew vertically arranged to 3D struc-
tures on fluorine-doped tin oxide (FTO) substrates,[36–38] where
they could also be used as photoelectrodes.[23,38–40] A key advan-
tage of these photoelectrodes is their single crystalline nature
which provides a much faster electron transport than obtained
in anodic, polycrystalline nanotubes, or nanoparticles/layers.[39]
Moreover, the defined faceting (typically minor [101] and domi-
nant [001] facets) is regarded as beneficial under photocatalytic
conditions as the close vicinity of facets of a different surface en-
ergy provides a homojunction that leads to facilitated charge sep-
aration, the (001) anatase facets being the dominant hole exit sites
and the (101) planes acting as electron exit sites.[41,42]
In the present work, we use these single crystalline structures
on FTO as substrates for dewetting of sputter-deposited Au thin
layers and evaluate the critical factors in view of dewetting, as
well as, establishing a most effective co-catalytic system toward
photocatalytic H2 production. On these single-crystalline TiO2
nanosheets, we observe facet-dependent but very uniform Au
deposition and highly defined spontaneous dewetting (high de-
gree of uniformity in Au nanoparticle size and distribution). We
show that the dewetting is not only facet-dependent, but impor-
tantly, that the dewetting is strongly affected by the level of F-
termination of the oxide surface. Most importantly, we observe a
strong synergy between the fluoride of an F-termination that ex-
erts strong effects on electron and hole transport and the dewet-
ted Au nanofeatures, and in-turn, on the effectiveness of the pho-
tocatalytic H2 generation.
2. Results and Discussion
We first fabricated vertically aligned TiO2 nanosheets (NSs) on
–FTO– substrates using the hydrothermal method described
in the Experimental Section. Figure 1a shows scanning elec-
tron microscope (SEM) images of the morphological features of
such as-formed TiO2 nanosheets with preferential (001) facets
(a schematic diagram of the facet orientation is given in the in-
set). The resulting layer of NSs has a layer thickness of 1.5 μm
(Figure 1, inset) and a single sheet-thickness of ≈150–200 nm.
These as-formed TiO2 nanosheets are F-terminated due to the
growth process in the HF environment.[17,38,42] In previous work,
we demonstrated that a suitable annealing process can reduce
this F-termination or completely eliminate it depending on
the annealing temperature.[39,23] For layers annealed at 450 °C,
X-ray photoelectron spectroscopy (XPS) shows an ≈50% reduc-
tion of the F termination compared to a non-annealed sample
(Figure S1 and Table S1, Supporting Information). We selected
this annealing temperature as this condition showed in previ-
ous work, the highest photoelectrochemical activity, that is, the
incident photocurrent conversion efficiencies (IPCE) from such
annealed sheets was higher than for as-formed layers (complete
F-termination) or layers annealed at a higher temperature, where
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the F-termination was completely removed,[39] and as confirmed
in Figure S5d, Supporting Information.
Figure 1b–d illustrates the morphology of such nanosheet
substrates after they were sputter-decorated with nominal thick-
nesses of 1, 5, and 10 nm of Au layers, and Figure 1e shows
a statistical evaluation of the particle (feature) size directly after
deposition. Obviously, the surface conditions of the single crys-
talline substrate lead to spontaneous dewetting of the Au film. In
the case of a nominally 1 nm thick Au sputtered layer, sponta-
neous dewetting leads to homogeneously sized Au particles with
a mean diameter 4.0 ± 2.5 nm on (101) facets and 3.4 ± 1.6 nm
on (001) facets (Figure 1e [1 nm]). Please note these nanoparti-
cles are not only very uniform in size but also very uniformly dis-
tributed on the surface of TiO2 nanosheets. This high degree of
regularity reflects the flat surface of the facets with no tips, pro-
trusions or holes, no visible crystalline defects or grain bound-
aries, and no chemical inhomogeneity (precipitates, inclusion,
and second phase material) due to the single-crystal structure.
Nevertheless, between the two crystal facets, there is a 0.6 nm dif-
ference in average particle size which can be ascribed to the dif-
ferent surface energies of the facets (see Table S2, Supporting In-
formation). With the increase of the nominal thickness of the ini-
tial Au layer, dewetting occurs into less regular and larger units.
The morphology of the 5 nm-Au decorated nanosheets yields Au
islands and connections between adjacent islands with an av-
erage coverage of 61.5% on the (101) facets, while in contrast,
(001) facets still show distinct Au nanoparticles with a mean size
of 4.5 ± 3.5 nm, that is, the differences between the (101) and
(001) facets become more obvious than for the 1 nm deposition.
When the nominal Au deposition is increased to 10 nm, contin-
uous layers are formed on the (101) facets, and 56% of the (101)
facets is completely covered by the Au. The average size of the
apparent particles on the (001) facets increases to 7.6 ± 4.5 nm
(Figure 1e [10 nm]). Evidently, and as intuitively expected, a
higher coverage of the facet occurs with an increasing film thick-
ness, and a higher degree of dewetting is observed on (001) facet
than on (101) facets under the same sputtering condition. These
differences in the dewetting behavior of the two facets can again
be attributed to differences in their surface energy (see Table S2,
Supporting Information).[17,43]
For all these Au decorated NSs, we then evaluated the photocat-
alytic H2 production in order to assess the effect of the different
levels of dewetting on the photocatalytic efficiency (Figure 1f).
For this, we examined the samples in a photoreactor using
365 nm LED 60 mW cm−2 illumination and a MeOH/H2 O
50 vol% solution. Figure 1f shows a linear photocatalytic H2 evo-
lution over time for all investigated sheets. Evidently, in com-
parison to the metal-free surfaces, the loading with Au signif-
icantly increased the photocatalytic H2 evolution (from <1 μL
h−1 up to H2 production rates of 7 μL h−1 ). The highest bene-
ficial effect of Au loading was observed for the nominal 5 nm
Au deposition. However, in this comparison for the differently
loaded surfaces, the variations in H2 productivity were not very
pronounced.
More pronounced changes in the dewetted features were ob-
tained by a second annealing of the samples (Figure 2a–c). In this
case, after the Au deposition, we annealed the surface for a second
time at 450 °C in air (this is an often-used annealing condition for
Au dewetting).[44]
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Figure 1. SEM images of a) as-formed TiO2 nanosheets (inset schematic diagram of nanosheet facets and the cross-sectional SEM image). b) TiO2
NS annealed at 450 °C, decorated with a 1 nm-thick Au film (A450 + 1 nm). c) TiO2 NS annealed at 450 °C, decorated with a 5 nm-thick Au film (A450
+ 5 nm). d) TiO2 NS annealed at 450 °C, decorated with a 10 nm-thick Au film (A450 + 10 nm). e) Statistical evaluation of the Au particles (film)
size/coverage on (101) and (001) facets of A450 + 1 nm, A450 + 5 nm, and A450 + 10 nm. f) Photocatalytic H2 evolution of A450 (annealed TiO2 NS
at 450 °C), A450 + 1 nm, A450 + 5 nm, and A450 + 10 nm samples.

For the 1 nm deposition, no obvious change was observed af-
ter post-annealing. Notably, for the 5 and 10 nm Au deposited
samples, facet depending Au-sintering was observed after post
annealing. While the size of Au remained almost the same on
(001) facets, the size of the Au islands on (101) facets increased
significantly by the post-annealing, with the average dewetting
particle size of 35 nm for 5 nm-Au and 55 nm for 10 nm-Au.
A factor that influences the surface energy even more
(and thus, is expected to affect dewetting) is the surface ter-
mination of the sheets (see Table S2, Supporting Informa-
tion). Fully F-terminated TiO2 surfaces have a considerably
lower surface energy than fully or partially oxide-terminated
TiO2 surfaces.[17] In order to assess the relevance of this fac-
tor, we examined fluoride-terminated surfaces (i.e., as-formed
samples).
Figure 2d–f illustrates the dewetted Au layers on the anatase
nanosheets that were used as-formed (F-terminated). Evidently,
the dewetting behavior of Au showed distinct differences if the
facets were F-terminated, compared to the samples that were
oxide exposed. In the case of the (101) facets, the average size of

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Figure 2. SEM images of a) A450 (annealed TiO2 NS at 450 °C) + 1 nm + A450 (thermal dewetting at 450 °C). b) A450 + 5 nm + A450. c) A450 +
10 nm + A450. d) 1 nm-thick Au on as-formed nanosheets (1 nm). e) 5 nm-thick Au on as-formed nanosheets (5 nm). f) 10 nm-thick Au on as-formed
nanosheets (10 nm). g) Photocatalytic H2 evolution: summary of H2 production rates for all samples.

1 nm-Au particles on the (101) facets increased to 4.8 ± 3.8 nm,
as shown in Figure S2a, Supporting Information. In addition, the
Au surface coverage decreased by 4.5% for 5 nm-Au (Figure S2b,
Supporting Information), and the area of fully covered facets was
reduced by 6% for 10 nm-Au. Figure S3, Supporting Information,
illustrates the dewetting behavior of samples with different heat
treatments, using 5 nm Au as an example. This behavior is fully
in line with the surface energies of the different facets (Table S2,
Supporting Information). The most Au-phobic behavior is pro-
vided by the (001) facets in F-terminated nanosheets, and accord-
ingly, Au particles are most dispersed (and show a high contact
angle). With a change in surface energy, either when establish-
ing a more oxide rich surface or when regarding a (001) versus
(101) facet, wetting is increased and wider structures (better Au
wetting) are formed.
It is noteworthy that only for the nanosheets deposited with
10 nm Au, a clear Au diffraction peak can be identified at 2𝜃
= 44.4° in X-ray diffraction (XRD) measurements (Figure 3a)
(JCPDS card no. 01-089-3697). For lower amounts of Au (1 nm,
5 nm), no Au-related XRD signal can be detected (Figure 3a,b).
–XPS– provides for Au-decorated samples clear Au 4f peaks, Au
4f7/2 at 86.7 eV, and Au 4f5/2 at 83.1 eV (Figure 3c,d). The peak
positions match the binding energy of zero-valent Au in the liter-
ature under all conditions.[33,45,46]
For all the above samples, we evaluated the photocatalytic
H2 production efficiency (Figure S4, Supporting Information),
and from the slopes of the plots, the H2 production rates were
determined—the results are shown in Figure 2g. From all data,
it is apparent that the most beneficial effect of Au for H2 genera-
tion either on F-terminated or oxidic nanosheets is obtained for
nominally 5 nm thick film, while larger Au amounts, such as 10
and 25 nm thick Au films, lead to a considerable drop. This de-
cay of the activity can be attributed to “shadowing effects” (i.e., the
coverage of the oxide surface limits the free TiO2 surface and the
absorption of light, negatively affecting the overall photocatalytic
process).[13,32,35]
Evidently, a second thermal dewetting affects significantly the
Au morphology but shows less effects on the photocatalytic ef-
ficiency, that is, the significant variations in the Au geometry by
the second annealing only slightly increase the amount of H2 pro-
duction.
Most remarkable is; however, the strong influence of F-
termination not only on Au dewetting but also on photocatalytic
H2 generation and accordingly, on interaction with Au.

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Figure 3. a,b) XRD patterns of all Au decorated TiO2 nanosheets samples. c) XPS high-resolution patterns of Au4f peaks of 1 nm, A450 + 1 nm, and
A450 + 1 nm + A450 samples. d) XPS high-resolution patterns of Au4f peaks of 10 nm, A450 + 10 nm, and A450 + 10 nm + A450.

Evidently, in terms of H2 evolution, using as-formed
nanosheets (F-terminated) is highly beneficial for photocat-
alytic H2 production in comparison to either way annealed
nanosheets. Again, the 5 nm-thick Au layer sputtered sam-
ple shows the best performance. However, all loadings from
1–10 nm Au show a nearly threefold improvement in H2
generation compared with the annealed (with oxide exposed
on surface) samples. This suggests that a synergistic effect of
surface fluoride and surface noble metal catalysts dominates the
efficiency. Note that the synergetic effects of Au and remaining
fluorine species at 450 °C annealing sample are negligible, as
nanosheets annealed at 600 °C (F completely removed) show a
very similar photocatalytic H2 production activity as the 450 °C
sample (Figure S5, Supporting Information). Beneficial effects
have been reported between surface fluoride and noble metal
catalysts for other TiO2 substrates.[47] Mostly, such effects have
been ascribed to the high electronegativity of fluorine that aids
trapping of photogenerated electrons; and thus, reduces the
overall charge recombination.[24,48]
In order to better understand this remarkable effect of F-
termination, we studied the photoelectrochemical behavior and
light reflectance properties for the different samples. Figure 4;
Figure S6, Supporting Information, show the IPCE for vari-
ous non-loaded and Au-loaded nanosheets measured in 0.1 m
Na2 SO4 at 0.5 V (vs Ag/AgCl) with and without sacrificial
agent.
Figure 4a provides the comparison of F-terminated (as formed)
and oxidized surface in an aqueous and in an MeOH contain-
ing solution. Remarkably, the as-formed TiO2 nanosheets that
carry a F-terminated surface show only very low photocurrents
with less than 1% IPCE, even at deep UV illumination. In con-
trast, for TiO2 nanosheets where this F-termination is partially re-
moved (annealed at 450 °C) and completely removed (annealed
at 600 °C) (Figure S5f, Supporting Information), much higher
photocurrents are obtained. This blockage of photocurrent by
the F-termination is still present, even when MeOH as a hole
capture agent is added. For annealed nanosheets with oxidized
surface, there is almost no change in photocurrent with and
without MeOH; that is, in comparison with an oxide surface,
the hole transfer to the electrolyte is strongly suppressed by the
fluoride layer. This blockage is still present after Au deposition
(Figure 4b), that is, Au does not aid the hole transfer. In fact,

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Figure 4. a) Comparison of the IPCE spectra for nanosheets (as-formed and annealed at 450 °C in air) in Na2 SO4 and Na2 SO4 + MeOH electrolytes.
b) IPCE spectra of non-Au loaded nanosheets and 10 nm Au sputtered samples with different thermal treatments, IPCE spectra for as-formed nanosheets
(non-Au, 1 nm, 5 nm, and 10 nm Au decorated) in c) Na2 SO4 and d) Na2 SO4 + MeOH electrolyte.

when the TiO2 nanosheets are decorated with 10 nm Au, the
photocurrent shows even a slight decrease which may be due to
shading effects (Figure 4b).
We further measured the IPCE spectra of as-formed
nanosheets deposited with different thicknesses of Au in
aqueous and in an MeOH containing solution (Figure 4c,d).
Again, still the magnitude of the photocurrent was drastically
lower than for the oxide surface. The results clearly indicate that
Au deposition does not affect the photoelectrochemical perfor-
mance too much, that is, there is no beneficial contribution to
hole transfer. This in turn means that the strongly beneficial ef-
fect of fluoride in the photocatalytic setting must come from the
interaction of F with Au on the electron transfer. The decrease
of the hole transfer by fluoride is not overall rate-determining.
It may be noted that the Au deposited annealed nanosheets
show a small peak in photocurrent around 500–600 nm,
which can be ascribed to plasmonic contributions by the Au
NPs (Figure S6c,d, Supporting Information); these plasmonic
contributions typically peak in this wavelength range[49,50] (Plas-
monic effects are also apparent in reflectance spectra given in
Figure S7a, Supporting Information). However, those plasmonic
effects do not contribute measurably to the photocatalytic H2
production, in accordance with visible light experiments, as
shown in Figure S8, Supporting Information. A band gap of
Eg ≈ 3.2 eV (Figure S6e,f, Supporting Information), that is,
typical for anatase TiO2 , can be determined in Au-deposited
annealed TiO2 nanosheets, and a slightly narrower bandgap is
observed for as-formed TiO2 nanosheets due to surface fluorine
termination.[51]
To summarize, the dewetting of Au thin films on single crys-
talline anatase nanosheets leads to highly active co-catalytic Au
nanostructures for photocatalytic H2 evolution. Due to the single
crystal nature, dewetting occurs very uniformly—this can be as-
cribed to the absence of crystalline defects such as grain bound-
aries (that for polycrystalline surfaces often represent preferen-
tial break-up points for thin films).[52] The photocatalytic activ-
ity drops at higher Au loading; this is likely due to the “shad-
ing effect”—larger amounts of Au optically shield the underlying
TiO2 structure. An optimum Au loading in terms of photocat-
alytic activity can be obtained using dewetted Au films of nominal
thicknesses of 1–5 nm. Most dominant for the photocatalytic ac-
tivity is however a synergistic interaction of F-termination and Au
that strongly enhances the electron transfer reaction; and thus,
the photocatalytic activity.
3. Conclusion
In the present work, we grew single crystalline anatase
nanosheets on FTO and studied the spontaneous and thermal
dewetting behavior of Au-thin layers on nanosheets that were ei-
ther oxide- or fluorine terminated. The control of the Au film
thickness and different annealing treatments enable a precise
manipulation of the Au particles size, shape and distribution.
Due to the single crystalline structure of the substrate, a very

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homogenous dewetting process can be established, leading to
a remarkably uniform dewetting morphology, and accordingly,
a narrow size distribution of formed Au nanoparticles. Dewet-
ting is controlled by the surface energy, and accordingly, it is in-
fluenced by the substrate crystal structure, the facet orientation,
and strongly, by the surface termination of the facets. As formed
anatase crystals are fluoride terminated and the F-terminated
(001) plane provides the lowest surface energy of all investigated
combinations—accordingly, this plane shows the highest degree
of Au-phobicity. If the different surfaces are compared for their
photocatalytic performance for H2 evolution, we observe a re-
markable and significant increase in photocatalytic activity for Au
decorated “F terminated” samples. Although F-termination leads
to severe hole-transfer-blocking, the synergistic effect of fluorine
and Au leads to enhanced electron transfer and a three times
higher photocatalytic H2 evolution performance than observed
for an oxidic surface.
4. Experimental Section
Preparation of Single Crystal Anatase Nanosheets: FTO substrates (7 Ω
m−2 , Pilkington) were first sonicated in acetone, ethanol, and deionized
water, respectively; and then, dried with a nitrogen stream. The hydrother-
mal synthesis process was carried out using a Teflon-lined stainless-steel
autoclave (250 mL capacity) at 150 °C for 15 h to grow TiO2 nanosheets
(NSs) directly on the FTO substrates. The basic formulation was prepared
by adding 1.5 mL of titanium isopropoxide (Sigma–Aldrich) dropwise into
a mixture of hydrochloric acid (37%, Sigma–Aldrich) and DI water with
equal volumes (30 mL: 30 mL) and stirring for 25 min. Afterward, 0.5 g am-
monium hexafluorotitanate (Sigma–Aldrich) was added and further stirred
for 15 min. The cleaned FTO substrates were then placed face down in the
solution with a resin support, followed by hydrothermal synthesis at 150 °C
for 15 h. Last, the as-prepared layers were washed with DI water and an-
nealed in air using a tubular furnace at 450 °C for 1 h (when indicated).
Au Decoration: To decorate the single crystal anatase nanosheets with
Au, a plasma-sputtering device (Leica-EM SCD500) was used. Different
nominal thicknesses of Au, ranging from 1 to 25 nm, were sputtered onto
the samples, which were controlled by an automated quartz crystal film-
thickness monitor, allowing for precise control of the amount of Au de-
posited. The deposition process was carried out at 10−2 mbar of Ar with
an applied current of 16 mA, using a 99.99% pure Au target (Hauner Met-
allische Werkstoffe, HMW). The average coating rate was 0.1 nm·s−1 . Fol-
lowing Au decoration, the samples were annealed in air at 450 °C for 1 h
to induce thermal dewetting.
Characterization of the Structures: For the morphological characteri-
zation, a field-emission scanning electron microscope (FE-SEM, Hitachi
S4800) was utilized. The crystallographic properties of the samples were
analyzed using X-ray diffraction (XRD), performed with X′pert Philips
MPD (equipped with a Panalytical X’celerator detector) using graphite
monochromized Cu K𝛼 radiation (𝜆 = 1.54056 Å). X-ray photoelectron
spectroscopy (XPS, PHI 5600, US) was used to analyze the chemical com-
position of the samples. The Ti 2p located at 458.5 eV was used to calibrate
the binding energy.
Photocatalytic Experiments: Photocatalytic hydrogen production was
carried out by exposing the sample to UV light (=365 nm; irradiation power
= 60 mW·cm−2 ) in a 50 vol% aqueous methanol solution. The experiments
were conducted in a photocatalytic cell made of quartz tube, sealed with
a rubber septum. To determine the amount of H2 generated, gas chro-
matography (GCMS-QO2010SE, Shimadzu) was used to analyze 200 μL
gas extracted from the headspace of the quartz reactor. Prior to the start
of the photocatalysis experiments, the 50 vol% aqueous methanol solution
in the reaction tube was purged with argon for 15 min.
Photoelectrochemical Experiments: Incident photon-to-current conver-
sion efficiency (IPCE) measurements were carried out in the 300–800 nm
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range using a setup consisting of an Oriel 6356 150 W Xe arc lamp as the
light source and an Oriel cornerstone 7400 1/8 monochromator. The spec-
tra were obtained by recording the photocurrent transients (10–20–10 s
light off-on-off cycles) under monochromatic illumination, with a 𝜆 step-
size of 5 nm. The measurements were performed in an electrochemical cell
equipped with a quartz window, using 0.1 m Na2 SO4 aqueous solution and
applying a potential of 0.5 V. The cell operated in a three-electrode configu-
ration, with the Au/TiO2 nanosheets as the working electrode, a saturated
Ag/AgCl electrode as the reference electrode, and a Pt foil as the counter
electrode.
Optical Measurements: The reflectance spectra were obtained using a
fiber-based UV–vis–IR spectrophotometer (Avantes, ULS2048) equipped
with an integrating sphere AvaSphere-30 and an AvaLight-DH-S-BAL bal-
anced power light source (PTFE was utilized as a reference standard).
Supporting Information
Supporting Information is available from the Wiley Online Library or from
the author.
Acknowledgements
The authors would like to acknowledge the DFG and the Operational Re-
search Program, Development and Education (European Regional De-
velopment 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 finan-
cial support.
Open access funding enabled and organized by Projekt DEAL.
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available from the cor-
responding author upon reasonable request.
Keywords
dewetting, photocatalytic H2 evolution, single crystalline anatase TiO2 ,
surface fluorination
Received: April 19, 2023
Revised: May 26, 2023
Published online: June 25, 2023
[1] A. Fujishima, K. Honda, Nature 1972, 238, 37.
[2] X. Chen, S. S. Mao, Chem. Rev. 2007, 107, 2891.
[3] P. Roy, S. Berger, P. Schmuki, Angew. Chem., Int. Ed. 2011, 50, 2904.
[4] K. Lee, A. Mazare, P. Schmuki, Chem. Rev. 2014, 114, 9385.
[5] N. Liu, S. Mohajernia, N. T. Nguyen, S. Hejazi, F. Plass, A. Kahnt,
T. Yokosawa, A. Osvet, E. Spiecker, D. M. Guldi, P. Schmuki, Chem-
SusChem 2020, 13, 4937.
[6] N. Denisov, J. Yoo, P. Schmuki, Electrochim. Acta 2019, 319, 61.
[7] Z. Zou, J. Ye, K. Sayama, H. Arakawa, Nature 2001, 414, 625.
[8] A. Fujishima, X. Zhang, D. Tryk, Surf. Sci. Rep. 2008, 63, 515.
[9] X. Chen, S. Shen, L. Guo, S. S. Mao, Chem. Rev. 2010, 110, 6503.
© 2023 The Authors. Small published by Wiley-VCH GmbH

www.advancedsciencenews.com
[10] M. D. Hernández-Alonso, F. Fresno, S. Suárez, J. M. Coronado, Energy
Environ. Sci. 2009, 2, 1231.
[11] I. Paramasivam, H. Jha, N. Liu, P. Schmuki, Small 2012, 8,
3073.
[12] X. Wang, Z. Li, J. Shi, Y. Yu, Chem. Rev. 2014, 114, 9346.
[13] N. T. Nguyen, M. Altomare, J. E. Yoo, N. Taccardi, P. Schmuki, Adv.
Energy Mater. 2015, 6, 1501926.
[14] X. Feng, K. Shankar, O. K. Varghese, M. Paulose, T. J. Latempa, C. A.
Grimes, Nano Lett. 2008, 8, 3781.
[15] J. Liu, H. Bai, Y. Wang, Z. Liu, X. Zhang, D. D. Sun, Adv. Funct. Mater.
2010, 20, 4175.
[16] Z. Sun, J. H. Kim, Y. Zhao, F. Bijarbooneh, V. Malgras, Y. Lee, Y.-M.
Kang, S. X. Dou, J. Am. Chem. Soc. 2011, 133, 19314.
[17] H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M.
Cheng, G. Q. Lu, Nature 2008, 453, 638.
[18] G. R. Bamwenda, S. Tsubota, T. Nakamura, M. Haruta, J. Photochem.
Photobiol., A 1995, 89, 177.
[19] M. Anpo, M. Takeuchi, J. Catal. 2003, 216, 505.
[20] K. Lee, R. Hahn, M. Altomare, E. Selli, P. Schmuki, Adv. Mater. 2013,
25, 6133.
[21] R. Su, R. Tiruvalam, A. J. Logsdail, Q. He, C. A. Downing, M. T. Jensen,
N. Dimitratos, L. Kesavan, P. P. Wells, R. Bechstein, H. H. Jensen, S.
Wendt, C. R. A. Catlow, C. J. Kiely, G. J. Hutchings, F. Besenbacher,
ACS Nano 2014, 8, 3490.
[22] S. Hejazi, S. Mohajernia, B. Osuagwu, G. Zoppellaro, P. Andryskova,
O. Tomanec, S. Kment, R. Zbořil, P. Schmuki, Adv. Mater. 2020, 32,
1908505.
[23] G. Cha, A. Mazare, I. Hwang, N. Denisov, J. Will, T. Yokosawa, Z.
Badura, G. Zoppellaro, A. B. Tesler, E. Spiecker, P. Schmuki, Elec-
trochim. Acta 2022, 412, 140129.
[24] J. Yu, L. Qi, M. Jaroniec, J. Phys. Chem. C 2010, 114, 13118.
[25] A. Naldoni, M. D’Arienzo, M. Altomare, M. Marelli, R. Scotti, F.
Morazzoni, E. Selli, V. Dal Santo, Appl. Catal., B 2013, 130–131, 239.
[26] M. Ni, M. K. H. Leung, D. Y. C. Leung, K. Sumathy, Renewable Sus-
tainable Energy Rev. 2007, 11, 401.
[27] N. Jaffrezic-Renault, P. Pichat, A. Foissy, R. Mercier, J. Phys. Chem.
1986, 90, 2733.
[28] M. Maicu, M. C. Hidalgo, G. Colón, J. A. Navío, J. Photochem. Photo-
biol., A 2011, 217, 275.
[29] J. M. Macak, B. G. Gong, M. Hueppe, P. Schmuki, Adv. Mater. 2007,
19, 3027.
[30] N. Zhang, S. Liu, X. Fu, Y.-J. Xu, J. Phys. Chem. 2011, 115, 9136.
[31] C. Zhang, H. He, Catal. Today 2007, 126, 345.
Small 2023, 19, 2303306 2303306 (8 of 8)
16136829, 2023, 43, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smll.202303306 by Nazarbayev University, Wiley Online Library on [18/12/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.small-journal.com
[32] N. T. Nguyen, J. Yoo, M. Altomare, P. Schmuki, Chem. Commun. 2014,
50, 9653.
[33] N. T. Nguyen, M. Altomare, J. Yoo, P. Schmuki, Adv. Mater. 2015, 27,
3208.
[34] N. T. Nguyen, S. Ozkan, O. Tomanec, X. Zhou, R. Zboril, P. Schmuki,
J. Mater. Chem. A 2018, 6, 13599.
[35] M. Altomare, N. T. Nguyen, P. Schmuki, Chem. Sci. 2016, 7, 6865.
[36] D. Zhong, Q. Jiang, B. Huang, W.-H. Zhang, C. Li, J. Energy Chem.
2015, 24, 626.
[37] T. Butburee, P. Kotchasarn, P. Hirunsit, Z. Sun, Q. Tang, P.
Khemthong, W. Sangkhun, W. Thongsuwan, P. Kumnorkaew, H.
Wang, K. Faungnawakij, J. Mater. Chem. A 2019, 7, 8156.
[38] F. Shahvardanfard, G. Cha, N. Denisov, B. Osuagwu, P. Schmuki,
Nanoscale Adv. 2021, 3, 747.
[39] X. Zhou, N. Denisov, G. Cha, I. Hwang, P. Schmuki, Electrochem.
Commun. 2021, 124, 106937.
[40] G. Cha, I. Hwang, S. Hejazi, A. S. Dobrota, I. A. Pašti, B. Osuagwu,
H. Kim, J. Will, T. Yokosawa, Z. Badura, Š. Kment, S. Mohajernia, A.
Mazare, N. V. Skorodumova, E. Spiecker, P. Schmuki, iScience 2021,
24, 102938.
[41] T. Ohno, K. Sarukawa, M. Matsumura, New J. Chem. 2002, 26, 1167.
[42] K. Lv, B. Cheng, J. Yu, G. Liu, Phys. Chem. Chem. Phys. 2012, 14, 5349.
[43] H. Tong, Y. Zhou, G. Chang, P. Li, R. Zhu, Y. He, Appl. Surf. Sci. 2018,
444, 267.
[44] M. Licklederer, R. Mohammadi, N. T. Nguyen, H. Park, S. Hejazi, M.
Halik, N. Vogel, M. Altomare, P. Schmuki, J. Phys. Chem. C 2019, 123,
16934.
[45] S. Hüfner, G. K. Wertheim, J. H. Wernick, Solid State Commun. 1975,
17, 417.
[46] C. Xu, J. Su, X. Xu, P. Liu, H. Zhao, F. Tian, Y. Ding, J. Am. Chem. Soc.
2006, 129, 42.
[47] S.-M. Wu, I. Hwang, B. Osuagwu, J. Will, Z. Wu, B. B. Sarma, F.-F. Pu,
L.-Y. Wang, Z. Badura, G. Zoppellaro, E. Spiecker, P. Schmuki, ACS
Catal. 2022, 13, 33.
[48] S.-M. Wu, P. Schmuki, Energy Technol. 2023, 2300052.
[49] K. Kimura, S. Naya, Y. Jin-nouchi, H. Tada, J. Phys. Chem. C 2012, 116,
7111.
[50] P. Peerakiatkhajohn, T. Butburee, J.-H. Yun, H. Chen, R. M. Richards,
L. Wang, J. Mater. Chem. A 2015, 3, 20127.
[51] X. F. Cheng, W. H. Leng, D. P. Liu, Y. M. Xu, J. Q. Zhang, C. N. Cao, J.
Phys. Chem. C 2008, 112, 8725.
[52] F. Leroy, Ł. Borowik, F. Cheynis, Y. Almadori, S. Curiotto, M.
Trautmann, J. C. Barbé, P. Müller, Surf. Sci. Rep. 2016, 71, 391.
© 2023 The Authors. Small published by Wiley-VCH GmbH