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Pd-catalyzed instant hydrogenation of TiO2

with enhanced photocatalytic performance†
Cite this: Energy Environ. Sci.,
2016, 9, 2410
Yingfeng Xu, Chen Zhang, Lingxia Zhang, Xiaohua Zhang, Heliang Yao and
Jianlin Shi*

Received 19th March 2016,
Accepted 8th June 2016
DOI: 10.1039/c6ee00830e
www.rsc.org/ees
Hydrogenated TiO2 with remarkably elevated photocatalytic activity has triggered great interest, which,
unfortunately, has been commonly obtained so far under severe conditions such as extraordinarily high
pressure (20.0 bar) and/or high temperature (up to 700 1C) over a long period of treatment (up to
several days). Here, through doping with a slight amount of Pd, hydrogenated TiO2 is obtained at room
temperature under non-pressurised H2 or H2/O2 gas flow within several minutes. This extremely facile
Pd-catalyzed hydrogenation strategy is based on the discovered fact that H2 could spontaneously
dissociate on the Pd surface to generate highly active atomic hydrogen species [H], which would diffuse
into and interact with the TiO2 lattice to generate durable point defects (Ti3+, oxygen vacancies) and
even surface disorder, resulting in the largely enhanced solar energy utilization of TiO2. Additionally, the
proposed Pd-catalyzed hydrogenation strategy turns out to be applicable to reduce other transition
metal oxides, providing a general methodology for oxide hydrogenation under ordinary conditions.

Broader context
Hydrogenation engineering of transition metal oxides to create intrinsic defects, such as abnormal-valence metal ions, oxygen vacancies and even lattice
disorder, for mid-gap state generation to significantly enhance their visible light absorption and photocatalytic activities, has been considered as one of the
promising methodologies to improve solar energy utilization. However, limited by the extremely sluggish interactions between molecular hydrogen and
transition metal oxides, high temperatures or pressures and huge doses of H2 or plasma activation with prolonged treatment periods have been inevitably
needed to generate sufficient reactive hydrogen species for efficient hydrogenation. Taking TiO2 as a typical example, in this work, we have developed an
especially facile and efficient Pd-catalyzed hydrogenation strategy at room temperature under non-pressurised hydrogen gas flow within several minutes. The
created point defects (Ti3+ and oxygen vacancies) or even a unique crystalline core/disordered shell structure significantly decreases the band-gap of TiO2 and
substantially improves its solar energy utilization. This study is the first paradigm of Pd catalyzing the hydrogenation of inorganic metal oxides without phase
and morphology-selectivity, and we believe that such a facile and general methodology will open up a new pathway to create intrinsic defects in oxides for
advanced photocatalytic systems.

1. Introduction which has mainly involved non-metal element doping, noble

Benefiting from its excellent photoactivity, photostability, non-
toxicity and abundance, titanium dioxide (TiO2) has become
the most appealing and promising photocatalyst among various
candidates for solar energy conversion.1,2 However, as a type of
wide band-gap semiconductor, the photo-conversion effect of
TiO2 can only be photo activated by ultraviolet light. Hence, great
efforts have been devoted to narrowing the band gap of TiO2 and
extending its light absorption spectrum to the visible region,
State Key Laboratory of High Performance Ceramics and Superfine Microstructure,
Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Ding-Xi Road,
Shanghai, 200050, P. R. China. E-mail: jlshi@mail.sic.ac.cn
† Electronic supplementary information (ESI) available: Detailed materials syn-
thesis and treatments, additional material characterization. See DOI: 10.1039/
c6ee00830e
metal coupling and surface sensitization.3–6 Recently, a break-
through on the hydrogenation of TiO2, giving rise to absorption
across the entire visible-light region and remarkable photo-
catalytic activity under sunlight, has been achieved and has
subsequently triggered great research interest worldwide.7–10
Theoretically, the hydrogenation of TiO2 could induce point
defects, surface disorder and other physical/chemical property
changes, which will generate mid-gap states, as mentioned in
other studies on methods generating intrinsic defects in TiO2
to give enhanced photocatalytic activities,11–14 to significantly
reduce the band gap of TiO2 and achieve efficient utilization of
solar energy.15–17
Different strategies have been explored to obtain hydroge-
nated TiO2 nanomaterials. Chen et al. reported the hydrogenation
of TiO2 nanoparticles under 20.0 bar pure H2 gas pressure at

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200 1C for 5 days, which resulted in extended optical absorption
to the near infrared region and substantially improved the
photocatalytic activity with prolonged stability.8 Wang et al.
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reported hydrogenated rutile TiO2 nanowire arrays as a photo-
anode by annealing the material in an ultrahigh-purity hydro-
gen atmosphere at 450 1C for 3 h, revealing a significantly
enhanced photo-current density with full-spectrum light
absorption.9 Other reported methods include hydrogen plasma
treatments or hydrogen–argon treatments at 400–700 1C for
several to tens of hours.18–20 Apparently, all these available
hydrogenation strategies suffer from the especially sluggish
interaction between molecular hydrogen and TiO2,21 where
high temperatures or pressures, huge doses of H2 or plasma
activation with prolonged treatment periods are inevitably
needed to generate sufficient reactive hydrogen species. Thus,
there is an urgent need to seek novel hydrogenation strategies
through substantially more efficient, facile and cost-effective
approaches with prospects for mass production.
By accident, when incorporating a small amount Pd in rutile
TiO2 (TiO2/Pd, Table S1, see ESI†) for administrating photo-
catalytic hydrogen evolution, the photocatalyst experienced a
significant colour change from light yellow to black in less than
10 min under light illumination (Fig. S1, see ESI†). The sub-
sequent comparison in the hydrogen production performance
showed a two-fold H2 production enhancement, with main-
tained photocatalytic performance in the successive second
round test (TiO2/Pd-2rd) or in a new round test by recycling
the colour-changed TiO2/Pd powders (TiO2/Pd-post, Fig. S2, see
ESI†). Judging from the electron paramagnetic resonance (EPR)
spectra (Fig. S3, see ESI†), typical Ti3+ species (g = 1.985) were
surprisingly detected in the TiO2/Pd-post sample,22 which were
absent in both TiO2/Pd and pure TiO2 before and after the hydrogen
evolution experiment (TiO2-post), implying that TiO2/Pd had been
irreversibly reduced during the photocatalytic water reduction
process. Inspired by these self-reduced discoveries and the vital
role of Pd in catalyzing the hydrogenation of unsaturated
hydrocarbons in general organic synthesis,23 we wondered if
the hydrogen molecules generated during the photocatalytic
process can reduce the TiO2 matrix in the presence of Pd,
consequently providing a possible strategy, based on the catalytic
role of Pd, to hydrogenate TiO2 at room temperature under
ordinary H2 gas flow in a simple device (Fig. S4, see ESI†).
2. Results and discussion
2.1 Feasibility demonstration of the Pd-catalyzed
hydrogenation on rutile TiO2
For verification of the supposition of Pd-catalyzed hydrogenation,
rutile TiO2 nanoparticles loaded with 0.43 mol% Pd (denoted as
R/Pd, Table S1, see ESI†) were first synthesized and then treated
directly under H2/Ar gas flow (200 sccm and 10 vol% H2).
Excitingly, the colour of R/Pd changed instantly from light yellow
to black in few seconds (Video 1, see ESI†). Moreover, in addition
to the fast colour transformation into black, with the open-air
treatment of R/Pd under the same H2/Ar gas flow, the sample was
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Fig. 1 Pd-catalyzed hydrogenation process and characteristics of rutile
samples. (a) Self-heating effect of R/Pd during the Pd-catalyzed hydro-
genation in H2/Ar gas flow in air atmosphere, compared with pure TiO2.
The insets are the photographs and corresponding thermal images of R
and R/Pd during the hydrogen treatment in air (the left one was recorded
after 4 s, and the right one after 8 s of the treatment, Video 2, see ESI†).
(b) EPR spectra of different samples measured at 100 K. (c) Diffuse
reflectance UV-vis spectra and (d) valence-band XPS spectra of the
different samples. Inset is the magnified image of the corresponding
region in (d).
quickly self-heated to above 250 1C (Fig. 1a and Video 2, see ESI†);
such a self-heating effect could not be observed in the absence
of oxygen. Consequently, the R/Pd samples were treated in two
different ways as follows: one was treated in H2/Ar flow for 10 min
and labeled as H-R/Pd, and the other was treated in O2 (2 vol%)-
containing H2/Ar flow for 10 min and labeled as O&H-R/Pd. The
same treatment conditions were applied to the pure rutile TiO2
(denoted as R) samples, and the consequent products were
respectively labeled as H-R and O&H-R as corresponding controls.
Encouraged by the significant darkening effect observed in
the treated Pd-loaded TiO2 samples (Fig. S5, see ESI†), EPR
spectroscopy was further employed to examine the possible
generation of paramagnetic species, which can provide direct
proof for the hydrogenation/reduction of TiO2. As shown in
Fig. 1b, asymmetric EPR signals at g = 1.98 of both H-R/Pd and
O&H-R/Pd can be clearly observed and undoubtedly assigned to
Ti3+ species.22 However, these signals are absent in R/Pd, R, H-R
and O&H-R, verifying that the rutile TiO2 matrix could be
efficiently reduced by the Pd-catalyzed hydrogenation at ambient
temperature. The resonances at g values in the range of 2.02
to 2.12 of H-R/Pd and O&H-R can be attributed to the super-
imposed signals of O2 radicals and oxygen vacancies.22,24 The
resonances at higher g values from 2.12 to 2.16 only observed in
O&H-R/Pd corresponds to a wider Zeeman splitting gap, which is
believed to be generated from the drastic self-heating effect.
According to the EPR results of the negative control a-Al2O3/Pd
under same treatments (Table S1 and Fig. S6, see ESI†), all these
above-mentioned signals are confirmed essentially from the
changes of the TiO2 matrix itself, excluding the potential influ-
ences of the Pd nanoparticles after H2 treatment.
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Diffuse reflectance ultraviolet-visible (UV-vis) spectroscopy
was then employed to investigate the optical properties of the
R, R/Pd, H-R/Pd and O&H-R/Pd samples (Fig. 1c). Compared
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with the R sample, the enhanced visible-light absorption of
R/Pd is commonly attributed to the localized surface plasmon
resonance of Pd nanoparticles.25 Noticeably, both the H-R/Pd
and O&H-R/Pd samples show substantial visible and even
infrared light absorptions. According to the UV-vis spectra of
the negative control a-Al2O3/Pd by the same treatment (Fig. S7,
see ESI†), the remarkably enhanced visible light absorption of
the H-R/Pd and O&H-R/Pd samples are reasoned to result from
the narrowed band gap through these proposed treatments.
From the valence band XPS (VBXPS) spectra, the substantially
blue-shifted VBM of both H-R/Pd and O&H-R/Pd further con-
firms the narrowed band gap of the H-R/Pd and O&H-R/Pd
samples, which should be related to the generated Ti3+ species
and oxygen vacancies during the H2 treatment (Fig. 1d).
Furthermore, the potential morphological and structural
changes of the rutile TiO2 through the proposed Pd-catalyzed
hydrogenation strategy were characterized by transmission
electron microscopy (TEM), XRD and Raman techniques. From
the overview transmission electron microscope (TEM) image of
R/Pd (Fig. 2a), the Pd nanoparticles are hard to find because of
their small loading amount. It was very fortunate to find a Pd
nanoparticle localized on the TiO2 matrix (Fig. 2d), revealing
the close linkage between the Pd nanoparticle and the matrix.
As shown in the high-resolution TEM (HRTEM) images, the
detailed structure of the O&H-R/Pd sample (Fig. 2e and f),
Fig. 2 Morphological and structural characterizations of different rutile
samples. Overview TEM (a) and HRTEM images (b) of R/Pd sample.
Pd-catalyzed hydrogenated TiO2 without (c) or in the presence of O2 (d).
HRTEM image (e) and corresponding structural line analysis (f) of O&H-R/Pd
sample. Scale bars are 100 nm for a, and 5 nm for b–e. XRD patterns (g) and
Raman spectra (h) of different samples.
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mainly at the particle surface, is quite different from those of
the R/Pd (Fig. 2b) and H-R/Pd samples (Fig. 2c). Obviously, the
R/Pd sample is well-crystallized, displaying clearly-resolved and
well-defined lattice fringes, even at the surface of the nano-
crystals, while the O&H-R/Pd sample exhibits a unique crystalline
core/disordered shell structure, characterized by a B1 nm-thick
disordered surface layer. The significant structural changes of the
O&H-R/Pd sample can also be confirmed by XRD patterns
(Fig. 2g), featuring a slight shift in the peaks of O&H-R/Pd
towards lower 2-theta values, which should be related to its
surface lattice distortion.
Raman scattering spectra were recorded to further examine
the potential defects and structural changes of the samples
after the Pd-catalyzed hydrogenation (Fig. 2h). All samples
show three typical Raman-active modes of a multi-proton
process (230 cm 1), Eg (440 cm 1) and A1g (610 cm 1), corres-
ponding to the tetragonal space group of P42/mnm. The broad-
ening of the Eg and A1g modes observed in both H-R/Pd and
O&H-R/Pd are due to the oxygen vacancies generated in the
oxides,26 and the relatively broader Raman bands of O&H-R/Pd
can be related to its more severely disordered surface structure,
which is also evidenced by the much stronger EPR signals
in Fig. 1b. Accordingly, despite the point defects generated in
H-R/Pd, the significant microstructural changes of the O&H-R/Pd
sample indicate a deeper hydrogenation state of rutile TiO2 by
self-heating effects.
The photocatalytic activities of the treated samples were
then investigated by measuring the amounts of hydrogen
production from water photo-reduction under a full-spectrum
simulator (AM 1.5 G) and visible light (l 4 400 nm) irradiation
(Fig. 3a and b). The amount of catalyst used was 50 mg in all
Fig. 3 Photocatalytic activities and stabilities of the hydrogenated rutile
TiO2. Photocatalytic hydrogen production on different samples (50 mg of
each sample) under AM 1.5 G irradiation (a) and visible light irradiation (b,
l 4 400 nm). The inset plots in (a) and (b) are the normalized time-course
record of hydrogen generation. (c) Photocatalytic degradation of MB
solution by different samples under AM 1.5 G irradiation. (d) Cycling
measurements of photocatalytic hydrogen evolution by O&H-R/Pd and
H-R/Pd under AM 1.5 G irradiation.
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photocatalytic experiments. Consistent with the discoveries
mentioned in the ‘‘Introduction’’ section, R/Pd is also self-
reduced (denoted as S-R/Pd) during the photocatalytic water
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reduction process with AM 1.5 G irradiation, since the colour
changed from yellow into black and Ti3+ species can be detected
from the EPR spectrum (Fig. S8, see ESI†). Consequently, the
S-R/Pd sample exhibited a comparable hydrogen generation rate
(1.58 mmol h 1 g 1) to H-R/Pd (1.67 mmol h 1 g 1) under AM
1.5 G irradiation. Attractively, the hydrogen generation rate of
O&H-R/Pd (3.32 mmol h 1 g 1) was almost double that of S-R/Pd
and H-R/Pd samples under the same conditions.
When irradiated by visible light (l 4 400 nm, Fig. 3b), the
O&H-R/Pd sample exhibited the highest hydrogen generation
rate (130 mmol h 1 g 1). At this given time, the photocatalytic
hydrogen generation rate of H-R/Pd sample (44 mmol h 1 g 1)
was four times that of S-R/Pd (11 mmol h 1 g 1), and no H2 gas
generation or colour change could be detected when testing
R/Pd under the same conditions, indicating that the self-
reduction of R/Pd was unprocurable under visible light irradiation.
Under the same measurement conditions, no H2 gas generation
could be detected in the negative control groups (R, H-Al2O3/Pd and
O&H-Al2O3/Pd) by both of AM 1.5 G and visible light irradiation,
excluding possible photocatalytic enhancement effects by Pd
and/or H, or their complex.
Accordingly, it is reasonable to conclude that through the
proposed Pd-catalyzed hydrogenation treatment, the created
Ti3+ species and oxygen vacancies in rutile TiO2 resulted in
effectively improved photocatalytic activities under visible light
Fig. 4 Mechanism probing of Pd-catalyzed hydrogenation strategy. Pd-M4,5 and Ti-L2,3 core-loss (a) and low-loss (b) EELS spectra of TiO2/Pd before
and after the hydrogen treatment. Ag-M4,5, Pt-M3,4,5, Au-M3,4,5 core-loss (c), Ti-L2,3 core-loss (d) and low-loss (e) EELS spectra of TiO2/Ag, TiO2/Pt,
TiO2/Au samples before and after the same hydrogen treatment of TiO2/Pd. (f) Schematics of the approach for facile hydrogenation of TiO2 in the
presence of Pd.
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illumination (Fig. 3b).27 Considering the similar light absorp-
tion behavior between O&H-R/Pd and H-R/Pd (Fig. 1c and d),
the remarkably enhanced photocatalytic activities of O&H-R/Pd
could be ascribed to the more efficient photo-excited electron
and hole (e /h+) separation, and subsequently stronger oxidizing/
reduction capability towards the absorbed molecules (water
and pollutants) under illumination, which can be related to
the induced crystalline core/disordered shell structure.15
Experiments to test the photocatalytic decomposition of
methylene blue (MB) were further conducted under aerobic
conditions under AM 1.5 G irradiation (Fig. 3c). In addition
to the most efficient photodegradation of MB observed in
O&H-R/Pd, H-R/Pd exhibited a substantially elevated degradation
rate compared to R/Pd, again evidencing the elevated and stable
photocatalytic activities of the O&H-R/Pd and H-R/Pd samples,
obtained through the proposed Pd-catalyzed hydrogenation strategy,
under both the presence and absence of oxygen, respectively.
The well-sustained long-term stabilities of the O&H-R/Pd and
H-R/Pd samples were also proved by 10 day cyclic photocatalytic
hydrogen evolution tests (Fig. 3d), and further confirmed by
the fact that Ti3+ and oxygen vacancies could be retained in the
O&H-R/Pd and H-R/Pd samples after 30 days of storage in an air
atmosphere (Fig. S9, see ESI†). Additionally, the unique crystal-
line core/disordered shell structure of O&H-R/Pd has been well
retained after 1 year of storage in an air atmosphere, as well as
the enhanced H2 evolution rates (Fig. S10 and S11, see ESI†).
Therefore, all these findings give comprehensive evidence of the
proposed Pd-catalyzed hydrogenation strategy for ultrafast defect
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generation in a TiO2 lattice at room temperature with substan-
tially improved photocatalytic activities and sustained stability.
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2.2 Mechanism of the Pd-catalyzed hydrogenation strategy
In order to reveal the proposed Pd-catalyzed hydrogenation
process more convincingly, electron energy-loss spectroscopy
(EELS) was employed to give qualitative evidence of the electro-
nic state changes in the Pd catalyst and the TiO2 matrix. In
theory, the intensity of the Pd-M4,5 signals in EELS mainly
reflects the density of the unoccupied electron states, which are
sensitive to the valence state of Pd.28 After H2/Ar gas flow
through the sample, the significantly observed M4,5 signals
corresponds to the generation of a high valence state in Pd
(Fig. 4a), which confirms the spontaneous dissociation of H2
molecules on the Pd surface, penetration into the bulk and the
subsequent formation of PdHx species, and consequently the
rapid activation of H2.29 The creation of non-zero-valance Pd
could be further evidenced by the XPS results (Fig. S12, see
ESI†). Correspondingly, the detected shift of the Ti-L2,3 edge
towards a lower energy after the treatment should be ascribed
to the generation of reduced Ti species (Ti3+, confirmed by the
above-mentioned EPR results), indicating that the dissociated
hydrogen species could efficiently diffuse from Pd to TiO2 and
fractionally reduce Ti4+ to Ti3+ (Fig. 4a and 1b). Furthermore,
the decreased t2g–eg crystal-splitting of Ti-L2,3 after the hydrogen
treatment, which changed from 2.23 eV to 2.05 eV in L3 and
2.61 eV to 2.12 eV in L2, confirms the generation of point defects
in the TiO2 matrix (Fig. 4a).30,31 The detected difference of low-
loss EELS reflects the increased free electron density in the TiO2
matrix through the reduction treatment,32 which could be
ascribed to the hydrogenation-induced intrinsic defects (Fig. 4b).
Accordingly, in the proposed Pd-catalyzed hydrogenation
strategy, most introduced H2 molecules will spontaneously
dissociate on Pd nanoparticles and transform into highly active
atomic hydrogen [H] species, which can further migrate along
the Pd surface to the titania nanoparticles in the vicinity and
react with them to reduce the lattice Ti4+ and create point
defects such as oxygen vacancies in the treated titania (Fig. 4f).
Furthermore, due to the highly efficient catalyzing effects of the
Pd nanoparticles in H2 dissociation, the increased Pd loading
amount is found to be of insignificant influence on the hydro-
genation process of TiO2 (Fig. S13, see ESI†). When introducing
an appropriate amount of O2 into the system, a small portion of
the highly-reactive [H] species will inevitably react with O2, in a
highly exothermic way, to generate a special heat flow on their
diffusion pathways (Fig. 1a), which will significantly promote
the reaction between the discrete [H] and TiO2, inducing a
strengthened hydrogenation (Fig. S14, see ESI†) and creating a
disordered surface in titania (Fig. 2e, f and Fig. S15, see ESI†).
The disordered shell could further stabilize the reduced Ti3+
species in the surface shell of the hydrogenated TiO2 (Fig. S14,
see ESI†), in addition to its confirmed positive effects on the
photocatalytic activity (Fig. 3, Fig. S16 and Table S2, see ESI†).
It is then understandable why the TiO2/Pd photocatalyst can
be irreversibly reduced during the photocatalytic water reduction
process, as afore-mentioned (Fig. S3 and S8, see ESI†); that is,
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under full-spectrum light illumination, the photocatalytic
generated hydrogen molecules could migrate from Pd to the
TiO2 nanoparticles to reduce partial lattice Ti4+ at the surface
into Ti3+ species, resulting in the self-reduction of TiO2/Pd with
enhanced photocatalytic activity (Fig. 3 and Fig. S2, see ESI†).
This self-reduction effect could helpfully compensate the fading of
point defects after long term storage in air, resulting in the
photocatalytic activity for hydrogen evolution being maintained
(Fig. S14 and S17, see ESI†).
However, the activation effect on H2 molecules to realize the
hydrogenation of the TiO2 matrix has only been discovered
in the presence of Pd, and could not be observed on other noble
metals with similar electron configurations. No traces of
valence-state changes in Ag, Pt and Ag have been detected,
indicating their lack of activity in the spontaneous dissociation of
H2 molecules under such mild conditions (Fig. 4c and Table S1,
see ESI†). Accordingly, no detectable change in the core-loss
and low-loss EELS can be observed in TiO2 after the treatments
(Fig. 4d and e). Logically, the unique revealed role of Pd in
catalysing the hydrogenation of TiO2 is based on the negligible
activation barrier for H2 molecules to dissociate on Pd, with the
special d10 electron configuration, and transform into highly
reactive [H] species, which may be attributed to the absence
of s orbital electrons, leading to the inappreciable dissociation
energy of H2 molecules.33,34
2.3 Phase independence of the Pd-catalyzed hydrogenation
strategy
In theory, such convenient hydrogenation of TiO2 based on the
H2 activation effect in Pd is of remarkable universality without
any phase and morphology selectivity, which is believed
to provide a general method to generate intrinsic defects in
various TiO2 species and expectably improve their solar energy
utilization. Thus, widely studied anatase TiO2 nanoparticles
and a TiO2 nanowire film on an FTO substrate as a photoanode
were further chosen as typical representatives, loaded with a
small amount of Pd (Table S1, see ESI†) and treated by a similar
hydrogenation process to rutile TiO2.
As expected, the successful reduction of the anatase TiO2
at room temperature through the proposed Pd-catalyzed hydro-
genation strategy (Fig. S18, see ESI†) is confirmed by the
observed Ti3+ species and oxygen vacancies in anatase nano-
particles (H-A/Pd and O&H-A/Pd) from the EPR spectra (Fig. 5a).
Interestingly, differently from rutile TiO2 (Fig. 1b), the density
of the Ti3+ species is much higher than the that of oxygen
vacancies in the hydrogenated anatase TiO2, suggesting that
the reduction of Ti4+ species in anatase TiO2 is relatively easier
than that in rutile TiO2 by the proposed hydrogenation strategy.
The substantially improved visible light absorption (Fig. 5b)
and elevated raised VBM (Fig. S19, see ESI†) of the H-A/Pd and
O&H-A/Pd samples confirm that the generated point defects
could create mid-gap states to decrease the band gap of anatase
TiO2. In addition to the highly crystallized features of A/Pd and
H-A/Pd, the lattice reconstruction of anatase TiO2 nanoparticles
also takes place after the oxygen-assisted Pd-catalyzed hydro-
genation treatment, as a noticeable crystalline core/disordered
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Fig. 5 Phase independence of the Pd-catalyzed hydrogenation strategy.
EPR spectra (a), diffuse reflectance UV-vis spectra (b) and Raman spectra
(c) of different anatase TiO2 samples. (d) Photocatalytic hydrogen produc-
tion on different anatase TiO2 samples under AM 1.5 G illumination. The
inset is the normalized time-course record of hydrogen generation.
shell structure is observed in the O&H-A/Pd sample (Fig. S20,
see ESI†) with significant XRD peak-shifts towards a lower angle
(Fig. S21, see ESI†). The point defects and even lattice imperfec-
tions of the H-A/Pd and O&H-A/Pd samples lead to significantly
broadened Raman peaks (Fig. 5c), indicating a deeper hydro-
genation state of anatase TiO2.
Consistent with the results discovered for rutile TiO2, the
O&H-A/Pd sample with the unique crystalline core/disordered
shell structure exhibited the highest photocatalytic activities in
both photocatalytic hydrogen evolution experiments (Fig. 5d)
and MB photodegradation (Fig. S22, see ESI†). A/Pd was also
self-reduced during the hydrogen evolution experiments, as
evidenced by the detected Ti3+ species (Fig. S23, see ESI†),
exhibiting a comparable hydrogen generation rate (0.63 mmol
h 1 g 1) to that of H-A/Pd (0.75 mmol h 1 g 1, Fig. 5d). For the
MB photodegradation under aerobic conditions to avoid the
self-reduction of the A/Pd sample, the photocatalytic activity of
H-A/Pd was significantly higher than that of the A/Pd sample
(Fig. S22, see ESI†). Accordingly, it is reasonable to conclude
that the generated intrinsic defects such as point defects
(Ti3+ and oxygen vacancies) and lattice defects could enhance
the photocatalytic activity of TiO2 for both rutile and anatase
phases. The long term stability of the hydrogenated anatase
TiO2 was characterized by the 10 day cyclic experiments
(Fig. S24, see ESI†) and the presence of Ti3+ species after 30 days
of storage in an air atmosphere (Fig. S25, see ESI†). The signal
intensity of Ti3+ species in the O&H-A/Pd sample was remarkably
higher than that in the H-A/Pd sample (Fig. S25, see ESI†), further
confirming that the surface disordering will help in enhancing
the long-term stability of the generated defects in the hydroge-
nated TiO2 obtained, in addition to its confirmed positive effects
in solar energy utilization.
Conventionally, reduction of the TiO2 film (labeled as TiO2-F)
is quite difficult even under severe hydrogenation conditions
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(high pressure, high temperature or plasma), with potential
mechanical disruption on the film and even the substrate.
Such shortcomings are expected to be avoidable by the facile
Pd-catalyzed hydrogenation strategy (Fig. S26, see ESI†). The
improved visible light absorption of the hydrogenated TiO2-F
samples (H-TiO2-F/Pd and O&H-TiO2-F/Pd) indicates the
generation of intrinsic defects by the facial Pd-catalyzed hydro-
genation treatment, reducing the band gap of TiO2 nanowires
(Fig. S26e, see ESI†).
The PEC performances of hydrogenated TiO2-F samples
were investigated by measuring the photocurrent densities
under AM 1.5 G illumination and the incident photon-to-
current efficiency (IPCE) in a three-electrode electrochemical
system. Noticeably, the O&H-TiO2-F/Pd sample exhibited the
highest photocurrent densities (Fig. S27, see ESI†) and the
lowest photocurrent onset potential (Fig. 6a), resulting in
the highest total photoconversion efficiency (Fig. 6b). The
steady photocurrent density of the O&H-TiO2-F/Pd sample was
double that of TiO2-F/Pd sample with reproducible photo-
response upon illumination (Fig. S28, see ESI†). The improved
PEC performance of the H-TiO2-F/Pd sample was also observed
compared with the control samples (Fig. 6a, b and Fig. S27, S28,
see ESI†). As seen with the hydrogenated titania, an appreciable
IPCE appears when l is less than 420 nm, indicating that the
enhanced photocatalytic activities are more strongly related to
the improved photo-excited e /h+ separation efficiency than the
broad visible light absorption (Fig. 6b). And from Nyquist and
Mott–Schottky plots, the smaller radius of the arcs and the less
steep slope of the hydrogenated TiO2-F samples further confirm
a more efficient charge transfer process and higher carrier density
in the treated TiO2-F samples, especially for O&H-TiO2-F/Pd
(Fig. 6c and d).
Fig. 6 PEC performances and characterizations of different TiO2-F
samples: (a) J–V curves of different TiO2-F samples under AM 1.5 G
illumination (scan rate, 5 mV s 1). (b) IPCE curves of different TiO2-F
samples (measured at 1.0 V vs. RHE). (c) Electrochemical impedance
spectra and (d) Mott–Schottky plots of different TiO2-F samples.
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Energy & Environmental Science
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Fig. 7 General feasibility of the Pd-catalyzed hydrogenation strategy. EPR
spectra of different CeO2 samples (a) and WO3 samples (b), showing the
enhanced Ce3+ and W5+ EPR signals generated after the Pd-catalyzed
hydrogenation process.
Accordingly, it is reasonable to conclude that the intrinsic
defects in the TiO2 nanowires in the film generated through the
facile Pd-catalyzed hydrogenation strategy could increase the
free donor density and the efficiency of the charge transfer
process, resulting in the enhanced PEC performance. Taken
together, all these results conceivably reflect the outstanding
advantages of the general Pd-catalyzed hydrogenation strategy
in TiO2, with no phase and morphology selectivity.
2.4 Generalization of the Pd-catalyzed hydrogenation strategy
to other transition metal oxides
Encouraged by the above-demonstrated convenience and uni-
versality in TiO2 reductions, such a Pd-catalyzed hydrogenation
strategy was further deduced feasible to reduce other transition
metal oxides under ambient conditions. To prove this deduction,
representative CeO2 nanowires and WO3 microrods were synthe-
sized, loaded with small amounts of Pd (Table S1, see ESI†)
and treated with the Pd-catalyzed hydrogenation process
(Fig. S29–S32, see ESI†). As expected, these nonstoichiometric
oxides were successfully hydrogenated into a deeply reduced
state, featuring significantly intensified Ce3+ species signals
(g = 1.95) in H-CeO2/Pd and W5+ species (g = 1.89) in H-WO3/Pd
(Fig. 7a and b),35,36 with no detectable phase transformation
(Fig. S29 and S31, see ESI†). These results undoubtedly confirm
the general feasibility of the present Pd-catalyzed hydrogenation
strategy for the room temperature reduction of transition metal
oxides.
3. Conclusions
In summary, an especially facile and efficient Pd-catalyzed
strategy for the hydrogenation of various TiO2 samples and
other transition metal oxides has been developed. The created
point defects in TiO2 (Ti3+ and oxygen vacancies) remarkably
narrow the band-gap and improve their solar energy utilization.
Furthermore, under additional oxygen assistance, the resultant
extra self-heating effect in the Pd-catalyzed hydrogenation
process will induce a unique crystalline core/disordered shell
structure, which is believed to prevent the photo-excited e /h+
from recombination and be helpful for the long-term stability
of the reduced TiO2. Analogous to the hydrogenation of
unsaturated hydrocarbons via the prevailing Pd catalyst, to our
2416 | Energy Environ. Sci., 2016, 9, 2410--2417
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Paper
best knowledge, this study is the first paradigm of Pd catalyzing
the hydrogenation of inorganic metal oxides. We believe that
such a facile and general Pd-catalyzed hydrogenation method-
ology will open up a new pathway for the creation of intrinsic
defects in oxides with greatly enhanced catalytic performance.
Author contributions
The manuscript was written with contributions from all authors.
All authors have given approval to the final version of the
manuscript.
Conflict of interest
The authors declare no competing financial interest.
Acknowledgements
This work was financially supported by the National Key Basic
Research Program of China (2013CB933200), National 863
plans projects (2012AA062703), National Natural Science Foun-
dation of China (21177137), and Youth Innovation Promotion
Association of CAS (2012200). We thank Jiafu Chen from Hefei
National Laboratory for Physical Sciences at the Microscale,
University of Science and Technology of China for the assistance
with EPR measurements. Thanks to Linlin Zhang and Jingwei
Feng from Shanghai Institute of Ceramics, Chinese Academy of
Sciences for useful discussions.
References
1 X. Chen, S. Shen, L. Guo and S. S. Mao, Chem. Rev., 2010,
110, 6503–6570.
2 L. T. Tracy and John T. Yates, Jr., Chem. Rev., 2006, 106,
4428–4453.
3 X. Chen and S. S. Mao, Chem. Rev., 2007, 107, 2891–2959.
4 Y. Ma, X. Wang, Y. Jia, X. Chen, H. Han and C. Li, Chem.
Rev., 2014, 114, 9987–10043.
5 L. Jiangtian, K. C. Scott, Z. Peng, S. Tess, M. Fanke,
D. B. Alan, M. Ayyakkannu and W. Nianqiang, J. Am. Chem.
Soc., 2014, 136, 8438–8449.
6 I. S. Cho, C. H. Lee, Y. Feng, M. Logar, P. M. Rao, L. Cai,
D. R. Kim, R. Sinclair and X. Zheng, Nat. Commun., 2013,
4, 1723.
7 X. Chen, L. Liu and F. Huang, Chem. Soc. Rev., 2015, 44,
1861–1885.
8 X. Chen, L. Liu, Y. Y. Peter and S. S. Mao, Science, 2011, 331,
746–750.
9 G. Wang, H. Wang, Y. Ling, Y. Tang, X. Yang, R. C.
Fitzmorris, C. Wang, J. Z. Zhang and Y. Li, Nano Lett.,
2011, 11, 3026–3033.
10 Y. H. Hu, Angew. Chem., Int. Ed., 2012, 51, 12410–12412.
11 Z. Zhang, M. N. Hedhili, H. Zhu and P. Wang, Phys. Chem.
Chem. Phys., 2013, 15, 15637–15644.
This journal is © The Royal Society of Chemistry 2016

Paper
12 Z. Zhang, X. Yang, M. N. Hedhili, E. Ahmed, L. Shi and
P. Wang, ACS Appl. Mater. Interfaces, 2014, 6, 691–696.
13 Q. Kang, J. Cao, Y. Zhang, L. Liu, H. Xu and J. Ye, J. Mater.
Published on 08 June 2016. Downloaded by Middle East Technical University (Orta Dogu Teknik U) on 8/21/2020 2:06:49 PM.
Chem. A, 2013, 1, 5766.
14 F. Zuo, L. Wang, T. Wu, Z. Zhang, D. Borchardt and P. Feng,
J. Am. Chem. Soc., 2010, 132, 11856–11857.
15 L. Liu, Y. Y. Peter, X. Chen, S. S. Mao and D. Shen, Phys. Rev.
Lett., 2013, 111, 065505.
16 S. Wendt, P. T. Sprunger, E. Lira, G. K. Madsen, Z. Li, J. O.
Hansen, J. Matthiesen, A. Blekinge-Rasmussen, E. Lægsgaard
and B. Hammer, Science, 2008, 320, 1755–1759.
17 A. Naldoni, M. Allieta, S. Santangelo, M. Marelli, F. Fabbri,
S. Cappelli, C. L. Bianchi, R. Psaro and V. Dal Santo,
J. Am. Chem. Soc., 2012, 134, 7600–7603.
18 Z. Wang, C. Yang, T. Lin, H. Yin, P. Chen, D. Wan, F. Xu,
F. Huang, J. Lin and X. Xie, Adv. Funct. Mater., 2013, 23,
5444–5450.
19 W. Zhou, W. Li, J.-Q. Wang, Y. Qu, Y. Yang, Y. Xie, K. Zhang,
L. Wang, H. Fu and D. Zhao, J. Am. Chem. Soc., 2014, 136,
9280–9283.
20 X. Yu, B. Kim and Y. K. Kim, ACS Catal., 2013, 3, 2479–2486.
21 V. E. Henrich and R. L. Kurtz, Phys. Rev. B: Condens. Matter
Mater. Phys., 1981, 23, 6280.
22 D. C. Hurum, A. G. Agrios, S. E. Crist, K. A. Gray, T. Rajh and
M. C. Thurnauer, J. Electron Spectrosc. Relat. Phenom., 2006,
150, 155–163.
23 D. S. Wang, Q. A. Chen, W. Li, C. B. Yu, Y. G. Zhou and
X. Zhang, J. Am. Chem. Soc., 2010, 132, 8909–8911.
24 N. Shi, X. Li, T. Fan, H. Zhou, J. Ding, D. Zhang and H. Zhu,
Energy Environ. Sci., 2011, 4, 172–180.
This journal is © The Royal Society of Chemistry 2016
View Article Online
Energy & Environmental Science
25 L. Christoph, Y. Zhe, Z. Igor and K. Bengt, Nano Lett., 2006,
6, 833–838.
26 V. Swamy, Phys. Rev. B: Condens. Matter Mater. Phys., 2008,
77, 195414.
27 A. C. Papageorgiou, N. S. Beglitis, C. L. Pang, G. Teobaldi,
G. Cabailh, Q. Chen, A. J. Fisher, W. A. Hofer and
G. Thornton, Proc. Natl. Acad. Sci. U. S. A., 2010, 107,
2391–2396.
28 A. Baldi, T. C. Narayan, A. L. Koh and J. A. Dionne,
Nat. Mater., 2014, 13, 1143–1148.
29 H. Okuyama, W. Siga, N. Takagi, M. Nishijima and T. Aruga,
Surf. Sci., 1998, 401, 344–354.
30 C. M. Wang, Z. Yang, S. Thevuthasan, J. Liu, D. R. Baer,
D. Choi, D. Wang, J. Zhang, L. V. Saraf and Z. Nie, Appl.
Phys. Lett., 2009, 94, 233116.
31 A. Naldoni, M. Allieta, S. Santangelo, M. Marelli, F. Fabbri,
S. Cappelli, C. L. Bianchi, R. Psaro and V. Dal Santo, J. Am.
Chem. Soc., 2012, 134, 7600–7603.
32 R. Egerton, Rep. Prog. Phys., 2008, 72, 016502.
33 G. Kyriakou, M. B. Boucher, A. D. Jewell, E. A. Lewis,
T. J. Lawton, A. E. Baber, H. L. Tierney, M. Flytzani-
Stephanopoulos and E. C. H. Sykes, Science, 2012, 335,
1209–1212.
34 F. Manchester, A. San-Martin and J. Pitre, J. Phase Equilib.,
1994, 15, 62–83.
35 P. Ratnasamy, D. Srinivas, C. Satyanarayana, P. Manikandan,
R. S. Kumaran, M. Sachin and V. N. Shetti, J. Catal., 2004, 221,
455–465.
36 S. Kuba, M. Che, R. K. Grasselli and H. Knozinger, J. Phys.
Chem. B, 2003, 107, 3459–3463.
Energy Environ. Sci., 2016, 9, 2410--2417 | 2417