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Hydrogenated TiO2 Nanocrystals: A Novel Microwave
Absorbing Material
Ting Xia, Chi Zhang, Nathan A. Oyler, and Xiaobo Chen*
Dipole rotation and ferromagnetic resonance are well-known
mechanisms normally responsible for microwave absorption
due to the alignment of the polar groups in the materials to
the electromagnetic field in the microwave field[1–3] or the
strongly interacting electron spins in the ferromagnet in the
ferromagnetic filler particles (e.g., iron or cobalt) dispersed
in a matrix.[1–3] TiO2 is not among the traditional microwave
absorbing material (MAM) candidates due to its poor response
in the microwave region. Here, we demonstrate that hydro-
genation successfully turns this inactive MAM into an exciting
MAM with an innovative collective-movement-of-interfacial-
dipole (CMID) mechanism. This study thus opens up new con-
cepts for MAM innovations, expands the applications of TiO2
and other oxide materials into new areas beyond photocatal-
ysis,[4–8] battery[5,9] and solar cells,[5,8–10] and will probably attract
the attention of materials scientists.
Gigahertz radar MAMs are very important in many civil (e.g.,
communications, noise reduction, signal and data protection)
and military (e.g., the stealth coating in B-2 bomber) applica-
tions.[11–18] Traditional candidates include ferroelectric ceramics
and carbonaceous materials.[3,11–18] Ferroelectric ceramics exam-
ples are ferrites and ferromagnetic materials,[11–15] barium and
lead zirconate titanate.[3] However, due to high reflection coef-
ficients at the interface with air, ceramic ferroelectrics cannot
be used as such.[3] Carbonaceous materials include carbonyl-
iron[17,18] and carbon nanotubes[11,16,18] with permittivity values
of 10–16 in the frequency range of 2–18 GHz[10] and concern of
flame resistance. Pure TiO2 is not among the traditional MAM
candidates, due to its poor response in the microwave gigahertz
region although it has a good static dielectric constant.[1,6]
Hydrogenation has recently emerged as an innovative
approach in effectively modifying the properties of materials,
and has shown great ability in TiO2 nanocrystals for intro-
ducing dramatic structural changes[7,19–21] and large improve-
ment in their optical,[5,7] electronic,[5,7] photocatalytic,[5,7]
lithium ion storage capability[22–24] and field emission.[25] As
we report here, hydrogenated TiO2 is an excellent MAM can-
didate benefiting from an innovative CMID mechanism which
induces the collective interfacial polarization amplified micro-
wave absorption (CIPAMA) in hydrogenated TiO2 nanocrystals,
distinct from the traditional dipole or ferromagnetic resonance
mechanisms. This CMID mechanism is based on the dramatic
T. Xia, C. Zhang, Prof. N. A. Oyler, Prof. X. Chen
Department of Chemistry
University of Missouri – Kansas City
Kansas City, Missouri 64110, USA
E-mail: chenxiaobo@umkc.edu
DOI: 10.1002/adma.201303088
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COMMUNICATION
property changes in the hydrogenated TiO2 nanocrystals caused
by the hydrogenation.
Here hydrogenation promoted the growth of pure TiO2
anatase nanocrystals and a phase transition into a mixture
of anatase and rutile phases at the temperature as low as
450 °C (Figure 1A).[20] Normally phase transition from anatase
to rutile TiO2 nanocrystals requires annealing at temperatures
above 600 °C.[8] The crystalline grain size was estimated with
the Scherrer equation from the XRD pattern:[21] 19.0 nm for
pure TiO2 nanocrystals, 45.0 nm for the anatase phase and
50.0 nm for the rutile phase in hydrogenated TiO2 nanocrys-
tals. Hydrogenation also induced amorphous phases as seen
from the broad photoluminescence background in the treated
TiO2 nanocrystals beyond the characteristic anatase Raman
features at around 142.8, 201.4, 399.1, 520.0, and 642.4 cm−1
(Figure 1B).[7,8] The disappeared Raman features and the
apparent XRD rutile features suggested rutile-anatase interior-
exterior structures of the hydrogenated TiO2 nanocrystals, as
Raman is more sensitive to the composition on the surface.[7]
The growth and surface amorphization from hydrogena-
tion were obvious from the transmission electron microscopy
(TEM) images and the fast Fourier transforms (FFT) results:
18 nm pure TiO2 nanocrystals (Figure 1C) with clearly-defined
lattice fringe edges (Figure 1D) and clear diffraction spots in
the FTT (Figure 1C) vs. 50 nm hydrogenated TiO2 nanocrystals
(Figure 1E) with an inner well-defined lattice fringe wrapped
with an outer 2-nm amorphous layer (Figure 1F) and a diffrac-
tion cloud around the central spot in the FTT (Figure 1E).[26,27]
The microwave absorption properties are evaluated with
the complex permittivity and permeability values: the real part
ε′ and μ′, related to the stored electrical and magnetic energy
within the medium, the imaginary part ε′′ and μ′′, related to the
dissipation (or loss) of electrical and magnetic energy, and their
ratios, the dielectric and magnetic dissipation factors tgδε =
ε′′/ε′ and tgδμ = μ′′/μ′, which provide a measure of how much
power is lost in a material versus how much is stored.[1–3,11–18]
We dispersed the nanocrystals in melting paraffin wax, and
cast the mixture into a ring for the microwave measure-
ments.[11] The anatase TiO2 nanocrystals/epoxy composites
displayed a relatively constant value of 6.1–6.5 for ε′ in the fre-
quency range of 1.0–18.0 GHz, while the hydrogenated TiO2
nanocrystals/epoxy composites showed much higher ε′ values
(Figure 2A). The ε′ decreased gradually from 25.7 at 1.0 GHz
to 17.4 at 14.50 GHz, then increased to 20.0 at 16.7 GHz, and
decreased to at 17.7 at 20.0 GHz. As the ε′ value of the epoxy
was 2.5 at X-band frequency,[11] the ε′ value of the hydrogen-
ated TiO2 nanocrystals was thus estimated to be about 4.3 times
as that of the pure TiO2 nanocrystals in the frequency range
of 1.0–18.0 GHz. Apparently, hydrogenated TiO2 nanocrystals
showed much higher efficiency in storing the electric energy
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o
o
A Hydrogenated TiO2
Pure TiO2
B
o

Intensity / a.u.

Intensity / a.u.
oo
o o o
oo
* oo o o
* * * * * *
Hydrogenated TiO2 nanocrystals
Pure TiO2 nanocrystals
100 200 300 400 500 600 700
o
o oo

20 30 40 50 60 70 80 500 1000 1500 2000 2500 3000

o -1
2Theta / Wavenumber / cm

Figure 1. Structural and morphologic properties. (A) XRD patterns, and (B) Raman scattering spectra of pure anatase and hydrogenated TiO2 nanocrys-
tals. (o) anatase phase, (*) rutile phase. TEM images of pure (C,D) and hydrogenated (E,F) TiO2 nanocrystals, with insets showing the FFT transforms.

inside, possibly due to they being more polarizable in the elec- As the epoxy has a ε′′ value of 0–0.02 at X-band frequency,[11]
tromagnetic field. Carbon nanotubes or Ni-coated, or Ag-filled thus hydrogenated TiO2 nanocrystals had 70.1 times higher
carbon nanotubes have shown permittivity value of 10–16 in ε′′ values as that of pure TiO2 nanocrystals in the frequency
the microwave range of 2–18 GHz.[11] Thus the high ε′ values range of 1.0–18.0 GHz. This suggests that hydrogenated TiO2
(17–25) of the hydrogenated TiO2 nanocrystals hereby dem- nanocrystals were more efficient in dissipating the electrical
onstrate their great potential as a new material for microwave energy under the electromagnetic field as well. Meanwhile,
absorption. after hydrogenation, the dielectric dissipation factor tgδε was
TiO2 nanocrystals/epoxy composites showed relatively improved over 15 times, on average, in the microwave region
constant ε′′ values of 0.03–0.3, in the frequency range of of 1.0–18.0 GHz (Figure S1A, Supporting Information),
1.0–18.0 GHz, but hydrogenated TiO2 nanocrystals/epoxy demonstrating that hydrogenated TiO2 nanocrystals were
composites had much higher ε′′ values in the same fre- more efficient in dissipating electrical energy than pure TiO2
quency range (Figure 2B). The ε′′ value first decreased gradu- nanocrystals.
ally from 5.9 at 1.0 GHz to 4.7 at 14.50 GHz, then increased Hydrogenation induced lower μ′ values (Figure 2C), or
to 10.6 at 17.50 GHz, and decreased to at 10.0 at 20.0 GHz. less susceptibility to the electromagnetic field, and higher

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24 A B
16
'
Hydrogenated TiO2
Pure TiO2
8 Hydrogenated TiO2
0
4 8 12 16
Frequency / GHz
1.1
C D
1.0
"
'
0.9
Pure TiO2
Hydrogenated TiO2
0.8
4 8 12 16
Frequency / GHz
Figure 2. Comparisons of microwave absorption performance. Frequency dependence of (A) the real part (ε′) and (B) the imaginary part (ε′′) of the
complex permittivity (ε), (C) the real part (μ′) and (D) the imaginary part (μ′′) of the complex permeability (μ), of pure anatase and hydrogenated
TiO2 nanocrystals.
μ′′ values in the low and high frequency ranges (1.0–5.7 and
16.4–20.0 GHz) but lower μ′′ values in the median frequency
range (5.7–16.4 GHz) (Figure 2D). The change of the mag-
netic dissipation factor tgδμ followed the same trend as μ′′
(Figure S1B). This suggested that the hydrogenated TiO2
nanocrystals were more efficient in dissipating magnetic energy
in the frequency regions, but less efficient in the median fre-
quency region.
Apparently, hydrogenation mainly induced the improvement
of the response of the electrical component in the microwave
region. To better understand this phenomenon, we conducted
static-state and low-frequency electrical impedance measure-
ments, as the dielectric constant depends on the frequency. The
results (Figure S2) suggested that hydrogenated TiO2 nanocrys-
tals show higher electrical resistivity than pure TiO2 nanocrys-
tals at static state or lower-frequency (<700 mHz) modulated
electric field, and lower electrical resistivity at higher-frequency
(>700 mHz). Apparently hydrogenated TiO2 nanocrystals
responded more to the modulated electric field at higher fre-
quencies, consistent with their higher microwave response.
Dipole rotation is the mechanism normally responsible for
microwave absorption due to the alignment of the polar groups
in the materials to the electromagnetic field in the microwave
field,[1–3,11,15] besides the ferromagnetic resonance caused by
strongly interacting electron spins in the ferromagnet in the
ferromagnetic filler particles (e.g., iron or cobalt) dispersed
in a matrix for microwave absorption.[1–3,12–15] Thus, hydroxyl
(OH) groups, Ti3+ ions or oxygen vacancies are the first species
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COMMUNICATION
10
8
6
"
4
2 Pure TiO2
0
4 8 12 16
Frequency / GHz
0.6
0.4 Pure TiO2
Hydrogenated TiO2
0.2
0.0
4 8 12 16
Frequency / GHz
suspected to be responsible for the improvement of hydrogen-
ated TiO2 nanocrystals, as they are either the polar groups or
they can induce polarization. The X-ray photoelectron spectro-
scopy (XPS) survey spectra were similar for both pure and
hydrogenated TiO2 nanocrystals (Figure 3A), the O 1s core-
level XPS spectra displayed the hydrogenated TiO2 nanocrystals
had less OH content from the smaller OH band at 532.5 eV
(Figure 3B) besides the lattice O2− peak around 530.0 eV,[7,8]
and the Ti2p XPS showed almost identical pattern from lattice
Ti4+ ions with peaks centering at 458.7, 464.3, and 472.2 eV
(Figure 3C).[7,8,28]
The lower OH concentration in hydrogenated TiO2 nanocrys-
tals was confirmed with Fourier transform infrared spec-
troscopy (FTIR) results (Figure 3D) with no OH absorption
bands, compared to the obvious OH bands in the pure TiO2
nanocrystals: a smaller and narrower band around 1640 cm−1
from O–H bending of molecularly physisorbed water and a
larger and broader band around 3250 cm−1 due to the stretch
region of the surface hydroxyl groups and molecularly chem-
isorbed water.[29,30] The lack of OH in the hydrogenated TiO2
nanocrystals was confirmed further with nuclear magnetic
resonance spectroscopy (NMR) results (Figure 3E) with much
smaller or barely seen peaks, compared to the obvious large
and broad peak in the pure TiO2 nanocrystals. One argument
for this could be that, the detected NMR signals could have
been reduced by the microwave absorption properties of hydro-
genated TiO2, as imagined from the increased electrical con-
ductivity of the hydrogenated TiO2 nanocrystals in the lower
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2-
O
A O1s XPS B
Intensity / a.u.

Intensity / a.u.
O
OH
Ti

C from atmosphere

O 1s

Pure TiO2 nanocrystals Pure TiO2

Hydrogenated TiO2 nanocrystals Hydrogenated TiO2

1000 800 600 400 200 0 538 534 530 526

Binding Energy / eV Binding Energy / eV

4+

Ti2p XPS
Ti
C D

Reflectance / %
Intensity / a.u.

OH OH

4+
Ti
4+
Ti

Ti 2p3/2, sat Ti 2p1/2

Ti 2p3/2 Pure TiO2
Pure TiO2 Hydrogenated TiO2
Hydrogenated TiO2
476 471 466 461 456 451 4000 3000 2000 1000
-1
Binding Energy / eV Wavenumber / cm

OH
E F
Intensity / a.u.

Intensity / a.u.

Pure TiO2 nanocrystals

Pure TiO2 Hydrogenated TiO2 nanocrystals
Hydrogenated TiO2

30 20 10 0 -10 -20 1.96 2.03 2.10

Chemical Shift / ppm g factor
Figure 3. Examination of polar groups, Ti3+ ion and oxygen vacany defects. (A) Survey, (B) O 1s and (C) Ti 2p core-level XPS, (D) FTIR, (E) NMR and
(F) ESR spectra of pure anatase and hydrogenated TiO2 nanocrystals.

frequencies shown in the impedance spectra from 10 Hz to the lack of Ti3+ or oxygen vacancy in the hydrogenated TiO2
100 kHz (Figures S2C and S2D) and in the higher frequencies nanocrystals. So, OH, Ti3+ or oxygen vacancy was unlikely to
in the microwave from 1 GHz to 18 GHz (Figures 2A and 2B). be responsible for the excellent microwave absorption of the
However, this suspicion seems unlikely since the probe tuning hydrogenated TiO2 nanocrystals.
required for the two TiO2 samples was essentially identical. We propose here that the enhanced microwave absorption
As XPS is a surface-probe technique with the information of the hydrogenated TiO2 nanocrystals is due to the CMID in
depth of 1–2 nm, we further used electron spin resonance the crystalline/disordered and anatase/rutile interfaces, which
spectroscopy (ESR) to see if Ti3+ or oxygen vacancy was respon- induces the CIPAMA as illustrated in Figure 4. Interfacial
sible for the microwave absorption for the hydrogenated TiO2 polarization occurs whenever there is a buildup of a charge
nanocrystals, as the information depth of the ESR can be up to at a boundary between two regions or materials.[1–3,15] Crystal
a few centimeters. Both hydrogenated and pure TiO2 nanocrys- defects, such as dislocations or grain boundaries, electronic
tals did not show observable signals (Figure 3F): suggesting defects or phase boundaries all can contribute to the interfacial

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Figure 4. Proposed mechanism of collective interfacial polarization
amplified microwave absorption (CIPAMA). The collective movements of
interfacial dipoles (CMID) at the anatase/rutile and crystalline/disordered
interfaces amplify the response to the incoming electromagnetic field and
thus induce enhanced microwave absorption performance. The positions
of the electronic band structure of the disordered layer are assumed to lie
between those of anatase and rutile phases. CBE: conduction band edge,
VBE: valence band edge.
polarization.[1–3,15] Charge transfers and accumulation are
expected on the rutile/anatase and crystalline/disordered inter-
faces as shown Figure 4, as rutile and anatase TiO2 have dif-
ferent electronic band structures and dielectric constants, inter-
facial band bending, and that hydrogenated TiO2 nanocrystals
have been shown previous to possess p-type characteristics,[7]
and they also displayed some structural characteristics between
anatase and rutile.[19] The assembled movements of collective
interfacial dipoles at these interfaces amplify the response to
the incoming electromagnetic field and thus induce enhanced
microwave absorption performance. To verify this hypoth-
esis, we measured the microwave absorption properties of
pure rutile TiO2 nanocrystals with size around 55 nanom-
eters (Figure S3) and a mechanically mixed anatase/rutile
TiO2 nanocrystal mixture (anatase 92%, rutile 8%, Figure S4)
with similar composition and sizes to the hydrogenated TiO2
nanocrystals. Pure rutile TiO2 nanocrystals showed similar
microwave absorption (Figures S5-S10) as pure anatase TiO2
nanocrystals. The mechanically mixed anatase/rutile mixture
displayed higher ε′ values (Figure S5) than pure anatase or
rutile TiO2 due to increased anatase/rutile interface, but much
lower values than the hydrogenated TiO2 nanocrystals, which
apparently had many more interfacial junctions on the nano-
meter scale not only due to the larger anatase/rutile interface
but also the much larger crystalline/disorder interfacial area.
The slightly increased microwave absorption of mechani-
cally mixed anatase/rutile mixture over that of pure anatase or
rutile also hinted that the main contribution of the microwave
absorption of the hydrogenated TiO2 nanocrystals was from
the crystalline/disorder interface after the hydrogenation reac-
tion, as both samples had similar compositions (anatase 92%,
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rutile 8%). As the anatase/rutile ratio may affect the interfacial
polarization effect, i.e. on the anatase/rutile interfaces, we are
currently conducting comprehensive research to further reveal
the detailed relationship between the microwave absorption
performance and the anatase/rutile ratio by varying the hydro-
genation treatment time or temperature as well as the relative
importance of the anatase/rutile interface and the crystalline/
disordered interface on the microwave absorption of hydrogen-
ated TiO2 nanocrystals.
In summary, we have shown that hydrogenation of TiO2
nanocrystals can induce excellent microwave absorption perfor-
mance, due to the CMID on the nanometer scale. The CMID
and the induced CIPAMA will inspire further developments of
other exciting MAM materials. And hydrogenation expands the
applications of TiO2 nanocrystals into new areas beyond photo-
catalysis, battery, and solar cells.
Experimental Section
Pure anatase and hydrogenated TiO2 nanocrystals were prepared
as follows. Briefly, we prepared crystalline TiO2 nanoparticles with
a precursor solution consisting of titanium butoxide, ethanol and
deionized water. The solution was maintained at room temperature for
24 hours under stirring and then dried at 120 °C overnight. The dried
white powders were calcinated in air at 500 °C for 2 hours in flowed
air to enhance their crystallinity. The pure TiO2 nanocrystals were then
placed in a sealed sample chamber under vacuum for 1 hour and then
hydrogenated in a 5.0 bar H2 atmosphere at about 450 °C for 4 hours to
obtain the hydrogenated TiO2 nanocrystals.
The XRD was performed using a Rigaku Miniflex XRD machine with
Cu Kα as the X-ray sources (wavelength = 1.5418 Å). The Raman spectra
were collected on an EZRaman-N benchtop Raman spectrometer with
the excitation wavelength of 785 nm. The spectrum range was from
100 cm−1 to 3100 cm−1. The spectrum collection time was 4 seconds
and was averaged over three measurements to improve the signal-
to-noise ratio. Both Raman spectra were normalized to the Raman peak
at 142.8 cm−1. The TEM study was performed on a FEI Tecnai F200 TEM.
The electron accelerating voltage was at 200 kV. A small amount of
sample was dispersed in water, dropped onto a thin holey carbon film,
and dried overnight before TEM measurement.
The complex permittivity and permeability of pure and hydrogenated
TiO2 nanocrystals were measured at the frequency range of
2–18 GHz using a HP8722ES network analyzer. The TiO2 nanocrystals
were dispersed in melting paraffin wax, and the mixture was cast into
a ring mold with thickness of 2.0 mm, inner diameter of 3 mm, and
outer diameter of 7 mm. The content of TiO2 nanocrystals was 60 wt%,
and the testing was performed at 0 °C. For comparison, the complex
permittivity and permeability of pure rutile TiO2 (from Alfa Aesar) and
a mechanically mixed anatase/rutile TiO2 nanocrystals mixture with
similar composition (anatase 92%, rutile 8%) were measured under
the same conditions. The anatase/rutile TiO2 nanocrystals mixture was
obtained by manually grinding suitable amount of rutile and anatase
TiO2 nanocrystals together.
The DC and frequency-dependent resistivity of the pure and
hydrogenated TiO2 nanocrystals were measured with a Biologic
potentiostat/EIS instrument. The samples were pressed into small
pellets with diameter of 10.0 mm, and thickness of 1.0 mm, using an
IR hand press. The pellets were sandwiched between two stainless
steel disks for the resistivity measurements. The frequency-dependent
resistivity was measured between 200 kHz and 100 mHz. The voltage
modulation applied was 500 mV.
The surface chemical bonding and valence band information of the
samples was obtained with XPS on a PHI 5400 XPS system equipped
with a conventional (non-monochromatic) Al anode X-ray source with
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Kα radiation. Small amounts of TiO2 nanocrystals were pressed onto
conductive carbon tape for XPS measurements. The binding energies
from the samples were calibrated, with respect to the C 1s peak, from
the carbon tape at 284.6 eV. The FTIR spectra were collected using a
Thermo-Nicolet iS10 FT-IR spectrometer with an attenuated total
reflectance (ATR) unit. TiO2 nanocrystals were pressed onto the ZnSe
crystal of the ATR unit, and the measurement were performed in air at
room temperature.
All 1H NMR experiments were performed on an 8.45 tesla Oxford
magnet with a three channel Tecmag Apollo NMR console, using a
home-built, doubly tuned, MAS solid-state NMR probe with a 3.2 mm
stator assembly from Revolution NMR. The magic angle spinning
rate was 8 kHz, the proton excitation pulse during the Bloch decay
experiment was ≈50 kHz, and each spectrum was acquired with
256 scans. The spectra were externally referenced to adamantane. NMR
spectra were acquired of the both samples as well as an empty rotor to
measure the hydrogen present. The contribution of the empty rotor was
then subtracted to obtain the information from the samples which was
further scaled by the mass of samples to give a quantitatively accurate
spectrum. The ESR spectra were collected on a Benchtop Micro-ESRTM
machine, at a microwave frequency of 9.70 GHz at room temperature
without light irradiation. The ESR data were calibrated in relation
to g = 2.0066 of 2,2,6,6-tetramethyl-4-hydroxylpiperidine-1-oxyl. The
scanning time was 30 s per sweep, and the spectrum was averaged after
30 sweeps. Quartz ESR tubes with an inner diameter of about 5.8 mm
were used.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
X.C. thanks the support from College of Arts and Sciences, University
of Missouri – Kansas City (UMKC), University of Missouri Research
Board and the generous gift from Dow Kokam. X. C. thanks the helpful
discussion and help on the measurement of ESR spectra from Professor
Thomas C. Sandreczki at UMKC, Department of Chemistry and
Mr. James White from Active Spectrum, Inc.
Received: July 6, 2013
Published online: September 17, 2013
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