Communication

pubs.acs.org/JACS

Large-Scale Synthesis of Transition-Metal-Doped TiO2 Nanowires

with Controllable Overpotential
Bin Liu,†,‡ Hao Ming Chen,†,‡ Chong Liu,†,⊥ Sean C. Andrews,†,⊥ Chris Hahn,† and Peidong Yang*,†,§,⊥
†
Department of Chemistry and §Department of Materials Science and Engineering, University of California, Berkeley, California
94720, United States
⊥
Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
*
S Supporting Information

significantly improves the nanowire yield while maintaining

ABSTRACT: Practical implementation of one-dimen- high crystal quality and illustrates the feasibility of large-scale
sional semiconductors into devices capable of exploiting production of semiconductor nanowires. We additionally
their novel properties is often hindered by low product demonstrate that this method allows for incorporation of
yields, poor material quality, high production cost, or various transition-metal (TM) dopants into the TiO2 lattice by
overall lack of synthetic control. Here, we show that a introducing the corresponding TM salt as a dopant source. The
molten-salt flux scheme can be used to synthesize large homogeneity of the dopant speciation exhibits simultaneous
quantities of high-quality, single-crystalline TiO2 nano- benefits in both the optical properties and photocatalytic
wires with controllable dimensions. Furthermore, in situ response of the TiO2 nanowires.
dopant incorporation of various transition metals allows In a typical synthesis, the present molten-salt flux method
for the tuning of optical, electrical, and catalytic properties. involves a blended mixture of TiO2 nanoparticles, NaCl, and
With this combination of control, robustness, and Na2HPO4, which is heated above the melting point of the salt
scalability, the molten-salt flux scheme can provide high- mixture to achieve a large-scale synthesis of TiO2 nanowires
quality TiO2 nanowires to satisfy a broad range of with a yield of about 99% (Figure 1a). X-ray diffraction (XRD)
application needs from photovoltaics to photocatalysis. collected under a synchrotron radiation light source (λ =
0.7749 Å) shows the absence of any peaks other than that for
the tetragonal rutile phase of TiO2 (Figure 1b). Scanning

O ver the past two decades, tremendous effort has been

directed toward the synthesis of one-dimensional (1D)
materials, whose unique chemical/physical properties can
electron microscopy (SEM) confirms the 1D nanowire
morphology and reveals both uniform diameters of 100 nm
and variable lengths from 5 to 40 μm, resulting in exceptionally
potentially be exploited in various fields, including optoelec- large aspect ratios of up to 400 (Figure 1c,d). A representative
tronic, photovoltaic, electrochemical, and electromechanical transmission electron microscopy (TEM) image and diffraction
devices.1−9 Many synthetic methods have been developed for pattern (Figure 1e) confirm that the nanowires are grown along
growing 1D semiconductors, including vapor−liquid−solid,10,11 the [001] direction and bounded by four {100} facets on the
vapor−solid,12 solution−liquid−solid,13 and hydrothermal/ side wall, as evidenced by the sharp selected area electron
solvothermal techniques.14−16 However, these methods typi- diffraction (SAED) patterns examined along the [100] zone
cally trade either yield for quality or vice versa. Since the future axis. The end tips, however, consist of four {011} facets focused
of 1D semiconductor nanotechnology depends on the balance to a point, where the tip angle matches nearly to the theoretical
between materials yield and subsequent device performance,17 value of 113.88° (along the [100] zone axis). Examination of
development of synthetic routes capable of simultaneously individual nanowire with high-resolution (HR) TEM shows
satisfying the needs of high yield, large-scale production, and that they are completely crystalline along their entire lengths
high material quality continues to require great ingenuity. (Figure 1f). Lattice fringes with interplanar spacings d100 = 4.5
Molten-salt flux synthesis is accomplished by utilizing a mixture ± 0.2 Å and d001 = 2.9 ± 0.1 Å are measured, consistent with
of molten salts as a highly reactive medium, where there is facile the rutile crystal structure.
diffusion in the liquid state. Eutectic salt compositions are To investigate the nanowire formation mechanism, aliquoted
commonly utilized for maximal reactivity at their respective products were examined ex situ. When the reaction was heated
minimal required temperature, where the mobility of ions in above 600 °C for more than 2 min, the percentage of anatase
these molten salts is approximately 1010 times higher than in diffraction in the product was reduced compared to that in the
the solid state.18 Once the product material is less soluble than unheated mixture of P25 nanoparticles, NaCl, and Na2HPO4
the reactants in the salt solution, various salt mixtures can be (Supporting Information, Figure S1 and S2). Concurrently, a
tailored to the reactants and subsequent products of choice.19,20 new phase of monoclinic tetrasodium titanium nonaoxodiphos-
Herein, we report a molten-salt route to synthesize large phate (Na4TiP2O9) was observed.21 After 8 min of heating at
quantities of high-quality, single-crystalline TiO2 nanowires. In 825 °C, the formation of the Na4TiP2O9 intermediate plays a
this technique, commercially available TiO2 nanoparticles and
common salt mixtures are chosen as the raw material and Received: April 18, 2013
reaction medium, respectively. This molten-salt flux scheme Published: July 1, 2013

© 2013 American Chemical Society 9995 dx.doi.org/10.1021/ja403761s | J. Am. Chem. Soc. 2013, 135, 9995−9998
Journal of the American Chemical Society Communication

dopants. Historically, a variety of TMs have been explored as

dopants in modifying the electronic structure of TiO2 to
improve its visible-light photocatalytic activity.25−28 Because of
the interaction between the t2g state of TM dopants and Ti
atoms, TM doping could create an additionally occupied state
in the bandgap of TiO2.25 Here, through the introduction of
TM dopants such as V, Cr, Mn, Fe, Co, Nb, Mo, and Rh during
the molten-salt synthesis, the as-prepared 2% TM-doped TiO2
nanowires (Figure S5) exhibit a variety of colors, departing
from the white color of the undoped product. For instance, Rh-
doped samples show a deep brown color resulting from strong
absorption in the visible region (Figure 2). Consequently, the

Figure 1. (a) Photograph of rutile TiO2 nanowires. (b) XRD pattern

of as-prepared TiO2 nanowires. (c,d) SEM images of rutile TiO2
nanowires. (e) TEM image of a single TiO2 nanowire examined along
the [100] zone axis; insets show the corresponding SAED pattern and
tip angle. (f) HRTEM image of a single TiO2 nanowire.
Figure 2. Photograph of various TM-doped TiO2 nanowires and UV/
critical role for rutile nanowire growth, as evidenced by the vis spectra of various TM-doped TiO2 nanowires.
necessity of its formation to produce TiO2 nanowires. Attempts
using only NaCl or Na2HPO4 resulted in only rutile TiO2 light absorption edge of TM-doped TiO2 nanowires extends
particles (Figure S3). A mixture of NaCl (80 wt%) and from ultraviolet to visible, increasing the overlap between light
Na2HPO4 (20 wt%) achieved the lowest eutectic temperature absorption and the solar spectrum, thereby widening the range
and is shown to be the eutectic composition with the present of sunlight that is able to be captured to generate carriers for
reaction temperature (825 °C) according to the phase photocatalytic reactions.
diagram,19 indicating that the molten environment maximizes Since the photocatalytic properties of TM-doped TiO2
the solubility and diffusivity of the reactant. nanowires can be strongly affected by the dopant speciation
In addition to the influence of the salt mixture, variations of and position, XRD via synchrotron radiation was used to
the reactant phase yielded controllable differences in the confirm that only the tetragonal rutile phase of TiO2 exists in
products. Anatase, the metastable phase of TiO2, readily reacts the doped samples (Figure 3a). This indicates that the optical
with Na4P2O7 to form Na4TiP2O9 at temperatures above 600 variation can be attributed to the metal doping rather than the
°C,22 while the thermodynamically stable rutile phase does not formation of undesired phases that may have been created as a
form this intermediate under the present condition. Con- result of adding dopant precursors to the reaction mixture. In
sequently, pure anatase particles could be used as the titanium order to probe short-range structure, extended X-ray absorption
source to synthesize rutile nanowires as well (Figure S4); fine structure (EXAFS) spectra were collected for specific
however, rutile nanowires synthesized from pure anatase nearest-neighbor interatomic distances and coordination
particles have broader size distributions, suggesting that the numbers (CNs).29 Rutile has a tetragonal crystal structure, in
synthesis of rutile nanowires is optimally performed through which each Ti atom is surrounded by six O atoms in octahedral
P25 nanoparticles containing both anatase and rutile phases, coordination, with two distinct bond lengths of 1.947 and 1.981
wherein they serve dual roles as both rutile seeds and TiO2 Å (Figure 3b). Correspondingly, three major peaks were
nutrients. Anisotropic crystal growth of nanowires along the present in the Fourier transforms (FTs) of the EXAFS data
rutile c-axis results from lower solid−liquid interfacial energy (Figure 3c). The first peak, at ∼1.8 Å, of the FT EXAFS signal
and free energy minimization for growth occurring parallel to (first shell) obtained after phase correction is due to both
the [001] direction.23 The (011) facets observed at the tips of families of O atoms. The second peak, at ∼2.7 Å, of the FT is
the nanowires work in concert with the (100) facet along the assigned to single scattering by Ti−Ti atoms occupying the
nanowire length to minimize the total surface energy, resulting centers of contiguous rectangular prisms (second shell), while
in the formation of rutile nanowires with rectangular cross the third peak, at ∼3.4 Å, is in part to the eight Ti atoms
sections.24 occupying the vertices of the prism and in part to multiple
In addition to the large yield of single-crystalline nanowires, scattering contributions from both Ti and O atoms (third
this synthetic scheme also allows for the introduction of TM shell). The second shell exhibits a significant change in both
9996 dx.doi.org/10.1021/ja403761s | J. Am. Chem. Soc. 2013, 135, 9995−9998
Journal of the American Chemical Society Communication

Figure 4. (a) Mott−Schottky plot of a TiO2 and 2% Nb-TiO2

nanowire electrode measured at 500 Hz. (b) Overpotential measure-
ment for OER using FTO and TiO2 nanowire with/without TM
doping of electrodes in basic solutions. Dashed vertical lines represent
the thermodynamic redox potential for water oxidation at pH ∼13.6.

electron charge, ε is the rutile TiO2 dielectric constant (ε =

86),30 εo is the vacuum permittivity, and Nd is the donor
density.31 The positive slope indicates n-type behavior of the
rutile nanowires. The low carrier density of the undoped
sample reflects the high crystalline quality of the rutile
nanowires, which is a result of the high temperature used in
the molten-salt synthesis.
Figure 3. (a) XRD patterns of TM-doped TiO2 nanowires, showing Dopant incorporation not only allows for flexibility to tune
that there were no impurities forming in various dopants samples. (b) the carrier concentration of TiO2 but also beneficially affects its
Rutile structure of TiO2 and scattering shell modes around the Ti photocatalytic performance. It is well-known that TiO2 can be
atom. (c) FT EXAFS spectra of various TM-doped samples. (d) used as a photocatalyst for the photoelectrolysis of water.32
HRTEM images of the rutile TiO2 nanowires doped with Mn, Nb, and However, the large overpotential for the oxygen evolution
Rh (scale bar, 2 nm).
reaction (OER) to occur commonly limits its performance.
However, the introduction of TM dopants uniformly into the
position and shape in various TM doping, revealing that the TiO2 lattice causes substantial decreases in the overpotential
TM atoms substitute for Ti atoms at the same site around Ti (Figure 4b), where the overpotentials are compared in a
atoms. Since the first shell was due to a single scattering of O specific current density of 0.5 mA/cm2. Since the OER
atoms, and several multiple scatterings were involved in the overpotential is affected by the binding energy with
third shell, these two shells give no additional information intermediates such as O*, HO*, and HOO*, TM dopants
about the dopant position. Therefore, only the second shell was can lead to lower overpotentials due to stronger interactions of
refined to extract quantitative structural parameters (Table S1). the adsorbed species on the surface.33 We obtained an
The Ti−Ti contribution at a distance of 3.01 Å for rutile TiO2 overpotential of 0.488 V on 2% Mn-doped TiO2 nanowires,
nanowires and the CN around 1.93 is consistent with the bulk which represents a ∼28% decrease in overpotential relative to
value for rutile TiO2 (JCPDS file no. 88-1175). With regard to that of pristine rutile TiO2 (Table 1), indicating that TM
the TM doping, considerable contributions from the single substitutions on TiO2 crystal are able to alter the adsorption
scattering of TMs around Ti atoms were present in various energy of reaction intermediates for OER in spite of the low
cases of doped TiO2 samples, revealing the TM atoms quantity of dopant. Several theoretical predictions of over-
significantly exist around absorbing Ti atoms. Although the potentials are listed in Table 1 for comparison, in which 6.25%
CN for the Ti−TM path cannot precisely reflect the doping Mn doped on a rutile TiO2 single crystal exhibited a 48%
amount in rutile crystal due to the low concentration of decrease in overpotential. While this prediction is greater than
dopants (2%), this result still demonstrates the effectiveness of
doping with TM in the present molten-salt method. HRTEM Table 1. Experimental Overpotential Associated with OER
images of TM-doped TiO2 nanowires further demonstrate that on TM-Doped TiO2 Nanowires and Theoretical Calculation
neither crystal defects nor other phases can be observed (Figure from TM-Doped Rutile TiO2 Single Crystal
3d). Furthermore, this synthetic route enables doping to occur
before the subsurface layer begins to suffer from phase overpotential (V)
transformation and degradation, which is a common problem
sample, 2% dopant exptl, at 0.5 mA/cm2 calcd, 6.25% dopant32
with diffusion-based, post-growth methods. In situ dopant
incorporation allows for homogeneous dopant distributions, FTO 0.836 −
which can exhibit higher charge carrier mobility and higher TiO2 0.681 1.3
visible-light absorbance than those of surface doping.25 V-TiO2 0.529 −
To examine the transport and photoelectrochemical proper- Cr-TiO2 0.623 −
ties, nanowire electrodes were fabricated by drop-casting Mn-TiO2 0.488 0.69
nanowires onto FTO substrates. From the slopes of the Fe-TiO2 0.644 −
Mott−Schottky plots (Figures 4a and S6), carrier densities of Co-TiO2 0.586 −
undoped and 2% Nb-doped TiO2 nanowires were estimated to Nb-TiO2 0.578 0.76
be ∼1015 and ∼1021 cm−3, respectively, using the following Mo-TiO2 0.514 0.74
relation: Nd = (2/eoεεo)[d(1/C2)/dV]−1, where eo is the Rh-TiO2 0.539 −

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Journal of the American Chemical Society Communication

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The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This work was supported by the Director, Office of Science,
Office of Basic Energy Sciences, Materials Sciences and
Engineering Division, U.S. Department of Energy under
Contract No. DE-AC02-05CH11231.

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