Journal of Colloid and Interface Science 392 (2013) 463464

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Journal of Colloid and Interface Science

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Short Communication

Titanium dioxide nanospheres with wide spectral absorption prepared by

low-voltage plasma electrolysis
Zhan Wu, Zhi-Kun Zhang, Deng-Zhu Guo
Key Laboratory for the Physics and Chemistry of Nanodevices, Department of Electronics, Peking University, Beijing 100871, Peoples Republic of China

a r t i c l e

i n f o

Article history:
Received 28 February 2012
Accepted 9 October 2012
Available online 22 October 2012
Keywords:
TiO2
Nanosphere
Optical absorption
Plasma electrolysis

a b s t r a c t
TiO2 nanospheres with diameters mostly in the range of 20200 nm are prepared by using cathodic
plasma electrolysis at low voltage of 70 V. It is found that the low voltage could efciently depress the
particle sizes and their distribution, and result in more anatase phases. The nanospheres have an excellent optical absorption from 240 nm to 2600 nm.
2012 Elsevier Inc. All rights reserved.

TiO2 nanomaterials are important in solar energy harvesting

and pollutant photodegradation [15]. But the wide band gap connes their optical absorption within ultraviolet (UV) region. In order to expand its absorption into visible region, many efforts have
been done by chemical doping [13] and surface sensitization [6
8]. These strategies have been proven to be effective in enhancing
the visible absorption. Nevertheless, more effective and costefcient strategies are still highly expected to expand the optical
absorption of TiO2 itself into the full solar spectrum.
Oxygen vacancies in metal oxides are known to induce electronic states within the band gap and result in absorption of low
energy photons [1,2,9,10]. The coexistence of multiphases of TiO2
could also expand the optical absorption [11]. We recently synthesized TiO2 nano-/micro-spheres by using cathodic plasma electrolysis, which generates abundant oxygen vacancies in TiO2 and
results in an excellent absorption from 240 nm to 2600 nm [12].
However, the diametric distribution of the particles is too wide
from nanometers to tens of micrometers, limiting their applications. Here we will focus on the preparation of TiO2 nanospheres
by using low-voltage plasma electrolysis.
The preparation of the TiO2 nanospheres was performed using a
plasma electrolysis technique as described in Ref. [12]. Here we
added two steps to improve the diametric distribution of the particles. Firstly, the Ti wire was electropolished in a solution of perchloric acid, n-butyl alcohol, and ethanol (volume ratio 1:6:9)
under 20 V DC potential, and then used as the cathode. Secondly,
the electrolyte (3 M NH4NO3 aqueous solution) for the plasma
Corresponding author. Fax: +86 10 62765112.
E-mail address: guodz@pku.edu.cn (D.-Z. Guo).
0021-9797/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.10.016

electrolysis was heated to 70 C, so that the voltage for plasma

ignition was lowered to 70 V (while room temperature ignition
requires 90 V). During the plasma electrolysis process, the solution
gradually became turbid, and the particles in the suspension were
then puried for characterization.
At the beginning, we found that there are a few big particles as
large as tens micrometers in the SEM observation. We supposed
that they were formed due to the locally enhanced Joule heating
at surface roughness. The tips of the surface roughness were
melted off and then oxidized to form big particles. It is found that
adding electropolishing step can effectively depress the big particles. It is also found that lowering voltage can dramatically improve the diametric distribution of particles. Shown in Fig. 1a
and b are typical SEM images of the particles prepared at 90 V
and 70 V, respectively. Spheres with diameter of several micrometers are obvious in Fig. 1a, but in Fig. 1b, the particle sizes and their
distribution are highly depressed (mostly in 20200 nm).
Two XRD patterns are shown in Fig. 2, in which the upper and
bottom spectra were obtained from the nanospheres (70 V) and
the nano-/micro-spheres (90 V), respectively. In both cases, three
phases of TiO2, i.e., rutile, anatase and oxygen-decient phases,
can be identied. The diffraction peaks are labeled according to
their crystal indices. A close comparison can nd some differences
between the two cases. Firstly, the anatase (1 0 1) peak in the upper
spectrum is stronger than the rutile (1 1 0) peak, implying more
anatase phase has been formed during low voltage plasma electrolysis. On the contrary, in the bottom spectrum the rutile (1 1 0) peak
is stronger than the anatase (1 0 1) peak, meaning the existence of
more rutile phase. Secondly, broadened peaks in the upper spectrum imply that most particles are very small, according to

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Z. Wu et al. / Journal of Colloid and Interface Science 392 (2013) 463464

Fig. 1. SEM images of TiO2 (a) nano-/micro-spheres synthesized at 90 V and (b) nanospheres synthesized at 70 V.

Fig. 2. XRD spectra of the TiO2 spheres, the upper and bottom curves are for
samples synthesized at 70 V and 90 V, respectively.

Fig. 3. Optical absorption spectrum of TiO2 nanospheres compared with that of

commercial P25.

Scherrer equation. This is in good agreement with the SEM observation. The oxygen-decient phases can be assigned to Ti10O19,
Ti5O9 or Ti3O5, etc., in which some oxygen atoms are absent comparing with stoichiometric TiO2. These phases were formed due to
the insufcient oxidization during the plasma electrolysis.
The optical absorption spectrum of the as-prepared TiO2 nanospheres was measured in the wavelength range between 240 nm
and 2600 nm (Fig. 3). For comparison, the absorption of Degussa
P25 was also measured in the same condition. One can see that
the P25 only absorbs photons within a wavelength below
400 nm, while the synthesized TiO2 nanospheres exhibit a strong
absorption in the full wavelength range, similar to the nano-/micro-spheres reported previously [12]. The insets in Fig. 3 are the
digital images showing the bright white color of P25 and black color of TiO2 nanospheres, respectively, in good agreement with the
optical absorption measurement. The black color comes from the
excellent wide-spectral absorption, which originates from the oxygen vacancies-mediated defect states within the band gap of TiO2,
as in our previous report [12].
In summary, TiO2 nanospheres are synthesized via plasma electrolysis at a low voltage of 70 V. The diametric distribution and
phase composition have been changed due to the improvement
of synthesis process, while the wide spectral absorption is retained.

The oxygen vacancies-mediated defect states within the band gap

of TiO2 are supposed to be the mechanism.
Acknowledgment
This work was nancially supported by the Natural Science
Foundation of China (Grant No. 60971002).
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