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Inorganic Chemistry Communications 91 (2018) 1–4

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Inorganic Chemistry Communications

journal homepage: www.elsevier.com/locate/inoche

Short communication

Steerable light-driven TiO2-Fe Janus micromotor


Qing-long Wang, Chun Wang, Ren-feng Dong ⁎, Qi-qi Pang, Yue-peng Cai ⁎
School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China

a r t i c l e i n f o a b s t r a c t

Article history: In order to reduce the cost and simplify the fabrication process of light-driven micro/nanomotors and, we pre-
Received 26 January 2018 pared TiO2-Fe Janus micromotors based on economic metal Fe and traditional photocatalyst TiO2 which have at-
Received in revised form 21 February 2018 tractive photocatalytic propulsion and efficient direction control. The Janus structure and the materials of TiO2-Fe
Accepted 25 February 2018
micromotors were characterized and confirmed by a scanning electron microscope, an Energy Dispersive Spec-
Available online 27 February 2018
trometer and an X-ray diffraction system. In addition, we systematically studied the effects of fuel concentration
Keywords:
and light intensity on the motor motion, the motor speed increasing with the enhancement of fuel concentration
Janus micromotor or light intensity. Finally, we investigated the direction control of such micromtors under an external magnetic
Light-driven field. The direction can be efficiently controlled by adjusting the direction of magnetic field.
Self-electrophoresis © 2018 Elsevier B.V. All rights reserved.
Direction control

Micro/nanomotors are at the forefront of the nanotechnology field in on the other hand, in order to control the moving direction of micro/
the 21st century [1,2]. The micro/nanomotor refers to motion controlled nanomotor, an extra magnetic layer [3] needs to be modified on it to re-
micro/nano-device at the micro/nanoscale which can perform different alize the direction control by external magnetic field, which process is
tasks under the stimulation of various kinds of energy (light [3–5], ultra- considerably complicated. Here we design the TiO2-Fe Janus
sound [6–9], magnetism [10–12], electricity [13,14], chemical energy micromotor that use directly of economic metal Fe both as a necessary
[15–18], etc.). They are like tiny motion controlled mobile platforms electron absorption layer to form self-electrophoresis which can propel
that are functionally modified to perform a variety of complex and pre- the motors, but also as a magnetic layer response to an external mag-
cise tasks in micro/nanoscale environment, such as detection [19,20], netic field which can realize direction control. After modification by sin-
controlled release [21,22], purification [23,24], targeted therapy gle-layer metal Fe, such Janus micromotor could achieve efficient
[25,26], biomedicine [16,27], etc. The application of micro/nanomotors photocatalytic propulsion and controllable movement direction which
is very extensive, penetrated to interdisciplinary such as chemistry, holds great potential for future practical applications.
physics, biomedicine, environmental science, fluid mechanics, etc.
Thus, the micro/nanomotor has broad prospects of application in the fu- 1. Results and analysis
ture micro/nanoscale environment.
Light-driven micro/nanomotors is one of the most important type of 1.1. The propulsion mechanism of Janus micromotor
micro/nanomotors. These devices can be controlled by light and show
excellent potential in environment remediation and biomedicine appli- Based on the understanding of the self-electrophoresis mechanism
cations. Until now, according to the propulsion mechanisms, the light- of traditional bimetallic nanowire motors, the TiO2-Fe Janus micromotor
driven micro/nanomotor can be divided into several types, such as uses the photocatalyst TiO2 instead of the metal-catalyzed Pt of the bi-
photo-induced self-electrophoresis [28], diffusion [29] and metallic nanowire. Under ultraviolet light irradiation, photocatalyst
thermophoresis [30], bubble-driven [31], photo-induced deformation TiO2 electrons are excited from the steady state to the excited state,
[32] and photo-induced surface tension changes [33]. Among these, the electrons flow rapidly from the catalytic TiO2 to the metal Fe
micro/nanomotor driven by photo-induced self-electrophoresis is one which acts as the electron absorption layer that the electrons are
of the most popular light-driven micro/nanomotor. However, such enriched. In order to balance the environment, the H+ around the
micro/naomotor usually use expensive metals as electronic receptor motor flows from the catalytic TiO2 to metal Fe consumes electrons
such as Au [5] and Pt [28] to enhance the charge separation, thereby and reacts with H2O2 to generate H2, and the positive charges gather
triggering the self-electrophoresis for propulsion, which cost is high; at the end of TiO2 and react with H2O2 to product O2 and H+ to complete
the redox reaction. As the motor generates a micro-flow of water from
⁎ Corresponding authors. the TiO2 to the metal Fe, then the micromotor is due to move in the op-
E-mail addresses: rfdong@m.scnu.edu.cn (R. Dong), caiyp@scnu.edu.cn (Y. Cai). posite direction to the water flow.

https://doi.org/10.1016/j.inoche.2018.02.020
1387-7003/© 2018 Elsevier B.V. All rights reserved.
2 Q. Wang et al. / Inorganic Chemistry Communications 91 (2018) 1–4

micromotor from pure water to 5% H2O2 under 20.7 mW/cm2 UV light


intensity. As Fig. 3 shows, the speed of micromotor is only 3.92 μm/s
in pure water, when added 1% H2O2, the speed increased by 31%. With
increasing the H2O2 concentration, the speed of micromotor reached
11.65 μm/s in 5% H2O2 fuel which 3 times faster than in pure water.
Thus, the speed of micromotor and the H2O2 concentration is positively
correlated. Due to the high concentration of H2O2, more H2O2 molecules
attached to the surface of micromotor, therefore, will consume more
photo-generated electrons at the same time, more violent reaction
leads to stronger electron flow from TiO2 to Fe, thus triggering stronger
self-electrophoresis, showing a gradually increase in velocity as H2O2
concentration increases.

1.4. Effect of light intensity on the micromotor

In this part, another important factor affecting movement of TiO2-Fe


Fig. 1. Schematic of catalytic TiO2-Fe Janus micromotor powered by UV light in H2O2. Janus micromotor is the light intensity. We investigated the effect of UV
light intensity from 0 to 20.7 mW/cm2 on the speed of micromotor with
3% H2O2. As can be seen from Fig. 4(a), the motor is in Brownian motion
1.2. TiO2-Fe Janus micromotor structure characterization without UV light and its speed value is 2.91 μm/s. When the UV lamp is
turned on, the micromotors move immediately. At 4.3 mW/cm2, the
In order to confirm that the micromotor is a Janus structure com- speed of the motor is 4.87 μm/s, doubled the light intensity and the
posed of TiO2 and Fe, we observed it under a scanning electron micros- speed of the motor grew by 25%. When UV light intensity reached
copy (SEM). The micromotor was spherical with 2 μm diameter and its 20.7 mW/cm2, the speed increased to 7.8 μm/s. Thus, the speed is pro-
hemispherical surface was covered by iron to form the Janus spherical portional to the light intensity obviously. The relationship between inci-
structure. The element distribution of as-synthesized samples was fur- dent light and the flux can be described as Eq. (1):
ther investigated by Energy Dispersive X-Ray Spectroscopy (EDX). Fig.
1(b–d) shows that Ti and O filled the entire micromotor while metal hc
I¼ϕ ð1Þ
Fe(thickness is about 50 nm) only covered the hemispherical surface, λ
and the result corresponded to the SEM image. In order to further deter-
mine the composition of the micromotor, X-ray diffraction (XRD) was The symbols in the Eq. (1) represent: Ι (light intensity), φ (number
used to analyze crystal form of micromotor. Typical X-ray diffraction of incident photons per unit area per second), h (Planck's constant,
patterns of the micromotor are presented in Fig. 1(e). The XRD patterns 6.626 × 10–34 J∙S), c (speed of light, 3 × 108 m/s), λ (the wavelength
indicate that the TiO2-Fe Janus micromotor are of high crystallinity, of UV, 330–380 nm). It can be seen that the stronger the light intensity,
from the spectrum can be seen characteristic peaks of anatase TiO2 the higher the flux, more electrons were excited per unit time, thus
and metal Fe, the consequence further proved that the motor is based forming a more intense electron flow between TiO2 and Fe in
on TiO2 microspheres with iron cover the hemispherical surface. (See micromotor, which in turn lead to the motor with a faster speed.
Fig. 2.)
1.5. Movement direction control of micromotor

1.3. Effect of H2O2 concentration on the micromotor The direction control is of great importance to the application of
micro/nanomotors. In general, the magnetic layer was additionally
Up to H2O2 as fuel, the influence of H2O2 concentration on the speed modified on micro/nanomotors to achieve magnetically direction con-
of micromotor has been investigated. We studied the speed of trol. The advantage of the TiO2-Fe Janus micromotor is that the magnetic

Fig. 2. Characterization of TiO2-Fe micromotor.(a) Scanning electron microscope(SEM) image of a spherical TiO2-Fe micromotor, and (b–d) the corresponding (EDX) elemental mappings
for Ti, Fe, O, respectively;(e) XRD patterns of the TiO2-Fe micromotor.
Q. Wang et al. / Inorganic Chemistry Communications 91 (2018) 1–4 3

Fig. 3. The velocity and track lines of TiO2-Fe Janus micromotors. (a) The speed of micromotors under 20.7 mW/cm2 UV light in 0%, 1%, 2%, 3%, 4%, 5% H2O2 and (b–g) are the time-lapse
images illustration of motors motion for 3 s.

iron layer not only plays an electronic adsorption layer of the role which 2.2. Synthesis of TiO2-Fe Janus micromotors
can efficiently enhance the photocatalytic propulsion, but also played
the role of magnetic layer which can realize the direction control by ex- Take 8 ml of absolute ethanol into a small beaker, 200 μl tetrabutyl
ternal magnetic field. Therefore, it is possible to effectively control the titanate added, shaking for a few minute, then set aside for 6 h, TiO2 mi-
direction of the motor by utilizing the external magnetic field with crospheres were collected by centrifugation at 7000 rpm for 1 min and
high efficiency propulsion. Fig. 5 is the time-lapse image of micromotor washed three times with ethanol and water, dried at 60 °C, then obtain
motion for 10.5 s in 4% H2O2 solutions and under 20.7 mW/cm2 of UV the amorphous TiO2 microspheres. Then put amorphous TiO2 into a
light intensity. There were two steering actions of the TiO2-Fe Janus muffle furnace, annealed at 400 °C for 2 h to obtain anatase TiO2 micro-
micromotor. This effective movement control is achieved by adjusting spheres. Take appropriate anatase TiO2 microspheres dispersed in abso-
the direction of the magnetic field, and we prove that this method is ac- lute ethanol, evenly spread onto a glass, dried at 60 °C, after that, the
curate and effective for repeated operations. This is of great practical sig- particles were sputter coated with a thin Fe at 40 sccm of Ar flow rate,
nificance to the application of the micro/nanomotor in the future 2.4 Pa air pressure, 140 W RF power by Dual Magnetron Sputtering In-
complicated environment, such as carrying, identifying and separating. strument sputtering for 2 h. Finally, TiO2-Fe Janus micromotors
prepared.

2. Experimental section 3. Conclusions

2.1. Materials and instrumentation In summary, the TiO2-Fe Janus micromotor with a single modified
metal Fe layer which realizes strong light induced self-electrophorestic
All reagents and solvents were obtained from commercial suppliers propulsion, and the speed can be controlled by adjusting the concentra-
and used without further purification. Morphology and crystal structure tions of H2O2 fuel or intensities of UV light. Moreover, the direction of
of TiO2-Fe Janus microsphere motor was analyzed by scanning electron the TiO2-Fe Janus micromotor can be efficiently controlled by an exter-
microscopy (SEM, Tescan MAIA 3) and X-ray diffraction (XRD, Bruker nal magnetic field. Such a novel concise Janus motor with a simplified
D8 Advance). Elemental analyses were carried out on an Oxford x-act preparation process and low cost has a valuable reference for the devel-
analyzer. The motion performance and direction control of TiO2-Fe opment of practical micro/nanomotor research.
Janus micromotors was analyzed by an inverted optical microscope
(Nikon ECLIPSE Ti-S). The velocity of motors has been calculated by Acknowledgements
the NIS-Elements AR 3.2 software. UV light was generated by Mercury
lamp. Dual Magnetron Sputtering Instrument (Beijing Ruifu Si Technol- We acknowledge the financial support from the Guangdong Provin-
ogy Co., Ltd. VTC300) was used to generate the iron hemispherical layer cial Natural Science Foundation (2017A030310432), China Postdoctoral
on motors. Science Foundation (2017T100639, 2016M602481), National Natural

Fig. 4. The relationship between the speed of micromotor and UV light.(a) The influence of the UV light intensity on the speed of micromotors in H2O2;(b)(c) time-lapse images illustration
of TiO2-Fe Janus micromotors moving status in 3% H2O2 with UV light (10.1 mW/cm2) and without UV light for 3 s.
4 Q. Wang et al. / Inorganic Chemistry Communications 91 (2018) 1–4

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