Materials Letters 71 (2012) 141144

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Enhanced photoelectrochemical water splitting on Pt-loaded TiO2 nanorods array thin lm

Fangfang Wang a, Zhi Zheng b, Falong Jia a,
a b

College of Chemistry, Central China Normal University, Wuhan 430079, PR China Institute of Surface Micro and Nano Materials, Xuchang University, Xuchang 461000, PR China

a r t i c l e

i n f o

a b s t r a c t
We demonstrate that appropriate Pt loading could signicantly enhance the ability of TiO2 nanorods array thin lm (TNTF) electrode to photoelectrochemically split water under solar light. The TiO2 nanorods array thin lm was directly grown on uorine-doped tin oxide glass through hydrothermal reaction. And platinum (Pt) nanoparticles were deposited uniformly on the surface of TiO2 nanorods by a convenient sputtering method. The Pt-loaded TNTF sample was highly stable during the photoelectrochemical water splitting process. Its activity did not decrease after 50 continuous potential scans. This study reveals that the Pt loaded TiO2 nanorods array thin lm electrode is promising for the photoelectrochemical water splitting to generate hydrogen. 2011 Elsevier B.V. All rights reserved.

Article history: Received 9 October 2011 Accepted 6 December 2011 Available online 21 December 2011 Keywords: TiO2 Photoelectrochemical water splitting Nanocomposites Thin lms

1. Introduction As one of the sustainable sources of energy, hydrogen fuel has been studied for many years for its unique advantages such as clean exhaust and light weight [1]. Electrolysis of water provides a clean and simplied way to get highly pure hydrogen. The photocatalytic production of H2 via water splitting over semiconductor photocatalyst attracted considerable attention and many semiconductor catalysts have been widely studied [2]. Among the exploited catalysts, titanium dioxide (TiO2) is one of the most popular catalysts for water splitting because of its high chemical stability, non-toxicity, as well as low cost [3]. One dimensional TiO2 was found to exhibit superior photoelectrochemical performances than TiO2 nanoparticles [4]. The reason is that one dimensional nanostructure could promote the electron transport rate, and also accelerate the ion diffusion at the semiconductorelectrolyte interface [5]. Pure TiO2 has very low photoresponse due to its wide band gap (~3.2 eV). Therefore, extensive efforts have been made to enhance its photoactivity through modifying the band structures by dopant materials [6] and sensitizing with semiconductor quantum dots [7]. It is reported that Pt modication could improve the photoactivity of TiO2 [8], because the deposition of Pt on TiO2 not only inhibits electronhole pair recombination, but also widens the spectral response to longer wavelengths [9]. By now, various TiO2 photocatalysts loaded with Pt have been prepared for the degradation of organic pollutants [10]. Although Pt-loaded TiO2 nanoparticles and

nanotubes were used for photoelectrochemical water splitting [11], Pt-loaded TiO2 nanorods were seldom studied. In this communication, we report that the Pt-loading could significantly enhance the ability of TiO2 nanorods array thin lm (TNTF) to photoelectrochemically split water at light and discuss the reason for this enhancement.

2. Experimental 2.1. Preparation of Pt-loaded TiO2 nanorods thin lm The TiO2 nanorod arrays were grown through hydrothermal reaction according to Liu's method [12]. Typically, 0.11 mL of titanium butoxide (97%, Aldrich) was dropped into the solution with 4.7 mL of deionized water and 4.7 mL of concentrated hydrochloric acid (AR, 37 wt.%) under vigorous stirring. And the solution was transferred into a 23 mL Teon-lined stainless steel autoclave. The well-cleaned uorine doped tin oxide (FTO glass, NSG, Japan) coated glass slides were put into the Teon reactor and the autoclave was kept at 150 C in an oven for 20 h. After cooling down to room temperature naturally, the FTO glass was taken out, washed with deionized water and dried at 50 C. Pt was sputtered onto TiO2 nanorods thin lms by using an auto ne coater (JFC-1600, Japan) with current of 20 mA and chamber pressure less than 10 5 Pa. The as-prepared sample was directly annealed in a furnace at 450 C for 2 h. The samples were characterized by eld emission scanning electron microscopy (FESEM, JEOL-6700F), transmission electron microscopy (TEM/HRTEM, JEOL JSM-2010), X-ray diffraction (XRD, MPD 18801, Cu K) and UVvisible absorption spectroscopy (S-3100, SCINCO).

Corresponding author. Tel./fax: + 86 27 6786 7953. E-mail address: jia@mail.ccnu.edu.cn (F. Jia). 0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.12.063

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F. Wang et al. / Materials Letters 71 (2012) 141144

Fig. 1. XRD patterns of the as-synthesized samples (a) and after annealing treatment at 450 C for 2 h (b). The peaks labeled with mark o resulted from FTO substrate.

2.2. Photoelectrochemical measurements All electrochemical experiments were performed on an electrochemical workstation (CHI660B, CHI Instruments, Shanghai). A standard three-electrode conguration was set up with TNTF/FTO glass as the working electrode (0.5 cm2 area), a platinum foil as counter electrode and a saturated Ag/AgCl reference electrode. The photoelectrochemical measurements were conducted in 0.05 mol/L KOH aqueous solution illuminated under 1.5 AM solar simulator (Shanghai lan sheng Co., 500 W xenon lamp). The intensity of light on the sample was 200 mW/cm2.

3. Results and discussion Fig. 1 shows the XRD patterns of the resulting TNTF samples with and without annealing treatment. The peaks located at 36.0 and 62.6 corresponded to the (101) and (002) crystal planes of rutile titania (JCPDS le No. 76-1939), respectively. The peak strength of the sample was enhanced greatly after annealing treatment at 450 C for 2 h, suggesting that the annealing treatment resulted in better crystallization. Fig. 2 shows the surface morphologies of TNTF sample with 20 s Pt sputtering. Uniform nanorods were found to grow on the FTO

Fig. 2. SEM (a, b), TEM (c), and HRTEM (d) images of TNTF samples with Pt sputtering for 20 s.

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substrate with ~100 nm in width and each nanorod consisted of bundles of smaller nanorods (Fig. 2a and b). The TEM image (Fig. 2c) reveals that the nanorod bundles consist of radially aligned nanorods of ~20 nm in diameter with narrow gaps among the nanorods. It can be seen that Pt nanoparticles with size of ~4 nm were deposited uniformly on the surface of TiO2 nanorods. The HRTEM result gives a better view of the sputtered Pt nanoparticles (see the circled area) with lattice fringe of 0.22 nm, which matches with the (111) plane of Pt. And the lattice fringes of TiO2 nanorods could also be observed and the value of 0.29 nm can be assigned to the (001) planes of rutile TiO2. EDS analysis showed that the compositions of Pt in the samples were 0.12, 0.18 and 0.25 at.% with Pt sputtering time of 10 s, 20 s and 30 s, respectively. Fig. 3 shows the linear sweep voltammograms recorded with different TNTF electrodes. All these electrodes exhibited very low current densities in the scale of A/cm 2 in dark (Fig. 3A). The anodic currents dramatically increased to the range of mA/cm2 after shining simulated solar light (Fig. 3B). The enhancement of current density is the lowest for the unannealed TNTF electrode among all the samples. The current density of annealed TNTF electrode at 1.0 V was about ve times that of the unannealed one and could be further enhanced by Pt loading. 10 second Pt sputtering only slightly improved the responsive current density. With the sputtering time prolonging to 20 s, the current density at 1.0 V (3.8 mA/cm2) increased nearly four times that (0.96 mA/ cm2) of bare annealed TNTF electrode. However, the current density tended to decrease with further prolonging the sputtering time. For TiO2-based photoelectrochemical system, quick recombination between photogenerated electrons and holes is the major factor to decrease the photoactivity. When the surface of TiO2 nanorods was loaded with platinum, the highly dispersed Pt nanoparticles not only facilitate the exciton separation, but also enhance photogenerated electrons

transport. As shown in Fig. S1, the loading of Pt could increase the optical absorption in the visible region effectively. No saturation of current at more positive potential for all Pt-loaded TNTF samples indicates efcient charge separation in nanorods upon illumination. Therefore, Pt-loading is effective for the improvement of the photoelectrochemical performance of the TNTF electrode. The reason for the decrease of current density with 30 second Pt loading may be attributed to the fact that excess Pt coating hindered the exposure of TiO2 to the electrolyte. To test the stability of Pt-TNTF electrode during the photoelectrochemical process, constant potential of 0.5 V was applied to the sample with the light on and off repeatedly. The It curve in Fig. 3C displays a very low dark current and a steady photocurrent quickly upon illumination of light. Even after a long time (e.g. 1 h) of onoff light cycle, the photoresponsive property of Pt-TNTF electrode almost remained the same. In Fig. 3D, the IV curve after 50 times continuous potential scan under light almost overlapped with that of the rst one, indicating that the Pt-loaded TNTF electrode is highly stable during the photoelectrochemical water splitting process.

4. Conclusions In summary, we demonstrate that an appropriate Pt loading could signicantly enhance the ability of TiO2 nanorods array thin lm electrode to photoelectrochemically split water under solar light. The TiO2 nanorods array thin lm was directly grown on uorine-doped tin oxide glass. The Pt-loaded TNTF/FTO sample was highly stable in the photoelectrochemical water splitting process. This study suggests that Pt loaded TNTF/FTO electrode is promising for the photoelectrochemical water splitting to generate hydrogen.

Fig. 3. Liner sweep voltammograms in dark (A) and light (B) with different samples. (a) and (b) are TNTF samples before and after annealing. (c), (d) and (e) are the annealed TNTF samples with Pt sputtering for 10, 20 and 30 s. (C) and (D) are the It curve at 0.5 V, and 1st and 50th liner sweep voltammograms in light with sample (d) as electrode.

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F. Wang et al. / Materials Letters 71 (2012) 141144 conducting oxide coated glass: synthesis details and applications. Nano Lett 2008;8:37816. Baxter JB, Aydil ES. Nanowire-based dye-sensitized solar cells. Appl Phys Lett 2005;86:053114. Kumaresan L, Mahalakshmi M, Palanichamy M, Murugesan V. Synthesis, characterization, and photocatalytic activity of Sr2 + doped TiO2 nanoplates. Ind Eng Chem Res 2010;49:14805. Sun WT, Yu Y, Pan HY, Gao XF, Chen Q, Peng LM. CdS quantum dots sensitized TiO2 nanotube-array photoelectrodes. J Am Chem Soc 2008;130:11245. Lee JS, Choi WY. Photocatalytic reactivity of surface platinized TiO2: substrate specicity and the effect of Pt oxidation state. J Phys Chem B 2005;109:7399406. Li FB, Li XZ. The enhancement of photodegradation efciency using PtTiO2 catalyst. Chemosphere 2002;48:110311. Daniele S, Battistel D, Gerbasi R, Benetollo F, Battiston S. Titania-coated platinum thin lms by MOCVD: electrochemical and photoelectrochemical properties. Chem Vap Deposition 2007;13:64450. Sasaki T, Koshizaki N, Yoon JW, Beck KM. Preparation of Pt/TiO2 nanocomposite thin lms by pulsed laser deposition and their photoelectrochemical behaviors. J Photochem Photobiol A 2001;145:116. Liu B, Aydil ES. Growth of oriented single-crystalline rutile TiO2 nanorods on transparent conducting substrates for dye-sensitized solar cells. J Am Chem Soc 2009;131:398590.

Supplementary materials related to this article can be found online at doi:10.1016/j.matlet.2011.12.063. Acknowledgments This work was supported by the National Science Foundation of China (Grant 21073070), the self-determined research funds of CCNU from the colleges' basic research and operation of MOE (CCNU11A02006), and the National Science Foundation of Hubei Province (Grant 2010CDB04004). References
[1] Payne TL, Bogomolny D, Brown G. Hydrogen PEM fuel cells: a market need provides research opportunities. Acs Symp Ser 2009;1026:10713. [2] Yao WF, Huang CP, Ye JH. Hydrogen production and characterization of MLaSrNb2NiO9 (M = Na, Cs, H) based photocatalysts. Chem Mater 2010;22: 110713. [3] Fang J, Shi FC, Bu J, Ding JJ, Xu ST, Bao J, et al. One-step synthesis of bifunctional TiO2 catalysts and their photocatalytic activity. J Phys Chem C 2010;114:79408. [4] Feng XJ, Shankar K, Varghese OK, Paulose M, Latempa TJ, Grimes CA. Vertically aligned single crystal TiO2 nanowire arrays grown directly on transparent

[5] [6]

[7] [8] [9] [10]

[11]

[12]