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A general strategy for synthesis of metal nanoparticles by a solid-state redox route under ambient conditions
Yizhao Li, Yali Cao and Dianzeng Jia*
A general strategy has been developed to synthesize metal nanoparticles by solid-state redox reaction under ambient conditions. A series of metallic nanoparticles, such as Ni, Fe, Sn, Co nanoparticles, and

Received 30th October 2013 Accepted 2nd January 2014 DOI: 10.1039/c3ta14427e www.rsc.org/MaterialsA

bimetallic NiCo nanoparticles were prepared by using inexpensive metal salts and sodium borohydride (NaBH4). The obtained Ni nanoparticles showed excellent catalytic activity toward the reduction of 4nitrophenol to 4-aminophenol. The protocol creates a novel and facile route for the synthesis of metal nanoparticles.

Introduction
Metal nanoparticles with excellent optical, electrical, magnetic, and catalytic properties are attractive candidates for applications in biomedicine, energy conversion, magnetic data storage, catalysis, and other elds.16 It is important to obtain metal nanoparticles by a facile approach, not only for fundamental scientic research, but also for various technological applications.712 Thus, a large number of researchers have dedicated eorts to the preparation of metal nanoparticles. In the past few decades, a variety of methods for the synthesis of metal nanomaterials have been proposed. Solutionbased reduction routes have been used for the preparation of various metal nanomaterials with dierent morphologies, especially noble metal nanoparticles, such as Rh, Pd, Ag, PtCu3, and AuPt.1318 However, the procedures of the solution-based method are complicated and time-consuming. In addition, it is dicult to fabricate 3d-transition metal (Fe, Co, and Ni) nanoparticles because of the oxidation of the products in aqueous media.1921 Thermal decomposition of the organometallic precursor was developed for the synthesis of various metal nanoparticles including metallic Fe and Co nanoparticles.2225 Nevertheless, its operation conditions are harsh, and expensive and toxic organic reactants are needed. Metal nanoparticles could also be obtained by solventless synthesis.26,27 A large number of nanoparticles, such as metallic Pd, Ag, and Au
Key Laboratory of Material and Technology for Clean Energy, Ministry of Education, Key Laboratory of Advanced Functional Materials, Autonomous Region, Institute of Applied Chemistry, Xinjiang University, Urumqi, Xinjiang 830046, China. E-mail: jdz@xju.edu.cn; Fax: +86-991-8580032; Tel: +86-991-8583083 This paper is dedicated to Professor Xinquan Xin on the occasion of his 80th birthday. Electronic supplementary information (ESI) available: XRD, EDS, and XPS patterns of the metal nanoparticles; BET and BJH results of the catalysts. See DOI: 10.1039/c3ta14427e

nanoparticles, were synthesized by heating the precursor metal salts in the absence of solvents.2830 But a high temperature is generally required in the route. The development of these methods introduces the possibility of synthesizing metal nanoparticles without solvent. However, it is still a challenge for materials scientists to develop a general facile process by using simple materials to synthesize metal nanoparticles. Here, we report on a general strategy for the synthesis of various metal nanoparticles by a solid-state redox route under ambient conditions. Metallic Ni, Fe, Sn, Co nanoparticles and bimetallic NiCo nanoparticles have been prepared through the one-pot redox route using the corresponding inorganic salts and sodium borohydride (NaBH4) in the solid-state form. The synthesis approach has several advantages, including mild conditions, easy handling, low cost, and easy scale-up. Furthermore, this general strategy may be extended for the synthesis of other types of metal nanoparticles. We also demonstrated one application of the obtained Ni nanoparticles which were tested as catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP).

Experimental section
Starting materials All chemicals were used without further puri cation. Nickel(II) chloride hexahydrate (NiCl2$6H2O, 99.0%), iron(III) nitrate nonahydrate [Fe(NO3)3$9H2O, 98.5%], tin(II) chloride dihydrate (SnCl2$2H2O, 98.0%), cobalt(II) acetate tetrahydrate [Co(CH3COO)2$4H2O, 99.0%], sodium borohydride (NaBH4, 98%), and 4-nitrophenol (4-NP, 99%) were obtained from Tianjin Fuchen Chemical Reagents Co., Ltd. Sodium chloride (NaCl), sodium dodecyl sulfate (SDS), and polyethylene glycol 400 (PEG-400) were purchased from Tianjin Guangfu Chemical Reagent Co., Ltd.

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Preparation of metal nanoparticles All metal nanoparticles in this work were prepared by the solidstate redox method under ambient conditions. Typical examples are given below. For Ni nanoparticles: NiCl2$6H2O (0.48 g, 2 mmol) and NaBH4 (0.15 g, 4 mmol) were mixed and ground in an agate mortar at room temperature. Subsequently, several drops of water were slowly added into the mixtures. Accompanied by the release of heat and vapor, the color of mixtures changed from green to black. Aer grinding for about 30 min, the resulting solid products were washed with distilled water and absolute ethanol several times. The products were then dried at 60  C for 2 h in a vacuum drying oven. The yield was 95.2%. In addition, NaCl (2.0 g) and SDS (5.77 g) were added into the mixtures to fabricate the Ni nanoparticles prior to the addition of water, respectively. For Fe nanoparticles: the same procedure was applied as for Ni nanoparticles except that NiCl2$6H2O was replaced by Fe(NO3)3$9H2O (0.81 g, 2 mmol). The yield was 92.7%. For Sn nanoparticles: the same procedure was applied as for Ni nanoparticles except that NiCl2$6H2O was replaced by SnCl2$2H2O (0.45 g, 2 mmol), and PEG-400 (1.0 mL) was added. The yield was 91.3%. For Co nanoparticles: the same procedure was applied as for Ni nanoparticles except that NiCl2$6H2O was replaced by Co(CH3COO)2$4H2O (0.50 g, 2 mmol). The yield was 92.5%. For NiCo nanoparticles: the same procedure was applied as for Ni nanoparticles except that NiCl2$6H2O (0.24 g, 1 mmol) and Co(CH3COO)2$4H2O (0.25 g, 1 mmol) were used simultaneously. The yield was 90.8%. Characterization The crystal structure of the obtained samples was characterized by X-ray diraction (XRD) using a DX-1000 X-ray diractometer X-ray photoelectron specwith Cu-Ka radiation (l 1.5418 A). troscopy (XPS) signals were collected on a Thermo ESCALAB 250 instrument using a monochromated Al X-ray resource at 1486.6 eV operated at 15 kW. Field emission scanning electron microscope (FESEM) images were obtained on a Hitachi U-3900H scanning electron microscope with an accelerating voltage of 20 kV. Transmission electron microscope (TEM) and high resolution transmission electron microscope (HRTEM) images of the products were obtained on a JEOL JEM-2010F electron microscope with an accelerating voltage of 200 kV. The product component measurement was carried out by energy dispersive X-ray spectroscopy (EDS) using a JEOL JEM-2010F electron microscope. The BrunauerEmmettTeller (BET) and BarrettJoynerHalender (BJH) results were obtained on a Micromeritics ASAP 2020 surface area and porosity analyzer. Catalytic reduction of 4-NP The reduction of 4-NP was studied as a model reaction to conrm the catalytic activity of the synthesized Ni nanoparticles. The following procedure was used for the catalytic test: 10.0 mL of fresh NaBH4 solution (0.1 M) was mixed with

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20.0 mL of 4-NP solution (0.1 mM) in a conical ask. Then, 2.0 mg of the as-prepared Ni nanoparticles was added to the mixture as a catalyst. Parts of the mixture were withdrawn every 2 min and the concentrations of 4-NP were determined by UV-vis absorption spectroscopy (Hitachi U-3900H UV-vis spectrophotometer) at a wavelength of 400 nm. In the recycling study, the catalyst was separated from the solution by centrifugation and rinsed with water. Then, it was reused in the next reaction run.

Results and discussion

The formation of metal nanoparticles The synthesis was carried out by a facile route of solid-state redox reaction under ambient conditions. The overall synthetic procedure for metal nanoparticles is depicted in Scheme 1. Firstly, metal salts were mixed with NaBH4 in an agate mortar at room temperature. The starting materials were ground to ensure full mixing of the reactants. Additives such as NaCl, SDS, and PEG-400 can be introduced into the system as capping agents and/or dispersing agents to inuence the morphology and size of the products. Then, several drops of water were slowly added into the mixtures to trigger the reaction. Accompanied by the release of heat and vapor, the color of the mixtures changed, which suggests that solid-state reaction occurred. Water was used as a reactant in the reaction. The overall solid-state redox reaction can be described by the following equation: 2Mx+ + 2xBH4 + 6xH2O / 2M0 + 2xB(OH)3 + 7xH2 (1)

where Mx+ represents the metal ions and M0 is the corresponding metal. The metal salts of the reactants can be reduced by NaBH4 to produce the metals in the presence of a small amount of water. Based on the solid-state reactions,31 the metal particles with nanometer size can be obtained. This solid-state synthesis of metal nanoparticles demonstrates several advantages: (1) toxic and expensive organic solvents are not used in the reaction and the starting materials are inexpensive and easily obtainable; (2) the synthesis is conducted at room temperature under atmospheric pressure, which is facile, cost-eective, and eco-friendly; (3) the composition, size, and morphology of the nanoparticles can be tuned by the types of metal salts and additives; (4) the synthesis can be easily up-scaled; and (5) the protocol may be further extended to synthesize other metal nanoparticles such as noble metals and bimetals.

Scheme 1 The synthesis of metal nanoparticles by a solid-state redox route under ambient conditions.

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Structure and morphology of the products Metallic Ni has excellent magnetic and catalytic properties, which are widely used as magnetic storage devices and catalytic materials.32,33 Herein, Ni nanoparticles have been prepared by the solid-state chemical reaction approach. The XRD pattern of the obtained sample is shown in Fig. 1a. All the reections are indexed to cubic phase Ni and are in agreement with JCPDS 04-0850. XPS was employed to investigate the compositions of the product in detail. Fig. 1b shows the photoelectron spectrum for the Ni 2p region of the Ni nanoparticles. The peaks at 852.3 and 855.8 eV appear, which indicates the presence of the metallic and oxidative Ni in the nanoparticles.34,35 The oxidized Ni may come from partial oxidation during the preparation and washing processes. Fig. 1c and d show the FESEM and TEM images of the Ni nanoparticles. Irregular nanoparticles with the size of 100500 nm were obtained when nickel chloride was used as a starting material without any additives. The inset of Fig. 1d clearly shows that the particle surface is enclosed with a layer of oxides. The morphology of nanoparticles can be inuenced by the additives. When NaCl was added, uniform Ni particles with a size of about 20 nm were obtained (Fig. 2a and b). As shown in Fig. 2c and d, nanoparticles of 2050 nm were prepared aer adding SDS. In addition, the XRD patterns (Fig. S1) show that the crystal structures of the samples are not changed with the addition of additives. The EDS analyses of the three kinds of Ni nanoparticles were conducted (Fig. S2). They illustrate that the as-prepared structures consist of Ni and O. Metallic Fe, Sn, Co nanoparticles and bimetallic NiCo nanoparticles have potential applications in magnetic data storage, catalysis, and energy storage.3639 They can also be fabricated by the general route. Fig. 3 shows XRD patterns,

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Fig. 2

FESEM and TEM images of Ni nanoparticles with dierent additives: (a and b) Ni nanoparticles with NaCl; (c and d) Ni nanoparticles with SDS and the insets are the corresponding HRTEM images.

FESEM images, and TEM images of the obtained Fe, Sn, and Co nanoparticles with dierent metal salts. The characteristic peaks of the XRD pattern in Fig. 3a can be indexed as the cubic Fe (JCPDS 06-0696). From Fig. 3b and c, it can be seen that spherical Fe nanoparticles with a diameter of about 10 nm were obtained when iron nitrate was used as a starting material. Tin chloride as a reactant led to the formation of tetragonal Sn

Fig. 1 (a) XRD pattern of Ni nanoparticles; (b) XPS spectrum of Ni 2p of Ni nanoparticles; (c) FESEM image of Ni nanoparticles; (d) TEM image of Ni nanoparticles and the inset is a HRTEM image of the nanoparticles.

Fig. 3 XRD patterns of metal nanoparticles (a: Fe; d: Sn; g: Co); FESEM images of metal nanoparticles (b: Fe; e: Sn; h: Co); TEM images of metal nanoparticles (c: Fe; f: Sn; i: Co).

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(JCPDS 04-0673) (Fig. 3d). The Sn nanoparticles with the size of 20100 nm are shown in Fig. 3e and f. When cobalt acetate was used as a starting material, cubic Co (JCPDS 15-0806) was obtained (Fig. 3g). The Co nanoparticles (Fig. 3h and i) have an irregular shape with a size of 2050 nm. In addition, the XPS spectra of the Fe, Sn, and Co nanoparticles are presented in Fig. S3. It shows that the metal nanoparticles are in zero valent and positive valent states.4042 This conrms that metals and oxides are included in the resulted samples. When two kinds of metal salts were added in the reaction system, bimetallic nanomaterials can be prepared by our proposed protocol. NiCo nanoparticles have been synthesized with nickel chloride and cobalt acetate as starting materials. The XRD pattern of the sample (Fig. 4a) is very similar to that of either Ni (JCPDS 04-0850) or Co (JCPDS 15-0806). The positions of peaks lie that of pure Ni or Co. XPS is applied to further conrm the formation of NiCo nanoparticles. The Ni 2p peaks at 849.2 and 854.6 eV are assigned to Ni(0) and Ni(II), respectively (Fig. 4b). For Co 2p, three peaks at 779.8, 795.2, and 782.2 eV indicate that Co(0) and Co(II) are dominant (Fig. 4c). The signals of metallic bonding energy in the as-obtained NiCo nanoparticles are slightly shied compared with pure Ni and Co metals due to the dierent environment of Ni and Co in the NiCo structure and pure Ni and pure Co metallic materials.43,44 The EDS pattern of NiCo nanoparticles (Fig. 4d) reveals that the atomic ratio of Ni to Co is 54.8 : 45.2. From Fig. 4e and f, it can be seen that a number of irregular nanoparticles with the size of 30100 nm were obtained. The stability of the metal nanoparticles has also been investigated. The samples were stored in air for two weeks. Then the crystal structure of the metal nanoparticles was characterized by XRD. As shown in Fig. S4, the XRD patterns of the samples exposed to air for two weeks remain almost unaltered, compared with those of fresh metal nanoparticles. It indicates that the metal nanoparticles prepared by a solid-state redox route have good stability. The layer of oxides on the surface of the particles oers protection to the metal nanoparticles from further oxidation.23

Catalytic properties of Ni nanoparticles Metal nanoparticles have potential applications in many areas. We chose Ni-catalyzed reduction of 4-NP as a model reaction to demonstrate the use of our metal nanoparticles as ecient catalysts. The catalytic properties of the as-prepared Ni nanoparticles with dierent additives were investigated. For simplicity, Ni nanoparticles obtained without additives, and with NaCl and SDS are designated as Ni-1, Ni-2 and Ni-3, respectively. Fig. 5ac show the UV-vis spectra as a function of reaction time for the reduction of 4-NP in the presence of three kinds of catalysts. Clearly, with the Ni nanoparticles, the characteristic absorption peak of 4-NP at 400 nm gradually decreased, while a new peak at 295 nm, ascribed to 4-AP, appeared. Fig. 5d and e show C/C0 and ln(C/C0) versus reaction time for the reduction of 4-NP over Ni-1, Ni-2, and Ni-3. It can be observed that Ni-2 and Ni-3 exhibited good performance compared with Ni-1. From Fig. 5d, we can observe that the induction time (t0) was 8, 0, and 2 minutes for Ni-1, Ni-2 and Ni-3, respectively. As shown in Fig. 5e, the rate constants (k) of Ni-1, Ni-2, and Ni-3 were calculated to be 0.176, 0.291 and 0.333 min1, respectively. Based on the rate constants, Ni-3 showed a higher catalytic activity than Ni-2. The nitrogen adsorptiondesorption isotherm measurements were carried out to examine the specic surface areas of the catalysts. As shown in Fig. S5, Ni-1, Ni-2, and Ni-3 manifest speci c surface areas of 25.6, 38.2, and 44.0 m2 g1, respectively. The excellent catalytic performance of Ni-3 may be ascribed to its large specic surface area, which renders to more active sites for the catalytic process.45 The catalytic activity of the Ni nanoparticles is comparable to those reported in the literature.4649 The reusability is very important in the catalytic reaction for practical applications. In the study, Ni-3 was employed as a representative catalyst in the reduction of 4-NP over ve cycles. From Fig. 5f, it is found that the conversion of 4-NP could still reach 86.6% aer ve cycles, indicating that Ni-3 exhibited good recyclability.

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Fig. 4 (a) XRD pattern of NiCo nanoparticles; (b) XPS spectra of Ni 2p of NiCo nanoparticles; (c) XPS spectra of Co 2p of NiCo nanoparticles; (d) EDS patterns of NiCo nanoparticles; (e) FESEM image of NiCo nanoparticles; (f) TEM image of NiCo nanoparticles.

Fig. 5 Catalytic performance of the obtained Ni nanoparticles: UVvis spectra during the catalytic reduction of 4-NP in the presence of Ni-1 (a), Ni-2 (b), and Ni-3 (c); plot of C/C0 versus reaction time (d) and plot of ln(C/C0) versus reaction time (e) for the reduction of 4-NP in the presence of Ni nanoparticles; (f) conversion of 4-NP in ve cycles with Ni-3.

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Conclusions
In summary, we have demonstrated a general strategy to prepare metal nanoparticles by solid-state redox reaction. The metallic Ni, Fe, Sn, Co and bimetallic NiCo nanoparticles have been successfully synthesized by using inexpensive metal salts and NaBH4. The route is facile, scalable, and cost-eective. It may be extended to the synthesis of other metal nanoparticles. The obtained metal nanoparticles with excellent properties are expected to have a wide range of applications, such as catalysts, electronic devices, and battery materials.

Acknowledgements
This work was nancially supported by the Doctoral Innovation Program of Xinjiang University (no. XJUBSCX-2012019), the Graduate Research Innovation Project of Xinjiang (no. XJGRI2013020), the National Natural Science Foundation of China (no. 21101132, 21361024 and 21271151) and the Program for Changjiang Scholars and Innovative Research Team in the University of Ministry of Education of China (IRT1081).

Notes and references

1 I. Capek, Adv. Colloid Interface Sci., 2004, 110, 49. 2 B. Lim and Y. Xia, Angew. Chem., Int. Ed., 2011, 50, 76. 3 R. Narayanan and M. El-Sayed, J. Phys. Chem. B, 2005, 109, 12663. 4 J. Wilcoxon and B. Abrams, Chem. Soc. Rev., 2006, 35, 1162. 5 Y. Xia, Y. Xiong, B. Lim and S. Skrabalak, Angew. Chem., Int. Ed., 2009, 48, 60. 6 L. Yang, X. Song, M. Qi, L. Xia and M. Jin, J. Mater. Chem. A, 2013, 1, 7316. 7 H. B onnemann and R. Richards, Eur. J. Inorg. Chem., 2001, 2455. 8 T. Udayabhaskararao and T. Pradeep, J. Phys. Chem. Lett., 2013, 4, 1553. 9 X. Wang, J. Zhuang, Q. Peng and Y. Li, Nature, 2005, 437, 121. 10 H. Yu, P. Gibbons, K. Kelton and W. Buhro, J. Am. Chem. Soc., 2001, 123, 9198. 11 J. Zhang and J. Fang, J. Am. Chem. Soc., 2009, 131, 18543. 12 P. Huang, J. Lin, Z. Li, H. Hu, K. Wang, G. Gao, R. He and D. Cui, Chem. Commun., 2010, 46, 4800. 13 S. Ayyappan, R. Gopalan, G. Subbanna and C. Rao, J. Mater. Res., 1997, 12, 398. 14 D. Chen, J. Li, C. Shi, X. Du, N. Zhao, J. Sheng and S. Liu, Chem. Mater., 2007, 19, 3399. 15 J. Hoefelmeyer, H. Liu, G. Somorjai and T. Tilley, J. Colloid Interface Sci., 2007, 309, 86. 16 M. Wu, D. Chen and T. Huang, Chem. Mater., 2001, 13, 599. 17 J. Martin, J. Wilcoxon, J. Odinek and P. Provencio, J. Phys. Chem. B, 2002, 106, 971. 18 C. Gumeci, D. Cearnaigh, D. Casadonte and C. Korzeniewski, J. Mater. Chem. A, 2013, 1, 2322. 19 D. Chen and S. Wu, Chem. Mater., 2000, 12, 1354. 20 J. Wilcoxon and P. Provencio, J. Phys. Chem. B, 1999, 103, 9809.

21 W. Wang, Z. Jin, T. Li, H. Zhang and S. Gao, Chemosphere, 2006, 65, 1396. 22 S. Park, S. Kim, S. Lee, Z. Khim, K. Char and T. Hyeon, J. Am. Chem. Soc., 2000, 122, 8581. 23 S. Peng, C. Wang, J. Xie and S. Sun, J. Am. Chem. Soc., 2006, 128, 10676. 24 V. Puntes, K. Krishnan and P. Alivisatos, Science, 2001, 291, 2115. 25 V. Puntes, K. Krishnan and P. Alivisatos, Appl. Phys. Lett., 2001, 78, 2187. 26 Y. Han, H. Cha, C. Kim, Y. Kim and Y. Kang, J. Phys. Chem. C, 2007, 111, 6275. 27 L. Seinberg, S. Yamamoto, R. Gallage, M. Tsujimoto, Y. Kobayashi, S. Isoda, M. Takano and H. Kageyama, Chem. Commun., 2012, 48, 8237. 28 H. Cha, D. Lee, Y. Kim, C. Kim, C. Lee and Y. Kang, Inorg. Chem., 2007, 47, 121. 29 D. Jose and B. Jagirdar, J. Solid State Chem., 2010, 183, 2059. 30 M. Nakamoto, Y. Kashiwagi and M. Yamamoto, Inorg. Chim. Acta, 2005, 358, 4229. 31 X. Ye, D. Jia, J. Yu, X. Xin and Z. Xue, Adv. Mater., 1999, 11, 941. 32 J. Park, E. Kang, S. Son, H. Park, M. Lee, J. Kim, K. Kim, H. Noh, J. Park, C. Bae, J. Park and T. Hyeon, Adv. Mater., 2005, 17, 429. 33 G. Bhaduri and L. Siller, Catal. Sci. Technol., 2013, 3, 1234. 34 Z. Zhao, Z. Wu, L. Zhou, M. Zhang, W. Li and K. Tao, Catal. Commun., 2008, 9, 2191. 35 R. Furstenau, G. McDougall and M. Langell, Surf. Sci., 1985, 150, 55. 36 X. Wei, X. Zhou, K. Wu and Y. Chen, CrystEngComm, 2011, 13, 1328. 37 S. Bose, A. Garcia-Garcia, M. Ugeda, J. Urbina, C. Michaelis, I. Brihuega and K. Kern, Nat. Mater., 2010, 9, 550. 38 C. Black, C. Murray, R. Sandstrom and S. Sun, Science, 2000, 290, 1131. 39 F. Dumestre, B. Chaudret, C. Amiens, P. Renaud and P. Fejes, Science, 2004, 303, 821. 40 H. Jung and A. Alfantazi, Electrochim. Acta, 2006, 51, 1806. 41 Y. Kim, Y. Yoon and D. Shin, J. Anal. Appl. Pyrolysis, 2009, 85, 557. 42 X. Li and W. Zhang, Langmuir, 2006, 22, 4638. 43 S. Zhou, M. Wen, N. Wang, Q. Wu, Q. Wu and L. Cheng, J. Mater. Chem., 2012, 22, 16858. 44 M. Wen, M. Cheng, S. Zhou, Q. Wu, N. Wang and L. Zhou, J. Phys. Chem. C, 2012, 116, 11702. 45 Y. Isomura, T. Narushima, H. Kawasaki, T. Yonezawa and Y. Obora, Chem. Commun., 2012, 48, 3784. 46 N. Sahiner, H. Ozay, O. Ozay and N. Aktas, Appl. Catal., A, 2010, 385, 201. 47 Z. Zhu, X. Guo, S. Wu, R. Zhang, J. Wang and L. Li, Ind. Eng. Chem. Res., 2011, 50, 13848. 48 F. Yuan, Y. Ni, L. Zhang, S. Yuan and J. Wei, J. Mater. Chem. A, 2013, 1, 8438. 49 K. Wu, X. Wei, X. Zhou, D. Wu, X. Liu, Y. Ye and Q. Wang, J. Phys. Chem. C, 2011, 115, 16268.

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