Hydrogen sensing properties of Pt-Au bimetallic nanoparticles loaded on ZnO nanorods
Introduction
Hydrogen is an important and promising energy sources because it is renewable, abundant, efficient, and environmental-friendly, and it is also an important raw material for the industry [1], [2], [3], [4], [5], [6], [7], [8]. However, the using of H2 has high risk of explosion if its concentration exceeds 4% in air, and the safety issues will always arise when hydrogen is used or produced [9], [10], [11], [12]. Therefore, the development of highly sensitive and fast-detecting hydrogen sensors for the detecting of H2 leakage from storage and transporting equipment is very important and urgent.
Semiconductor based gas sensors is one of the most important equipment for the detection of gases, and they have been widely used to detect the H2S, ethanol, CO, CH4, NO2 etc. [13], [14], [15], [16], [17]; however, the sensitivity to H2 is very low. It is reported that the deposition of noble metal can enhance the H2 sensing performances of sensors due to the strong oxygen dissociation and spillover effect of noble metals with unique electric and catalytic properties and the synergic electronic interaction with the oxide materials [18], [19], [20], [21], [22]. Ghim Wei Ho, et al. [23] reported that Pd based sensor has excellent H2 sensing performance. Leu et al. [24] prepared Pd nanoparticles decorated ZnO nanorods with superior sensing properties to the H2 even at room-temperature. Xie et al. [25] also reported that Pt-functionalized NiO nanotubes show superior gas sensing performance. Wang et al. [18] has prepared Au functionalized ZnO nanowires, and the results demonstrated that the sensor with Au functionalized exhibited not only faster response and recovery but also higher sensitivity to benzene and toluene than the pristine ZnO senor. However, the response of those reported sensors to H2 is still low or the operation of these sensors requires high temperature.
The bimetallic nanoparticles consisting of two or more components usually exhibit different properties from their mono-metal analogues because of the geometric and electronic effect between the two metals [26], [27], [28], [29]. PdAu bimetallic nanoparticles shows excellent stability for the oxygen reduction reaction [30]. Bert D. Chandler et al. reported that incorporating small amounts of Pd into supported Au catalysts has been shown to have beneficial effects on selective hydrogenation reactions [31]. In addition, it is reported that the bimetallic materials have showed superior sensing properties to the gases, such as H2, oxygen, and liquefied petroleum gas [32], [33]. Therefore, it is of great interest to investigate the gas sensing properties of the bimetallic nanoparticles modified gas sensing materials. As is well known, the Pt is an excellent hydrogenation and oxygen reduction reaction catalyst [34], [35], [36], [37]; while the Au based catalysts have been identified as highly active for many oxidation reactions, such as CO oxidation [38], and the selective oxidation of alcohols [39], [40], because of their excellent hydrogen and oxygen adsorption and/or dissociation properties. As the sensing response of the sensor to H2 is defined as the resistance changes of the sensor in air and in H2, and that depends on the both adsorption of hydrogen and oxygen onto the materials, so it is very necessary to study the effect of the Pt-Au bimetallic nanoparticles on the H2 sensing performance since the coexistence of Pt and Au will promote both the adsorptions of H2 and O2 onto the materials.
Herein, we have prepared Pt-Au bimetallic nanoparticles with Pt and Au homogeneously distributed, and then the Pt-Au nanoparticles were loaded onto the ZnO nanorods. The gas sensing performance of the ZnO-supported Pt-Au nanoparticles (Pt-Au/ZnO) to H2 were tested, and the Pt-Au/ZnO exhibits higher sensing response to H2 than the mono-metal modified ZnO, and the Pt-Au/ZnO also shows high sensing response to H2 even operated at room temperature.
Section snippets
Materials
The sodium hydroxide (NaOH), Hexadecyltrimethy Ammonium Bromide (CTAB), zinc nitrate (Zn(NO3)2·6H2O), H2PtCl6&903;6H2O, HAuCl4&903;4H2O, polyvinyl alchol (PVA, MW ≈ 2000), and NaBH4 were analytic grade and used without further purification. The water used in all the experiments was deionized and had an electrical conductivity <10−6 s cm−1.
Preparation of the noble metal nanoparticles modified ZnO nanorods
The ZnO nanorods were obtained by a hydrothermal method [41]. For the synthesis of the Pt-Au alloys nanoparticles, 4.24 mg of PVA, 0.5 mL of 20 mM HAuCl4 solution,
Structure and morphology of the samples
Fig. 1(a) shows the XRD pattern of the Pt-Au colloidal sol. The pattern exhibits two diffraction peaks that can be indexed to diffraction peaks of the (111) and (200) of the metallic Pt-Au [44]. The diffraction peaks of bimetallic Pt-Au located between Au and Pt demonstrate the formation of Pt-Au nanoalloys. Fig. 1(b) shows the UV–vis absorption spectra of Au and Pt-Au colloidal sols. The appearance of the peaks at ∼540 nm is characterized for gold nanoparticles, while no absorption peaks
Conclusions
In conclusion, ZnO supported Pt-Au bimetallic nanoparticles has been prepared. The bimetallic nanoparticles with Pt and Au homogeneously distributed are uniformly and stably coated onto the ZnO nanorods, and a gas sensor based on the Pt-Au bimetallic nanoparticles loaded ZnO has been manufactured. The gas sensing testing results indicate that the obtained Pt-Au bimetallic nanoparticles loaded ZnO shows higher sensing response to 250 ppm H2, which is 9.6 times higher than the ZnO supported Au, 47
Acknowledgments
This work was supported by the National Natural Science Foundations of China, Beijing Engineering Center for Hierarchical Catalysts, the Fundamental Research Funds for the Central Universities (YS1406), Qinghai Science&Technology Projects (2016-ZJ-927Q, 2016-GX-103), and the funds of the Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lake, Chinese Academy of Sciences.
Faying Fan received her PhD degree in 2015 at BUCT. She is a lecturer in the Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lake, Chinese Academy of Sciences. Her research project involves sensing materials and environmentally friendly catalytic materials.
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Faying Fan received her PhD degree in 2015 at BUCT. She is a lecturer in the Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lake, Chinese Academy of Sciences. Her research project involves sensing materials and environmentally friendly catalytic materials.
Jiajun Zhang is currently pursuing a postgraduate degree at BUCT. His research project involves sensing materials and application.
Jiao Li received her postgraduate degree in 2016 at BUCT. Her research project involves sensing materials and application.
Na Zhang received her postgraduate degree in 2016 at BUCT. Her research project involves catalytic materials and application.
Runrun Hong received her bachelor's degree from BUCT and is currently pursuing a PhD degree at BUCT. His research project involves environmentally friendly catalytic materials.
Xiaochuan Deng is a researcher in the Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lake, Chinese Academy of Sciences. His research interests include the development of new method and technique of salt resource materials application.
Pinggui Tang received his PhD degree in 2011 at BUCT. He is a lecturer in the College of Science in BUCT. His research is focused on intercalation chemistry of layered double hydroxides and inorganic functional materials.
Dianqing Li received his MS degree in 1989 at Beijing Institute of Chemical Technology and PhD degree in 2001 at Tianjin University. His research interests are the development and application of functional inorganic materials. He is currently a professor in the State Key Laboratory of Chemical Resource Engineering at Beijing University of Chemical Technology (BUCT).