Pt-based metals are very effective catalysts widely adopted in many fields. But the high cost prevents its further industrial application. One of the effective ways to solve the problem is to replace platinum with relatively cheap palladium and its alloy with copper. However, producing Pd/Cu bimetallic catalysts efficiently and economically with controllable particle size and uniform distribution is still challenging, especially when trying to reduce the consumption of precious metals. In this paper, ultrasmall palladium/copper (Pd/Cu) bimetallic catalysts with even dispersion were prepared on multi-walled carbon nanotubes (MWCNTs) by adding polyethylene glycol 400 (PEG 400) as a reducing agent and stabilizer under visible light irradiation at room temperature. The catalytic performance was studied in the catalysis of p-nitrophenol (p-NP) reduction. Of all the bimetallic catalysts produced in different conditions, the best one was obtained under the reaction condition of pH = 7 and violet light irradiation (wavelength 380-435 nm). The average particle size of 0.85 nm, and the apparent rate constant in the catalysis is 1.47 min-1. This research probes the role of visible light as a key kinetic controlling method in the formation of ultrasmall particles (UPs). It proves the effectiveness of using visible light irradiation as an effective and more "green chemistry" approach to get precious metal UPs as catalysts beyond the traditional ultraviolet or laser photochemistry methods.

以可见光作为冷光源,多壁碳纳米管(MWCNTs)为载体,在聚乙二醇(PEG)的水溶液体系中用简单的一步法可控合成了超细铂铜纳米催化剂,并就其在对硝基苯酚(p-NP)还原反应中的催化活性进行了研究.透射电子显微镜(TEM)图显示该催化剂为分散均匀的球状超细铂铜纳米粒子,平均粒径为0.99 nm.X射线衍射(XRD)表征结果显示催化剂的衍射峰介于Pt(fcc)和Cu(fcc)标准衍射峰之间,这说明该催化剂中Pt与Cu以面心立方晶格(fcc)结构的合金形式存在.X射线光电子能谱(XPS)结果证明该催化剂主要以PtCu双金属的同质结构形式存在,但还有少量Pt11和CuⅡ氧化态物质,这与少量Pt0 和Cu0 纳米粒子的自催化氧化有关.研究表明,当Pt:Cu的摩尔比为1∶ 1,反应溶液的pH值为10时,在350～455 nm可见光的照射下合成的催化剂对p-NP的反应速率常数为0.92 min-1,是铂/多壁碳纳米管(Pt/MWCNTs)催化剂的2倍,且稳定性良好.可见光照加速了反应体系的水解速率,影响了水解产物的物种分布.同时,由于双金属催化剂中一定量Cu原子的引入压缩了原来的Pt晶格,这种晶格应变及双金属的协同作用影响了催化剂的选择性和活性.

Here, platinum nanoparticles were synthesized on multi-walled carbon nanotubes (MWCNTs) in one step under the irradiation of visible light without any extra additives except ethylene glycol (EG) as the reducing agent and stabilizer, and Pt/MWCNTs composites were successfully prepared. The catalytic performance of Pt/MWCNTs was studied in the reduction of p-nitrophenol (p-NP). The morphology and crystal structure of as-synthesized materi-als were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Visible light irradiation promotes the hydrolysis of a [PtCl4]2-precursor in EG aqueous solution. By the electronic effect of the metal interface, the reduc-tion of platinum precursors makes the formation of the uniformly dispersed Pt metal ultra-small particles with an average of 2.1 nm size. The as-prepared Pt/MWCNTs effectively catalyzed the reduction of p-NP to p-aminophenol (p-AP) with NaBH4, exhibiting a high catalytic performance with an apparent rate constant of 0.25 min-1. Further-more, high reusability without significant activity loss presents that Pt/MWCNTs prepared can be an excellent and stable catalyst. The experimental results prove that besides traditional light irradiation methods, e.g. ultraviolet, the proper utilization of visible light is also a very effective method for preparing platinum metal catalysts and the morphology control can be achieved in some simple ways rather than complex reaction conditions.

利用湿化学法的可见光动力学控制策略,在未添加表面活性剂的乙二醇水溶液体系中,以多壁碳纳米管(MWC-NTs)为载体,通过一步法合成了钯多晶纳米催化剂,其平均粒径为16.5 nm.并通过傅立叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)、X射线衍射仪(XRD)和透射电子显微镜(TEM)完成了催化剂的微结构、组成和形貌的表征研究.结果表明,在可见光辅助下,乙二醇可以作为还原剂和稳定剂来制备纳米催化剂.由于金属的界面电子效应的影响,钯前驱体倾向于形成粒径比较大的多晶状颗粒.在对硝基苯酚(p-NP)的还原反应中,该催化剂的活化能为29.29 kJ/mol,室温下速率常数为0.2484 min-1,显示出了较高的催化活性.

This paper presents the visible light-assisted synthesis of surfactant-free Pt nanoparticles (Pt-NPs) supported on multi-walled carbon nanotubes (MWCNTs) at ambient condition. Transmission electron microscopy (TEM) images indicate that Pt-NPs with high density and relative small in size (about 2 nm) were monodispersed on the surface of MWCNTs. The characterizations of Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffractometer (XRD) and ultraviolet–visible spectroscopy (UV–Vis) prove that visible light irradiation significantly affect the species distribution of [PtCl4]2− precursor in the hydrolysis and then promote hydrolysate Pt oxides loading on MWCNTs. The loading process decides the morphology of Pt-NPs rather than the following precursor reduction, which does not change the morphology but only the valance state of platinum. The catalytic activity of Pt/MWCNTs was tested in subsequent methanol electrochemical reactions and 4-nitrophenol (4-NP) reduction.