化学学报 ›› 2010, Vol. 68 ›› Issue (04): 320-324. 上一篇    下一篇

研究论文

缺碳型介孔空心球状WC制备及其对甲醇氧化的电化学行为

陈赵扬,马淳安*,赵峰鸣,乔芸,屠晓华   

  1. (浙江工业大学化材学院 绿色化学合成技术国家重点实验室培育基地 杭州 310032)
  • 投稿日期:2009-01-14 修回日期:2009-08-04 发布日期:2010-02-28
  • 通讯作者: 马淳安 E-mail:science@zjut.edu.cn
  • 基金资助:

    浙江省重大科技专项(2008C14040);国家自然科学基金(20476097)

Synthesis of Mesoporous Tungsten Carbide with Low Carbon Content and Its Electrocatalysis Toward Methanol Oxidation

Chen Zhaoyang Ma Chunan* Zhao Fengming Qiao Yun Tu Xiaohua   

  1. (State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032)
  • Received:2009-01-14 Revised:2009-08-04 Published:2010-02-28

采用喷雾干燥法制得空心球状结构偏钨酸铵, 通过固定床气固反应, 以CO/H2为还原碳化气氛在700~900 ℃下制备了介孔结构空心球状碳化钨(WC). 经XRD, SEM及EDS测试表明, WC粉末样品在保持了单相WC的前提下, 样品存在一个微量缺碳的原子比例, 其W/C>1, 且在高氢环境中WC球体表面有部分纳米颗粒依附于片状碳化钨基体上. 将制备得到的WC粉末样品制成微电极, 采用电化学测试技术研究了WC在硫酸介质中对甲醇的电催化氧化反应. 结果表明, 缺碳的介孔结构空心球状WC催化剂对甲醇氧化有着良好的电催化活性, 并对动力学参数进行了研究, 结果显示其反应的表观活化能为105.06 kJ/mol, 且其在微电极中的氧化行为受扩散控制.

关键词: 介孔结构, 碳化钨, 甲醇氧化, 电催化

The precursors ammonium metatungstate (AMT) microspheres were prepared by using an airflow spray drying method. Tungsten carbide (WC) samples were prepared by gas-solid reaction in the atmosphere of CO/H2 in 700~900 ℃. XRD, SEM and EDS results showed that the samples were pure WC, with a ratio of W/C>1. SEM images show that the structure of WC is hollow microsphere with nanoparticles around the surface. The WC was applied to a catalytic electrode for methanol electro-oxidation reaction by a PME (powder microelectrode) method. The results showed that the lower carbide content meso-WC-PME exhibited catalytic activity and stability in the methanol electro-oxidation, with the activation energy being 105.06 kJ/mol. The electrode reaction was controlled by liquid diffusion.

Key words: >mesoporous structure, tungsten carbide, methanol electro-oxidation, electrocatalysis

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