缺碳型介孔空心球状碳化钨制备和其对甲醇氧化的电化学行为.pdfVIP

2010 年第68 卷 化 学 学 报 Vol. 68, 2010 第4 期, 320～324 ACTA CHIMICA SINICA No. 4, 320～324 ·研究论文· 缺碳型介孔空心球状碳化钨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 (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) 摘要 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 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 (State Key Laboratory Breeding Base for Green Chemistry Synthesis Technology, College of Chemical Engineering and Materials Science , Zhejiang University of Technology, Hangzhou 310032) Abstract The precursors ammonium metatungstate (AMT) microspheres were prepared by using an air- flow spray drying method. Tungsten carbide (WC) samples were prepared by gas-solid reaction in the at- mosphere 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 nanoparti- cles 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