以HKUST-1为前驱体的Cu@Pt/C催化剂的结构及对甲醇的催化氧化性能研究  

Structure of Cu@Pt/C catalyst derived from HKUST-1 and its catalytic activity for methanol oxidation

作　　者：龙翔宇 雷霆[1] 王坤婵 詹振翔 LONG Xiangyu;LEI Ting;WANG Kunchan;ZHAN Zhenxiang(State Key Laboratory of Powder Metallurgy, Central South University, Changsha 410083, China)

机构地区：[1]中南大学粉末冶金国家重点实验室

出　　处：《粉末冶金材料科学与工程》2019年第3期289-295,共7页Materials Science and Engineering of Powder Metallurgy

基　　金：国家自然科学基金资助项目(21673297)

摘　　要：以硝酸铜和均苯三甲酸为原料,水热合成八面体结构的金属有机物框架(HKUST-1)前驱体,前驱体在 Ar保护下煅烧发生热分解和碳热还原,得到 Cu/C 纳米颗粒,再与氯铂酸钾通过置换反应得到 Cu@Pt/C 催化剂。利用扫描电镜、X 射线衍射仪以及 X 射线光电子能谱仪对 Cu@Pt/C 催化剂的形貌与结构进行表征,并测试其对甲醇溶液的电催化氧化性能。结果表明,Cu@Pt/C 催化剂保留了前驱体 HKUST-1 的八面体结构,Pt 包覆在 Cu 表面形成核壳结构。根据 Cu@Pt/C 催化剂在 H2SO4溶液中的循环伏安曲线,计算出其电化学活性面积为 74.3 m^2/g,约为商业 Pt/C 的 1.47 倍,并且 Cu@Pt/C 催化电极在 H2SO4与甲醇混合溶液中的循环伏安扫描曲线的正扫过程中的峰值电流密度(Jf)与负扫过程中的峰值电流密度(Jb)的比值(Jf/Jb)为 2.18,远高于商业 Pt/C 电极,表现出优异的对甲醇的电催化氧化活性和抗 CO 中毒性能。Copper nitrate and trimesic acid were used as raw materials to fabricate octahedral HKUST-1 by hydrothermal method. HKUST-1 was calcined in Ar protective atmosphere and Cu/C nanoparticles were derived through carbothermal reduction reaction. The Cu@Pt/C catalyst was obtained by soaking Cu/C in potassium chloroplatinic acid solution by galvanic displacement. The morphology and microstructure of Cu@Pt/C catalyst as well as its electrocatalytic activity towards methanol were further characterized by SEM, XRD, XPS and cyclic voltammetry (CV). The results show that the as-prepared Cu@Pt/C catalyst retains special octahedral structure of HKUST-1 and has a core-shell structure formed by Pt coating on the surface of Cu. The electrochemically active surface areas (ECSA) measured by cyclic voltammetry curves in H2SO4 solution is 74.3 m^2/g, about 1.47 times as much as that of commercial Pt/C. The cyclic voltammetry curves in H2SO4+CH3OH solution shows the ratio of positive sweep peak current density to reverse sweep peak current density Jf/Jb is 2.18, which is much higher than that of commercial Pt/C. Thus Cu@Pt/C catalyst has better electrocatalytic activity to methanol oxidation and better CO tolerance.

关 键 词：核壳结构 甲醇氧化 电催化 金属有机框架 置换反应 

分 类 号：TB333[一般工业技术—材料科学与工程]