[中文文摘]以无定形硒溶胶为模板制备了不同硒覆盖度(θSe)(θSe=0.49,0.39,0.06,0)的Pt-Se和Pt纳米空球(分别记为(Pt-Se)HN和PtHN),发展了利用亚硫酸盐彻底除去核壳纳米粒子上Se的方法.对获得的纳米空球进行了形貌和结构的表征,结果表明所制备的(Pt-Se)HN粒径均匀,分散性好,球壳呈多孔结构.以其作为电催化剂制备了(Pt-Se)HN修饰的玻碳(GC)电极((Pt-Se)HN/GC),利用常规电化学方法比较该电极与PtHN/GC和商用碳载铂(Pt/C)修饰GC(Pt/C/GC)电极对甲酸的催化氧化作用,发现对甲酸氧化的活性顺序为(Pt-Se)HN/GC>PtHN/GC>Pt/C/GC.三种电极催化甲酸氧化的机理有所不同:前者更倾向于通过弱吸附中间体直接氧化成CO2的单途径机理进行,后两者则通过强吸附和弱吸附中间体的双途径机理进行.在一定Se覆盖度条件下,(Pt-Se)HN/GC对甲酸的氧化有助催化作用.[英文文摘]Platinum-selenium and platinum hollow nanospheres(denoted as(Pt-Se)HN and PtHN,respectively) with different coverages of Se(θSe)(θSe=0.49,0.39,0.06,0) were prepared using amorphous Se colloids as a sacrificial template.Sulfite was used to completely remove Se from the core-shell nanoparticles.The morphology and structure of the nanoparticles were characterized using various methods,which revealed a hollow structure with a very uniform size distribution and a porous structure on the shell.Assembly of Pt-Se hollow nanospheres ((Pt-Se)HN) on a glassy carbon (GC) electrode produced a (Pt-Se)HN/GC electrode. The electrocatalytic activity of the electrode for the oxidation of formic acid was compared with the PtHN/GC and commercial Pt/C/GC electrodes by cyclic voltammetry and chronoamperometry. The activity followed the order:(Pt-Se)HN/GC > PtHN/GC >Pt/C/GC. The electrooxidation of formic acid on (Pt-Se)HN/C, PtHN/C, and Pt/C catalysts follows different mechanisms: the former tends to directly oxidize formic acid to CO2 via weakly adsorbed intermediates, and the latter two via both weakly and strongly adsorbed intermediates.(Pt-Se)HN with a suitable selenium content showed optimal electrocatalytic activity for the oxidation of formic acid. ; Corresponding authors. Email: zhqiling@163.com,bren@xmu.edu.cn; Tel:+86-13879159319. ; 国家自然科学基金(20663002); 厦门大学固体表面物理化学国家重点实验室基金(200511)资助项目