School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou, 510275, P. R. China.
Collaborative Innovation Center of Sustainable Energy Materials, Guangxi University, Nanning, 530004, P. R. China.
Adv Mater. 2018 Nov;30(45):e1804074. doi: 10.1002/adma.201804074. Epub 2018 Sep 25.
Mastery over the architecture and elemental distribution of metal nanocrystals at the nanoscale can effectively tailor and improve their catalytic properties. Herein, the vertex-type-selective growth of metallic nanohorns on a central nanocrystal is constructed via a one-pot solvothermal synthesis, despite the fact that the site-selective epitaxy of the second phase proceeds on all the vertices of the seeds. The prepared vertex-type-selective Pt-Cu-Rh heterogeneous nanocages (HNCs) are composed of a Rh-decorated Pt-Cu rhombic dodecahedral nanocage and six Pt-Cu-Rh nanohorns protruding from the {100} rather than the {111} vertices of rhombic dodecahedron. Impressively, the Pt-Cu-Rh HNCs exhibit 8.1 times higher specific and 6.8 times higher mass activity toward the ethanol oxidation reaction under acidic conditions than commercial Pt/C catalysts. Besides, the peak potential for CO oxidation on Pt-Cu-Rh HNCs (370.4 mV vs SCE) is 182.0 mV more negative than that on Pt/C, indicating the dramatically enhanced CO tolerance. The excellent electrocatalytic property is attributed to the synergistic effect between Pt, Cu, and Rh components, high specific surface area of nanocages and nanohorns, as well as abundant concave/convex sites and various high-index facets around the surface.
在纳米尺度上对金属纳米晶体的结构和元素分布进行精确控制，可以有效地调整和改善其催化性能。在此，通过一锅溶剂热合成，在中心纳米晶体上构建了顶点型选择性生长的金属纳米角，尽管第二相的选择性外延在种子的所有顶点上进行。所制备的顶点型选择性 Pt-Cu-Rh 异质纳米笼（HNC）由 Rh 修饰的 Pt-Cu 面心立方十二面体纳米笼和从{100}而不是{111}面心立方十二面体顶点突出的六个 Pt-Cu-Rh 纳米角组成。令人印象深刻的是，在酸性条件下，Pt-Cu-Rh HNCs 对乙醇氧化反应的比表面积特异性和质量活性分别比商业 Pt/C 催化剂高 8.1 倍和 6.8 倍。此外，Pt-Cu-Rh HNCs 上 CO 氧化的峰电位（相对于 SCE 为 370.4 mV）比 Pt/C 负 182.0 mV，表明 CO 耐受性显著增强。优异的电催化性能归因于 Pt、Cu 和 Rh 组分的协同作用、纳米笼和纳米角的高比表面积以及表面周围丰富的凹凸位和各种高指数晶面。
