RESUMO
Tiara-like metal nanoclusters (TNCs) have attracted a great deal of attention because of their high stability and easy synthesis under atmospheric conditions as well as their high activity in various catalytic reactions. Alloying is one of the methods that can be used to control the physicochemical properties of nanoclusters, but few studies have reported on alloy TNCs. In this study, we synthesized alloy TNCs [NixPt6-x(PET)12, where x = 1-5 and PET = 2-phenylethanethiolate] consisting of thiolate, nickel (Ni), and platinum (Pt). We further evaluated the stability, geometric structure, and electronic structure by high-performance liquid chromatography and density functional theory calculations. The results revealed that NixPt6-x(PET)12 has a distorted structure and is therefore less stable than single-metal TNCs.
RESUMO
Practical electrochemical water splitting and carbon-dioxide reduction are desirable for a sustainable energy society. In particular, facilitating the oxygen evolution reaction (OER, the reaction at the anode) will increase the efficiency of these reactions. Nickel (Ni) compounds are excellent OER catalysts under basic conditions, and atomically precise Ni clusters have been actively studied to understand their complex reaction mechanisms. In this study, we evaluated the geometric/electronic structure of tiara-like metal nanoclusters [Nin(PET)2n; n = 4, 5, 6, where PET refers to phenylethanethiolate] with the same SR ligand. The geometric structure of Ni5(SR)10 was determined for the first time using single-crystal X-ray diffraction. Additionally, combined electrochemical measurements and X-ray absorption fine structure measurements revealed that Ni5(SR)10 easily forms an OER intermediate and therefore exhibits a high specific activity.