Improved activity for the oxygen evolution reaction using a tiara-like thiolate-protected nickel nanocluster

Abstract

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 [Ni_n(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.