Hydrogen Evolution Electrocatalyst Design: Turning Inert Gold into Active Catalyst by Atomically Precise Nanochemistry

作者：Yingwei Li, Site Li, Anantha Venkataraman Nagarajan, Zhongyu Liu, Sarah Nevins, Yongbo Song, Giannis Mpourmpakis, Rongchao Jin · 发表于：Journal of the American Chemical Society · 年份：2021 · DOI：10.1021/jacs.1c04606 · 被引用次数：114 · 研究领域：Nanocluster Synthesis and Applications、Advanced Nanomaterials in Catalysis、Advanced biosensing and bioanalysis techniques

Electrocatalytic hydrogen evolution reaction (HER) holds promise in the renewable clean energy scheme. Crystalline Au and Ag are, however, poor in catalyzing HER, and the ligands on colloidal nanoparticles are generally another disadvantage. Herein, we report a thiolate (SR)-protected Au 36 Ag 2 (SR) 18 nanocluster with low coverage of ligands and a core composed of three icosahedral ( I h ) units for catalyzing HER efficiently. This trimeric structure, together with the monomeric I h Au 25 (SR) 18 – and dimeric I h Au 38 (SR) 24, constitutes a unique series, providing an opportunity for revealing the correlation between the catalytic properties and the catalyst’s structure. The Au 36 Ag 2 (SR) 18 surprisingly exhibits high catalytic activity at lower overpotentials for HER due to its low ligand-to-metal ratio, low-coordinated Au atoms and unfilled superatomic orbitals. The current density of Au 36 Ag 2 (SR) 18 at −0.3 V vs RHE is 3.8 and 5.1 times that of Au 25 (SR) 18 – and Au 38 (SR) 24, respectively. Density functional theory (DFT) calculations reveal lower hydrogen binding energy and higher electron affinity of Au 36 Ag 2 (SR) 18 for an energetically feasible HER pathway. Our findings provide a new strategy for constructing highly active catalysts from inert metals by pursuing atomically precise nanoclusters and controlling their geometrical and electronic structures.