Methanol-Enhanced Low-Cell-Voltage Hydrogen Generation at Industrial-Grade Current Density by Triadic Active Sites of Pt 1 –Pd n –(Ni,Co)(OH) x

作者：An Pei, Ruikuan Xie, Lihua Zhu, Fengshun Wu, Zinan Huang, Yongyu Pang, Yu‐Chung Chang, Guoliang Chai, Chih‐Wen Pao, Qingsheng Gao, Congxiao Shang, Guang Li, Jinyu Ye, Huaze Zhu, Zhiqing Yang, Zhengxiao Guo · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.4c12665 · 被引用次数：155 · 研究领域：Electrocatalysts for Energy Conversion、Fuel Cells and Related Materials、Advanced battery technologies research

Methanol (ME) is a liquid hydrogen carrier, ideal for on-site-on-demand H 2 generation, avoiding its costly and risky distribution issues, but this “ME-to-H 2 ” electric conversion suffers from high voltage (energy consumption) and competitive oxygen evolution reaction. Herein, we demonstrate that a synergistic cofunctional Pt 1 Pd n /(Ni,Co)(OH) x catalyst with Pt single atoms (Pt 1 ) and Pd nanoclusters (Pd n ) anchored on OH-vacancy(V OH )-rich (Ni,Co)(OH) x nanoparticles create synergistic triadic active sites, allowing for methanol-enhanced low-voltage H 2 generation. For MOR, OH* is preferentially adsorbed on Pd n and then interacts with the intermediates (such as *CHO or *CHOOH) adsorbed favorably on neighboring Pt 1 with the assistance of hydrogen bonding from the surface hydrogen of (Ni,Co)(OH) x . The enhanced selectivity of the *CHOOH pathway, instead of *CO, sustains the MOR activity to a practically high current density. For HER, triadic Pt 1, Pd n, and OH-vacancy sites on (Ni,Co)(OH) x create an “acid–base” microenvironment to facilitate water adsorption and splitting, forming H* species on Pt 1 and Pd n, and *OH at the vacancy, to promote efficient H 2 evolution from the asymmetric Pt 1 and Pd n sites via the Tafel mechanism. The triadic-site synergy opens new avenues for the design and synthesis of highly efficient and stable cofunctional catalysts for “on-site-on-demand” H 2 production, here facilitated by liquid methanol.