Frustrated Lewis Pairs Enable Continuous Short-Range Hydrogen Spillover for Industrial-Scale Hydrogen Evolution
Zhaozheng Zhang, Xianbiao Hou, Tengjia Ni, Jian Zhou, Canhui Zhang, Kecheng Tong, Shuixing Dai, Lei Chu, Huanlei Wang, Minghua Huang
Abstract
High Resolution Image Download MS PowerPoint Slide Efficient hydrogen evolution reaction (HER) in alkaline and neutral media remains a major challenge due to sluggish water dissociation and limited proton availability. Hydrogen spillover presents a promising strategy to couple proton generation and utilization; yet, its application in single-component catalysts is greatly limited by the absence of effective driving forces for hydrogen migration. Herein, we report an amino-functionalized NiRu-based metal–organic framework (MOF) as a single-component catalyst, wherein spontaneously formed frustrated Lewis pairs (FLPs) composed of Ni sites and amino groups function as cooperative active sites to drive coupled water dissociation and hydrogen spillover, establishing a continuous short-range spillover pathway. Experimental and theoretical results reveal that Ni-NH 2 FLPs promote water adsorption and dissociation, generating a locally acidic microenvironment conducive to proton transport. Meanwhile, the amino groups modulate the electronic structure of neighboring Ru sites, lowering the energy barrier for hydrogen desorption and promoting spillover-mediated hydrogen release. As a result, the catalyst achieves Pt-beyond HER activity and durability under alkaline and neutral conditions at industrial current densities. The assembled alkaline electrolyzer further demonstrates a low cell voltage (1.76 V at 0.5 A cm –2 ), high energy efficiency (71.2%), and hydrogen production cost ($0.94 per GGE) below the U.S. Department of Energy target.