Frustrated Lewis Pairs Enable Continuous Short-Range Hydrogen Spillover for Industrial-Scale Hydrogen Evolution.

Abstract

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-NH₂ 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.