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

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Efficient hydrogen evolution reaction (HER) in alkaline and neutral media is crucial for clean energy but faces challenges in water dissociation and proton availability.
• Hydrogen spillover is a promising strategy, but its use in single-component catalysts is limited by a lack of effective hydrogen migration driving forces.

Purpose of the Study:

• To develop a single-component catalyst for efficient HER by addressing limitations in water dissociation and hydrogen migration.
• To investigate the mechanism of cooperative active sites and hydrogen spillover in a novel amino-functionalized NiRu-based MOF.

Main Methods:

• Synthesis and characterization of an amino-functionalized NiRu-based metal-organic framework (MOF).
• Electrochemical evaluation of the catalyst for HER in alkaline and neutral media.
• Experimental and theoretical studies (e.g., DFT) to elucidate the catalytic mechanism involving frustrated Lewis pairs (FLPs) and hydrogen spillover.

Main Results:

• The NiRu-MOF catalyst, featuring Ni-NH2 FLPs, demonstrated efficient water adsorption, dissociation, and proton transport.
• Amino groups modulated Ru sites, lowering desorption barriers and promoting spillover-mediated hydrogen release.
• The catalyst achieved platinum-beyond HER activity and durability at industrial current densities.

Conclusions:

• The developed NiRu-MOF catalyst effectively couples water dissociation and hydrogen spillover via Ni-NH2 FLPs, overcoming key HER challenges.
• The catalyst exhibits superior performance in alkaline and neutral media, suitable for industrial applications.
• An assembled alkaline electrolyzer using this catalyst showed high efficiency and low hydrogen production cost, meeting U.S. DOE targets.