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Updated: Oct 26, 2026

Hydrogen Production and Utilization in a Membrane Reactor
Published on: March 10, 2023
A review on the hydrogen spillover effect for boosting the electrocatalytic hydrogen evolution reaction
Zhong-Qiu Liu1, Jing-Hao Zhou1, Qing-Qing Sun1
1School of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, China. sunqingqing08@126.com.
Abstract:
Hydrogen spillover effect (HSE) has emerged as an important interfacial transport paradigm that connects hydrogen activation on metal sites with utilization on adjacent supports, enabling multi-site cooperative electrocatalysis for the hydrogen evolution reaction (HER). By spatially coupling hydrogen generation, interfacial migration, and recombination, HSE provides a promising route to overcome limitations imposed by hydrogen adsorption scaling relationships. However, it remains a qualitatively recognized yet quantitatively underdefined phenomenon, particularly regarding interfacial hydrogen migration mechanisms and its contribution to catalytic performance. This review critically summarizes recent progress in HSE-enabled HER catalysts, focusing on mechanistic understanding, advanced characterization techniques, and rational design strategies. We highlight experimental and operando methods, including spectroscopy, isotope-tracing, electrochemical analysis, and theoretical modeling, for probing hydrogen migration pathways. Representative catalyst systems spanning metal-oxide, hydroxide, carbide, sulfide, phosphide, and metallic interfaces are discussed, emphasizing interfacial electronic coupling and hydrogen transport behavior. Key design principles are distilled, including work function regulation, pathway shortening, interface engineering, and single-atom construction. Finally, we discuss remaining challenges in unambiguous identification, quantitative description, and realistic modeling of HSE. We propose that HSE should be recognized as a general multi-site hydrogen transport mechanism, and that integrating operando characterization with predictive theory is essential for rational catalyst design and next-generation HER optimization.
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