Concurrent alloying and vacancy engineering for intensifying hydrogen spillover towards alcohol-water co-electrolysis

Overcoming the thermodynamic and kinetic barrier of the hydrogen spillover process is of vital significance for improving the electrocatalytic hydrogen evolution reaction (HER) activity of the metal-supported binary catalysts. Here, we innovatively develop an alloying and vacancy engineering strategy to synergistically narrow the work function difference between the metal and support (& UDelta;& phi;) and sequentially intensify the effective interfacial hydrogen transfer by constructing a metallene-like PdRu-RuO2 heterostructure with a well-designed PdRu alloy phase and abundant oxygen vacancies. Experimentally, the optimal PdRu-RuO2 heterostructures can concurrently drive hydrogen production and the alcohol oxidation reaction (AOR) by delivering ultrahigh catalytic activity, which enables them to act as promising bifunctional electrocatalysts for hydrogen production from an aqueous solution of alcohols. Based on a combination of theoretical simulations and experiments, it is rationalized that the formation of the heterostructure of PdRu alloy and oxygen-vacancy-enriched RuO2 synergistically decreases the & UDelta;& phi; and facilitates interfacial hydrogen spillover, endowing the PdRu alloy with efficient hydrogen adsorption and RuO2 with facile hydrogen desorption.

Automated summary

Overcoming the barrier of hydrogen spillover process is crucial for improving the catalytic activity of metal-supported binary catalysts in hydrogen evolution reaction (HER). In this study, an alloying and vacancy engineering strategy was innovatively developed to narrow the work function difference between the metal and support (& UDelta;& phi;) and enhance the interfacial hydrogen transfer. The constructed PdRu-RuO2 heterostructure exhibited efficient catalytic activity for hydrogen production and alcohol oxidation reaction (AOR), making it a promising bifunctional electrocatalyst for hydrogen production from alcohol aqueous solutions.