Carbon‐zero co‐production of hydrogen and chemicals boosted by directional hydrogen spillover via terminated interface

Abstract

Acceptorless dehydrogenation of biomass‐alcohol provides an appealing route for co‐producing green H2 and high‐value chemicals. However, the sluggish H species binding step severely inhibits reaction equilibrium and cause C‐C cleavage. Herein, we propose a unique directional H spillover strategy driven by controlling electron transport direction via constructing Au‐O‐Cu‐O‐Mg/Al interfacial structure, to allow H species transfer from O‐H dehydrogenation Cu2+ site to C‐H dehydrogenation Au site to promote H2 formation. The structure that each Cu precisely terminated by Mg/Al is inherited from layered double hydroxides with orderly dispersed atom arrangement. Comprehensive studies substantiate that the unreducible Mg2+/Al3+ blocks electron transfer toward support, whereas Au‐O‐Cu electronic interaction drives H spillover from the support to Au. The Au/CuMgAl catalyst demonstrated unprecedentedly high glycerol dehydrogenation activity, showing 3–10 times turnover frequency (1.18 × 104 h−1) than other biomass‐derived H2 formation system, co‐producing lactic acid with selectivity up to 98.8%.