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 H 2 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 Cu 2+ site to C‐H dehydrogenation Au site to promote H 2 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 Mg 2+ /Al 3+ 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 × 10 4 h −1 ) than other biomass‐derived H 2 formation system, co‐producing lactic acid with selectivity up to 98.8%.