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

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%.