Lignin‐Derived Construction of Ternary Heterojunctions with Electronic Bridge Interfaces for Efficient Photothermal Conversion of α‐Cellulose Into Hydrogen and 1,5‐Anhydro‐D‐glucitol

Abstract The strategic development of sustainable hydrogen production technologies from lignocellulosic biomass is critical for advancing carbon‐neutral energy systems. This work presents a ternary photothermal catalyst anchored on lignin‐derived carbon (LC), where lignin serves as a sustainable carbon source and stabilizing scaffold to enhance metal dispersion and coke resistance. The synergistic effect of Ni plasmonic heating, ZnO photocatalysis, and a Ni 3 ZnC 0.7 electronic bridge enable charge redistribution, broad solar absorption, and localized heating, thus delivering high activity, stability, and selectivity for both hydrogen evolution and α‐cellulose valorization. The optimized NiZn‐1:1 composite achieves a hydrogen evolution rate of 28.34 mmol g cat −1 h −1 in a 10% EtOH/H 2 O solvent, that is 8.2 times higher than that of conventional photocatalytic or thermal systems. Density Functional Theory calculation and operando characterization reveal that the ethanol solvent facilitates α‐cellulose solubilization and optimizes adsorption energetics, while the heterojunction balances d‐band electron localization and oxygen vacancy generation. Notably, the system maintains 80% stability over five cycles and produces a high value byproduct (1,5‐Anhydro‐D‐glucitol) through self‐supplied hydrogen‐assisted glucose reduction. This work provides a scalable strategy for converting biomass to hydrogen and offers mechanistic insights into photothermal catalysis within complex reaction networks.