Ni‐Doped ZnIn ₂ S ₄ Piezophotocatalysts for 100% Selective Stoichiometric Conversion of Glucose to Arabinose and Formic Acid With Concurrent Hydrogen Evolution From Water

ABSTRACT This study demonstrates that glucose can be stoichiometrically converted to arabinose and formic acid with 100% selectivity through a piezophotocatalytic process on ZnIn 2 S 4 ‐based nanosheets, while simultaneously driving the hydrogen evolution from water. A series of Ni‐doped ZnIn 2 S 4 catalysts with varying doping concentrations is hydrothermally synthesized. Structural characterizations confirm substitutional incorporation of Ni at Zn lattice sites, accompanied by vacancy formation, whereas the surface layers of self‐assembled nanosheets remain Ni‐free. Under intensified fluid‐induced shear stress, the ZnIn 2 S 4 ‐based catalysts exhibit significantly enhanced piezophotocatalytic performance for both hydrogen production and glucose valorization. An optimal Ni doping level is identified that maximizes piezoelectric polarization, delivering a fivefold increase in the yields of H 2 , arabinose, and formic acid compared to pristine ZnIn 2 S 4 , thereby highlighting the critical role of Ni doping in amplifying piezoelectric effects. Multiscale simulations reveal that Ni incorporation in ZnIn 2 S 4 primarily modulates vacancy concentrations and bulk electronic properties, including dielectric response, elastic modulus, and piezoelectric potential, to boost charge separation efficiency. Mechanistic insights establish that protons for H 2 evolution originate from water, while photogenerated holes and hydroxyl radicals produced via hole‐driven water oxidation under piezophotocatalytic conditions govern the highly selective stoichiometric conversion of glucose to arabinose and formic acid on ZnIn 2 S 4 ‐based catalysts.