Architecting Core–Shell S‐Scheme Interfaces for Photocatalytic Conversion of Cellulosic Biomass‐Based Feedstock to Biofuel and H ₂ Generation: A Paradigm for Photo‐Biorefinery

Abstract Solar‐to‐fuel production via integration of light energy and the valorization of biomass‐based feedstock over a photocatalytic system to produce green fuel and essential chemicals can be a game changer toward sustainable development. The production of γ‐valerolactone (GVL) – a biofuel in synergism with H ₂ generation– a sustainable fuel from levulinic acid (LA) – a biomass‐derived renewable feedstock utilizing a cost‐effective photocatalytic system represents an important reaction. Moving forward in this direction, we synthesized and applied core‐shell based interfacial nanostructured material (ZIS/aTO) employing high‐surface area ZnIn ₂ S ₄ (ZIS) nanosheets grown over amorphous phase TiO ₂ (aTO) nanorods for the transfer hydrogenation of levulinic acid in iso‐propanol (i‐PrOH) as hydrogen donor. The optimal heterojunction showed excellent conversion activity (>99%) to produce GVL and GHV (γ‐hydroxyvaleric acid) along with the generation of high H ₂ amounts (>1 mmol g ⁻¹ ) from i‐PrOH using simulated solar light. The developed heterostructure showed enhanced charge separation and migration properties along with efficient interfacial electron transfer from aTO to ZIS in an S‐scheme manner. The in situ EPR analysis provided insights into the mechanistic pathway through the detection of hydroxyl carbon radical. Thus, photocatalytic protocol demonstrates an easy way of integrating solar energy utilization and valorization of renewable feedstock as a promising route toward sustainable production of bio‐fuels and chemicals along with hydrogen.