Sunlight‐Driven Concurrent Synthesis of Jet Fuel Precursors and Hydrogen From Biomass‐Derived Furfuryl Alcohol Over Oxygen‐Doped Zn ₂ In ₂ S ₅

Photoreforming of biomass‐derived furfuryl alcohol (FA) offers a green and economic route for the concurrent production of jet fuel precursor hydrofuroin (HF) and hydrogen. However, conventional FA photoreforming is generally hampered by low quantum yield and poor HF selectivity. Herein, an oxygen‐doping strategy to modify the Zn 2 In 2 S 5 (ZIS) photocatalyst is reported, which markedly enhances both quantum yield and HF selectivity. Oxygen dopants fulfill multiple critical roles: engineering shallow donor levels to facilitate photocarrier separation and extend their lifetime, accelerating the conversion of the furfural (FF) byproduct, and strengthening FA adsorption. Notably, the O‐doped Zn 2 In 2 S 5 (ZIS‐O) achieves 95% HF selectivity under simulated sunlight alongside high apparent quantum yields (AQY) for HF: 37.6% at 380 ± 20 nm and 12.4% at 420 ± 20 nm. Pilot‐scale tests under natural sunlight reveal a long‐term average HF selectivity of 90% with a turnover number (TON) of 1390. Theoretical investigations confirm that oxygen dopants thermodynamically and kinetically favor the FA‐to‐HF conversion. These findings provide valuable mechanistic insights for the rational design of high‐performance photocatalysts tailored for the selective conversion of biomass‐derived platform molecules into value‐added chemicals.