Photocatalytic Glucose Reforming for Formic Acid on 2D Amorphous MoO3‐x/TNTs Heterojunction in Pure Water

Formic acid is a promising hydrogen‐storage material and biohydrogen production intermediate, offering sustainable biomass‐derived alternative processes. Herein, a two‐dimensional amorphous molybdenum oxide/titanium oxide nanotubes (MoO3‐x/TNTs) heterojunction with amorphous/crystalline interfaces, is designed and fabricated by supercritical CO2, with which the photocatalytic reforming of glucose for formic acid is realized in pure water. The HCOOH yields of 14.8% for glucose and 22% for glycerol are achieved in pure water at room temperature with 2 bars O2 atmosphere within 6 hours under 365 nm light with 5 mW/cm2. The photoinduced Mo6+‐catalyzed ligand‐to‐metal charge transfer (LMCT) and the enhanced adsorption energy of glucose molecules on the MoO3‐x surface in the MoO3‐x/TNTs heterojunction facilitate the cleavage of C‐C bonds in polyhydric alcohol skeletons, leading to the formation of HCOOH. Under light excitation, MoO3‐x transfers electrons to TNTs due to defect state, synergizing with the generated •OH radicals in the system. This results in reversible cycling between Mo6+ and Mo5+, thereby ensuring catalytic persistence. Therefore, this study demonstrates a photocatalytic strategy for the sustainable production of value‐added chemicals from biomass under eco‐friendly conditions, using easily recyclable heterogeneous catalysts in pure water.