A Photocatalytic Tandem Process Drives Flavor Ingredient Production from Biomass

Oscillatory transition is a cyclical process of “balance→ imbalance→ new balance” in nature, which achieves continuous generation of a new substance through structural reorganization. In this work, we proposed a “chemical oscillatory transition” to drive the sustainable production of flavor ingredients from the biomass resources, where the photocatalytic tandem process of “acetalization → dehydrogenation → hydrolysis” has been established for achieving the transformation of bioderived furfurals to alkyl furoates. At ambient temperature, a 99.9% conversion of furfural (FUR) with 92.0% selectivity of methyl-2-furoate (MF) is obtained using a nickel-doped zinc indium sulfide (Ni/ZIS) catalyst, simultaneously generating 340 μmol of H 2 . Mechanistic investigations revealed that the oscillatory system transformations from “FUR ↔ 2-(dimethoxymethyl)furan (DMMF)” to “DMMF ↔ 2-(trimethoxymethyl)furan (TMMF)” in methanol are crucial to MF production. This provides a sustainable and atom-economical strategy for synthesizing the flavor ingredient from renewable biomass feedstocks.