Single atom–cluster synergy in Ag catalysts enables chiral glyceric acid from biomass
S. L. XU, Jianmei Li, Jiong Cheng, Ruoyu Li, Xiaoyan Wang, Shengqi Liao, Hua‐Qing Yang, Changwei Hu, Ning Yan
Abstract
Accessing optically pure chemicals directly from biomass via chemical catalysis remains challenging because of the need for high selectivity across complex, multistep transformations. Here, we report a robust silver-based catalyst featuring synergistic single atoms and nanoclusters that function as complementary active sites in the anaerobic oxidative carbon-carbon cleavage of bio-derived feedstocks. This catalyst enables the production of optically pure glyceric acid from a broad range of biomass sources including raw biomass with unprecedented yield (59 to 96%) and enantiomeric excess (97 to >99%). Structural and mechanistic studies reveal that silver clusters, stabilized by surface oxygen vacancies, activate dioxygen through π-backbonding, while electron-deficient silver single atoms preferentially bind the chiral substrate via ionic interactions, increasing the energy barrier for mutarotation and preserving its stereochemical identity. Oxygen spillover between the two sites facilitates precise oxidative Cα-Cβ bond cleavage. Together, these features overcome the longstanding dual challenges of low productivity and poor enantioselectivity in chemocatalytic biomass upgrading.