▎ 摘　　要

The development of electrocatalytic systems for efficient biomass conversion under mild conditions and understanding their mechanisms are of profound significance but remain challenging. Here, we report the development of a two-dimensional polymer-based mesoporous electrocatalyst (meso-PA/PmPD/GO) for biomass conversion, which comprises phytic acid (PA)-doped mesoporous poly(m-phenylenediamine) layers coated on graphene oxide. Meanwhile, a ternary electrolyte containing 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF(4)), acetonitrile, and H2O is selected. The combination of meso-PA/PmPD/GO and the electrolyte realizes efficient conversion of two important biomass derivatives. One involves the oxidation of furfuryl alcohol to 6-hydroxy-2,3-dihydro-6H-pyrano-3-one with high faradic efficiency (FE: 82.2%) and selectivity (86.1%). The other involves the oxidation of furfural to 5-hydroxy-2(5H)-furanone with record-high FE (98.2%) and selectivity (93.1%). A mechanistic study unveils that N-heterocyclic carbenes (Bmim*) generated from BmimBF(4) act as the reaction-determining species. The synergistic effect of the PA doping and mesoporous polymeric structure in meso-PA/PmPD/GO favors mass transport and electron-hole separation/transfer to the reactants, thus boosting catalytic performance.