摘要
Using natural resources to construct electrocatalysts for biomass conversion and elucidating their catalytic mechanisms are of great significance,but have remained challenging.Here,a series of two-dimensional(2D)biomass-based Pb/PbO@C nanoparticles catalysts with Pb/PbO anchored on carbon nanosheets were synthesized using natural-derived humate as the precursor.By adjusting the carbonization temperature,an electron-deficient Pb0/Pb^(2+)dual-center-site catalyst can be achieved.The optimized Pb/PbO@C catalyst showed an excellent performance for the electrochemical hydrogenation of 5 hydroxymethylfurfural(HMF)to high value-added 2,5 bis(hydroxymethyl)furan(BHMF),with high Faradaic efficiency(FE:91.9%)and selectivity(Sel:89.7%),achieving comparable performance to those of the reported noble metal-based electrocatalysts.Mechanism study revealed that the electron-deficient Pb^(0)/Pb^(2+)dual-center-site provided abundant Lewis acidic sites and promoted the dissociation of water to the active hydrogen(H^(*))species,thus enhancing the adsorption of HMF on Pb^(2+)sites and the coverage of H^(*)species on Pb0 sites.The high coverage of H*species and the synergistic effect of dual-center sites substantially promoted the binding of H*and HMF to form H-HMF^(*)and inhibited the recombination of H^(*)species,thereby accelerating the reaction kinetics of HMF reduction.
基金
This work was supported by the National Natural Science Foundation of China(Nos.22225501 and 52073173)
the Key Research Projects of Universities in Henan Province(No.23A530005)
the National Key Laboratory of Biobased Transport Fuel Technology(No.KFKT2022002)of China
Program of Shanghai Academic/Technology Research Leader(No.23XD1431700)
Shanghai Engineering Research Center of Specialized Polymer Materials for Aerospace(No.18DZ2253500).
