Platinum modification of metallic cobalt defect sites for efficient electrocatalytic oxidation of 5-hydroxymethylfurfural  

作　　者：Haoyu Zhan Baixue Cheng Yankun Lu Danning Xing Xingshuai Lv Huining Huang Thomas Frauenheim Tao Wang Peng Zhou 

机构地区：[1]State Key Laboratory of Bio-fibers and Eco-textiles,College of Materials Science and Engineering,Collaborative Innovation Center of Shandong Marine Biobased Fibers and Ecological Textiles,Institute of Marine Biobased Materials,Qingdao University,Qingdao 266071,Shandong,China [2]Shandong Institute of Advanced Technology,Jinan 250100,Shandong,China [3]College of Chemistry and Chemical Engineering,Ocean University of China,Qingdao 266100,Shandong,China [4]Tianjin Key Laboratory of Advanced Functional Porous Materials,Institute for New Energy Materials & Low-Carbon Technologies,Schoolof Materials Science and Engineering Tianjin University of Technology,Tianjin 300384,China [5]School of Science,Constructor University,Bremen 28759,Germany [6]Beijing Computational Science Research Center,Beijing 100193,China [7]College of Chemistry and Molecular Engineering,Qingdao University of Science and Technology,Qingdao 266042,Shandong,China

出　　处：《Journal of Energy Chemistry》2025年第2期463-473,I0010,共12页能源化学(英文版)

基　　金：financially supported by the Natural Science Foundation of Shandong Province(ZR2023QB235,ZR202111240183,ZR2021QF120);the Postdoctoral Science Foundation of China(2022M711956);the Taishan Scholar Program of Shandong Province(tsqnz20231216).

摘　　要：Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)on OH-and HMF are weak,which limits its further application.Metal defect engineering can regulate the electronic structure,optimize the adsorption of intermediates,and improve the catalytic activity by breaking the symmetry of the material,which is rarely involved in the upgrading of biomass.In this work,we prepare Co_(3)O_(4)with metal defects and load the precious metal platinum at the defect sites(PtVco).The results of in-situ characterizatio ns,electrochemical measurements,and theoretical calculations indicate that the reduction of Co-Co coordination number and the formation of Pt-Co bond induce the decrease of electron filling in the antibonding orbitals of Co element.The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH species,thus exhibiting excellent HMF oxidation activity(including a lower onset potential(1.14 V)and 19 times higher current density than pure Co_(3)O_(4)at 1.35 V).In summary,this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail,provides a new option for improving the HMF oxidation activity of cobalt-based materials,broadens the application field of metal defect based materials,and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.

关 键 词：ELECTROCATALYSIS Biomass upgrading Metallic defect Coordination environment Adsorption enhancement 

分 类 号：TQ251.11[化学工程—有机化工] TQ426