Defect engineering improves the catalytic performance of metal-organic frameworks(MOFs)loaded metal nanoparticles(MNPs@MOFs),but there is still a challenge in defining the structure-activity relationships.Herein,the c...Defect engineering improves the catalytic performance of metal-organic frameworks(MOFs)loaded metal nanoparticles(MNPs@MOFs),but there is still a challenge in defining the structure-activity relationships.Herein,the content of linker-missing defects in UiO-66(Ce)was systematically regulated via formic acid as the modulators,and defective UiO-66(Ce)loaded Ni nanoparticles(NPs)were constructed for dicyclopentadiene(DCPD)hydrogenation.The fine regulation of defect engineering and reduction conditions affected the structure properties of UiO-66(Ce)and the electronic metal-support interaction between MOFs and Ni NPs,thereby optimizing the microenvironment and electronic state of Ni NPs.The optimized U(Ce)-40eq with suitable defects,small size and structure stability effectively promoted the production of highly dispersed abundant electron-deficient Ni^(0) active sites,enhancing the adsorption and activation of H_(2) and C=C bonds,especially accelerating the rate-determining step.Therefore,U(Ce)-40eq loaded 5 wt%Ni NPs achieved DCPD saturated hydrogenation to tetrahydrodicyclopentadiene(70℃,2 MPa,90 min),superior to most high-loading Ni-based catalysts.This work reveals the synergistic mechanism of MOFs defect engineering and electronic structure of Ni NPs,providing effective guidance for the precise preparation of highly efficient and stable MNPs@MOFs heterogeneous catalysts.展开更多
文摘Defect engineering improves the catalytic performance of metal-organic frameworks(MOFs)loaded metal nanoparticles(MNPs@MOFs),but there is still a challenge in defining the structure-activity relationships.Herein,the content of linker-missing defects in UiO-66(Ce)was systematically regulated via formic acid as the modulators,and defective UiO-66(Ce)loaded Ni nanoparticles(NPs)were constructed for dicyclopentadiene(DCPD)hydrogenation.The fine regulation of defect engineering and reduction conditions affected the structure properties of UiO-66(Ce)and the electronic metal-support interaction between MOFs and Ni NPs,thereby optimizing the microenvironment and electronic state of Ni NPs.The optimized U(Ce)-40eq with suitable defects,small size and structure stability effectively promoted the production of highly dispersed abundant electron-deficient Ni^(0) active sites,enhancing the adsorption and activation of H_(2) and C=C bonds,especially accelerating the rate-determining step.Therefore,U(Ce)-40eq loaded 5 wt%Ni NPs achieved DCPD saturated hydrogenation to tetrahydrodicyclopentadiene(70℃,2 MPa,90 min),superior to most high-loading Ni-based catalysts.This work reveals the synergistic mechanism of MOFs defect engineering and electronic structure of Ni NPs,providing effective guidance for the precise preparation of highly efficient and stable MNPs@MOFs heterogeneous catalysts.
