Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,...Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,remained challenging.Herein,we fabricated a frustrated single-atom Cu/O Lewis pair catalyst(Cu/O-FLP)by coupling epoxide group(C-O-C)with atomdispersed Cu-cis-N_(2)C_(2)Cl center to address this challenge.The basic epoxy site modulated the electron-deficient state of Lewisacidic Cu center and paired with the Cu-cis-N_(2)C_(2)Cl moiety to preferentially break HCl into different electronegative Cu-Clδ-and C-O-H^(δ+)intermediates,which further induced both an extra localized electric field to polarize acetylene and a upshift of the dband center of catalyst,thereby promoting adsorption and enrichment of acetylene by enhancing the dipolar interaction between acetylene and active intermediates.Moreover,the generated Cu-Clδ-and C-O-H^(δ+)drastically reduced the energy barrier of ratelimiting step and made vinyl chloride easier to desorb from the Lewis-basic oxygen-atom site rather than traditional Lewis-acidic Cu center.These superiorities ensured a higher activity of Cu/O-FLP compared with its counterparts.Meanwhile,preferential dissociation of HCl endowed single-atom Cu with the coordination-saturated configuration,which impeded formation of explosive copper acetylide by avoiding the direct interaction between Cu and acetylene,ensuring the intrinsic safety during catalysis.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.22062021)the Science and Technology Project of Xinjiang Bingtuan supported by Central government(No.2022BC001)+2 种基金the Opening Project of Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan(No.KF2019010)the Start-Up Foundation for high-level professionals of Shihezi University(No.RCZK201932)the research project of Shihezi University(No.CXFZ202205).
文摘Simultaneously boosting acetylene hydrochlorination activity and avoiding formation of explosive copper acetylide over Cu-based catalyst,which represented a promising alternative to Hg-based and noble metal catalysts,remained challenging.Herein,we fabricated a frustrated single-atom Cu/O Lewis pair catalyst(Cu/O-FLP)by coupling epoxide group(C-O-C)with atomdispersed Cu-cis-N_(2)C_(2)Cl center to address this challenge.The basic epoxy site modulated the electron-deficient state of Lewisacidic Cu center and paired with the Cu-cis-N_(2)C_(2)Cl moiety to preferentially break HCl into different electronegative Cu-Clδ-and C-O-H^(δ+)intermediates,which further induced both an extra localized electric field to polarize acetylene and a upshift of the dband center of catalyst,thereby promoting adsorption and enrichment of acetylene by enhancing the dipolar interaction between acetylene and active intermediates.Moreover,the generated Cu-Clδ-and C-O-H^(δ+)drastically reduced the energy barrier of ratelimiting step and made vinyl chloride easier to desorb from the Lewis-basic oxygen-atom site rather than traditional Lewis-acidic Cu center.These superiorities ensured a higher activity of Cu/O-FLP compared with its counterparts.Meanwhile,preferential dissociation of HCl endowed single-atom Cu with the coordination-saturated configuration,which impeded formation of explosive copper acetylide by avoiding the direct interaction between Cu and acetylene,ensuring the intrinsic safety during catalysis.
