In Fenton-like reaction activated by peroxymonosulfate(PMS),compared to SO_(4)^(•-)produced via the electron acceptance path,^(1)O_(2)generated from electron donation path were more attractive.Herein,PMS activation pa...In Fenton-like reaction activated by peroxymonosulfate(PMS),compared to SO_(4)^(•-)produced via the electron acceptance path,^(1)O_(2)generated from electron donation path were more attractive.Herein,PMS activation path was altered from SO_(4)^(•-)to^(1)O_(2)through improving Lewis acidity on catalytic sites.During ZIF-67 preparation,vanillin(VAN)was introduced to regulate the chemical environment around the Co^(3+/2+)nodes.The coordinated N atoms in 2-methylimidazole were partially substituted by O atoms in VAN,leading to the enhanced Lewis acidity on Co^(3+/2+)sites.In this case,Lewis base PMS were likely to donate electrons to electron-deficient Co^(3+/2+)sites,and 1O_(2)were generated as the primary radicals.Besides,coordinatively unsaturated metal sites(CUMSs)were produced during the substitution process,since Co^(3+/2+)nodes were not fully bridged by VAN ligands.This improved the PMS utilization efficiency and ^(1)O_(2)yield.Previous studies have indicated the metal leaching would be worsened by CUMSs,owing to the lack of ligand protection.To solve this problem,a Co_(2)SiO_(4)shell was coated on VAN-ZIF-x surface.VAN-ZIF-x@Co_(2)SiO_(4)yolk@shell nanoreactor not only suppressed the metal leaching,but also improved the environmental adaption.This paper gave a novel insight on altering the PMS activation path,together with the CUMSs creation on catalyst surface.展开更多
基金supported by State Key Laboratory of Urban-rural Water Resources and Environment(Harbin Institute of Technology,No.2025TS45)Natural Science Foundation of Heilongjiang Province,China(No.PL2024B019).
文摘In Fenton-like reaction activated by peroxymonosulfate(PMS),compared to SO_(4)^(•-)produced via the electron acceptance path,^(1)O_(2)generated from electron donation path were more attractive.Herein,PMS activation path was altered from SO_(4)^(•-)to^(1)O_(2)through improving Lewis acidity on catalytic sites.During ZIF-67 preparation,vanillin(VAN)was introduced to regulate the chemical environment around the Co^(3+/2+)nodes.The coordinated N atoms in 2-methylimidazole were partially substituted by O atoms in VAN,leading to the enhanced Lewis acidity on Co^(3+/2+)sites.In this case,Lewis base PMS were likely to donate electrons to electron-deficient Co^(3+/2+)sites,and 1O_(2)were generated as the primary radicals.Besides,coordinatively unsaturated metal sites(CUMSs)were produced during the substitution process,since Co^(3+/2+)nodes were not fully bridged by VAN ligands.This improved the PMS utilization efficiency and ^(1)O_(2)yield.Previous studies have indicated the metal leaching would be worsened by CUMSs,owing to the lack of ligand protection.To solve this problem,a Co_(2)SiO_(4)shell was coated on VAN-ZIF-x surface.VAN-ZIF-x@Co_(2)SiO_(4)yolk@shell nanoreactor not only suppressed the metal leaching,but also improved the environmental adaption.This paper gave a novel insight on altering the PMS activation path,together with the CUMSs creation on catalyst surface.
