Peroxidase-Like Activity Of Cl-Doped Metal Oxide Nanozymes And Their Applications

Nanozymes with enzyme-like activity are a new frontier of chemical research.However,the low catalytic activity and poor substrate selectivity of nanozymes limited their application.Therefore,designing nanozymes with high catalytic activity and unique substrate specificity has become a hot spot in this research field.Herein,chloride ions were successfully incorporated into metal oxides such as Cu₂O NCs and Co₃O₄ NCs by solid-phase grinding method,which enhanced the peroxidase-like（POD-like）activity of materials.Combined with material structure characterization and catalytic data,the study mainly explores the structure-activity between structure and excellent catalytic performance.Based on the high POD-like activity of these materials,they were applied to the catalytic oxidative decolorization degradation of organic dye molecules and the treatment of skin wounds in diabetic mice resistant to methicillin Staphylococcus aureus（MRSA）.At the same time,the synthesis method can be successfully applied to the doping of Cu₂O NCs and Co₃O₄ NCs by other halogen ions and can also be applied to the halogen doping of other metal oxide nanocrystals.The research content is as follows:（1）Cl^-doped Cu₂O NCs were successfully prepared by the solid phase grinding method.Cl^-doping enhanced the ability of Cu₂O NCs for H₂O₂ decomposition to hydroxyl radicals（·OH）and made the production of superoxide anion radicals(O₂^·-)possible.Therefore,the POD-like catalytic activity of Cl^-doped Cu₂O NCs was significantly improved.Furthermore,combined with the characterization results,the newly formed O-Cu-Cl active site on the surface of Cu₂O nanocrystals and the change of electronic structure may be the main reasons for the significant enhancement of POD-like catalytic activity.Due to the high-efficiency POD-like activity of Cl^-doped Cu₂O NCs,it can be effectively applied to catalyze oxidative degradation of organic dyes and promote skin wound healing in diabetic mice infected with MRSA.Further studies show that the doping method based on solid-phase grinding can be successfully applied to the doping of Cu₂O NCs by halogen ions other than Cl^-.（2）Cl^-doped Co₃O₄ NCs were successfully prepared by the solid phase grinding method.Cl^-doping enhanced the ability of Co₃O₄ NCs for H₂O₂ decomposition to O₂^·-and made the production of·OH possible.The EPR and XPS investigation implied that the increased oxygen vacancy and the change of electronic structure after doping were the primary reasons for the significant enhancement of POD-like activity.As the high redox potential of·OH than that of O₂^·-,the catalytic oxidation of organic dye methyl orange degradation by Cl^-doped Co₃O₄ NCs was significantly improved.The solid-phase grinding method can be applied to other halogen ions doped Co₃O₄ NCs or Cl^-doped other metal oxide NCs.The halogen doping enhanced these materials’catalytic ability of H₂O₂decomposition to·OH,enhancing their POD-like activity.In summary,we developed an efficient,green,and environmentally friendly synthesis method for Cl^-doped metal oxide.By studying the structure-activity relationship between material structure and catalytic performance,the reaction mechanism of chlorine doping enhances the activity of nanozymes was elucidated.The materials were successfully applied to catalyze the degradation of organic dyes and the healing of skin wounds in diabetic mice infected with drug-resistant bacteria.The synthesis strategy based on halogen doping provides a new way for the development of metal oxide nanozymes with higher POD-like activity,and related research will promote the application of nanozymes in the fields of bacteriostasis and water treatment.