Full reaction mechanism of hydrogen peroxide catalyzed by reductive CoP nanoparticles:the enzyme-like activity

作     者：Kaiwei Wan Chang Long Bing Jiang Minmin Liang Zhiyong Tang Hui Wang Xinghua Shi Kaiwei Wan;Chang Long;Bing Jiang;Minmin Liang;Zhiyong Tang;Hui Wang;Xinghua Shi

作者机构：Laboratory of Theoretical and Computational NanoscienceCAS Key Laboratory of Nanosystem and Hierarchical FabricationCAS Center for Excellence in NanoscienceNational Center for Nanoscience and TechnologyChinese Academy of SciencesBeijing 100190China University of Chinese Academy of SciencesBeijing 100049China Molecular Electrochemistry LaboratoryInstitute of Fundamental and Frontier SciencesUniversity of Electronic Science and Technology of ChinaChengdu 610054China Experimental Center of Advanced MaterialsSchool of Materials Science&EngineeringBeijing Institute of TechnologyBeijing 100081China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2023年第66卷第4期

页      面：1221-1227页

核心收录：

学科分类：0710[理学-生物学] 08[工学] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0703[理学-化学] 

基　　金：supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB36000000) the Natural Science Foundation of Beijing(2222085,1202023,2194092) the National Natural Science Foundation of China(11672079,12072082)。 

主　　题：CoP nanoparticle peroxidase,catalase DFT calculations heterogeneous catalysis 

摘      要：The hydrogen peroxide(H2O2)catalyzed by nanoparticles(NPs)demonstrates potential broad applications in the field of biomedicine and environmental protection.However,a systematic understanding of the catalytic mechanism severely limited the rational design of NPs with better enzyme-like activity and selectivity.Here,compared with the widely concerned Fe3O4NPs,the decomposition process of H_(2)O_(2) on reductive Co P NPs and p H-regulated peroxidase-and catalase-like activities with 3,3′,5,5′-tetramethylbenzidine(TMB)as reductive substrates were explored.All results show that OH·radical intermediates generated from the decomposition of H2O2*/OOH*at acidic conditions and complexed with TMB via H-bonds(complexed OH·)are the principal oxidant of TMB rather than free OH·as reported.Besides,the produced O*/OH*on Co P NPs shows negligible oxidation activity due to the strong reducibility of catalysts.The high coverage of O*/OH*from the dissociation of H2O2(H2O)at neutral(alkaline)p H conditions on Co P NPs enhances the dehydrogenation of H_(2)O_(2) to O2,leading to the transition between peroxidase-and catalase-like activities.