A novel heterogeneous Co(Ⅱ)-Fenton-like catalyst for efficient photodegradation by visible light over extended pH  

作　　者：Wu-Hua Chen Jin-Hua Xiong Xue Teng Jin-Xiao Mi Zhi-Biao Hu Haifeng Wang Zuofeng Chen 

机构地区：[1]Fujian Provincial Colleges and University Engineering Research Center of Solid Waste Resource Utilization(Longyan University),College of Chemistry and Material Science,Longyan University,Longyan 364012,China [2]Shanghai Key Laboratory of Chemical Assessment and Sustainability,School of Chemical Science and Engineering,Tongji University,Shanghai 200092,China [3]Key Laboratory for Advanced Materials,Centre for Computational Chemistry and Research Institute of Industrial Catalysis,East China University of Science and Technology,Shanghai 200237,China [4]Department of Materials Science and Engineering,College of Materials,Xiamen University,Xiamen 361005,China

出　　处：《Science China Chemistry》2020年第12期1825-1836,共12页中国科学（化学英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(21872105,22072107,21802142);the Natural Science Foundation of Fujian Province(2020J01367);the Natural Science Foundation of Longyan City(2018LYF8010);the Science&Technology Commission of Shanghai Municipality(19DZ2271500);We are indebted to Prof.Xuxu Wang(Fuzhou University)for valuable comments and suggestions.

摘　　要：A novel Co^Ⅱ-Fenton-like heterogeneous catalyst,(H3O)2[Co^Ⅱ(phen)(H2O)2]2[Mo^Ⅵ5O15(PO4)2]·4H2O (phen=1,10-phenanthroline,C12N2H8)(1),is synthesized and utilized for photocatalytic degradation of organic dyes and antibiotic in a wide range of pH.The experimental results show that 1 acting as the Fenton-like catalyst with H2O2 exhibits remarkable activity at pH 3–9 under vis-light irradiation and is merited with excellent recyclability and reusability.A variety of analytical methods,including in-situ electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations,are applied to study the mechanism on generation of·OH and O2^·-radicals for photocatalytic degradation.It suggests that,unlike the classical Fenton process involving the redox transformation of the central cations,the generation of·OH and O2^·-radicals is associated with the substitution of the coordinating water molecules at Co(Ⅱ) by H2O2 and/or OOH^-,followed by the light-driven O–O bond cleavage and dissociation.The outcomes of this study are striking which overcome the obstacles in the classical Fe^Ⅱ-Fenton process,including the slow redox transformation between Fe(Ⅱ) and Fe(Ⅲ) and the production of massive iron precipitates especially at elevated pH.It opens up new avenues for the development of the high-performance Fenton(-like) catalysts for photocatalytic degradation over extended pH and provides new insight into the related process.

关 键 词：Co^Ⅱ-Fenton-like reagent POLYOXOMETALATE photocatalytic degradation density functional theory(DFT)calculations in-situ EPR spectroscopic analysis 

分 类 号：X703[环境科学与工程—环境工程] O643.36[理学—物理化学] O644.1[理学—化学]