文献类型：期刊文献

中文题名：Fe_(3)O_(4)/MoO_(x)S_(y)表面缺陷实现自由基与非自由基类芬顿反应历程的切换

英文题名：Switching of radical and nonradical pathways through the surface defects of Fe_(3)O_(4)/MoO_(x)S_(y) yin a Fenton-like reaction

作者：刘昕玥[1];闫心怡[1];刘文元[1];闫青云[1];邢明阳[1,2]

机构：[1]Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering,Feringa Nobel Prize Scientist Joint Research Center,Frontiers Science Center for Materiobiology and Dynamic Chemistry,Institute of Fine Chemicals,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China;[2]Shanghai Engineering Research Center for Multi-media Environmental Catalysis and Resource Utilization,East China University of Science and Technology,Shanghai 200237,China

年份：2023

卷号：68

期号：6

起止页码：603

中文期刊名：Science Bulletin

外文期刊名：科学通报（英文版）

收录：CSTPCD;;Scopus;CSCD:【CSCD2023_2024】；PubMed;

基金：supported by the National Natural Science Foundation of China (22176060);Shanghai Municipal Science and Technology Major Project (2018SHZDZX03);the Program of Introducing Talents of Discipline to Universities (B16017);Science and Technology Commission of Shanghai Municipality (20DZ2250400);Shanghai Sailing Program (20YF1410600);the Fundamental Research Funds for the Central Universities (222201717003)。

语种：中文

中文关键词：Fenton-like;Defect;Peroxymonosulfate;Radical;Nonradical

摘要：自由基与非自由反应历程共同主导的高级氧化技术,无法实现对有机污染物的高效且高选择性降解,难以满足不同废水的降解需求.本研究通过引入缺陷和调节Mo^(4+)/Mo^(6+)比例,在Fe_(3)O_(4)/MoO_(x)S_(y)活化过一硫酸氢盐(PMS)体系中实现了自由基与非自由基分别主导的类芬顿反应历程的切换.通过表面包硅修饰破坏了Fe_(3)O_(4)和MoO_(x)S_(y)的晶格结构,引入了表面缺陷.丰富的缺陷电子使得催化剂表面暴露更多的Mo^(4+),进一步促进了PMS活化分解产生自由基,最大反应k值可达1.530 min^(-1),自由基反应历程主导降解有机污染物的贡献率则达到了81.33%.Fe含量的改变也会影响催化剂表面暴露Mo^(4+)/Mo^(6+)的比例.Mo^(6+)有助于产生^(1)O_(2),因此,随着Mo^(6+)占比的提高可实现从自由基向非自由基反应历程的切换,且非自由基反应历程主导的降解污染物的贡献率最高可达68.26%.自由基反应历程主导的类芬顿体系可实现对实际有机废水化学需氧量(COD)的高效去除;而非自由基反应历程主导的类芬顿体系则可显著提高废水的可生化性(BOD/COD=0.997).Fe_(3)O_(4)/MoO_(x)S_(y)/PMS类芬顿体系中自由基与非自由基反应历程的切换,拓展了高级氧化技术在废水处理中的靶向应用.
Coexistence of radical and nonradical reaction pathways during advanced oxidation processes(AOPs)makes it challenging to obtain?exible regulation of high ef?ciency and selectivity for the requirement of diverse degradation.Herein,a series of Fe_(3)O_(4)/MoO_(x)S_(y) ysamples coupling peroxymonosulfate(PMS)systems enabled the switching of radical and nonradical pathways through the inclusion of defects and adjustment of Mo^(4+)/Mo^(6+)ratios.The silicon cladding operation introduced defects by disrupting the orig-inal lattice of Fe_(3)O_(4)and MoO_(x)S_(y).Meanwhile,the abundance of defective electrons increased the amount of Mo^(4+)on the catalyst surface,promoting PMS decomposition with a maximum k value up to 1.530 min^(-1) and a maximum free radical contribution of 81.33%.The Mo^(4+)/Mo^(6+)ratio in the catalyst was similarly altered by different Fe contents,and Mo^(6+)contributed to the production of ^(1)O_(2),allowing the whole system to attain a nonradical species–dominated(68.26%)pathway.The radical species-dominated system has a high chemical oxygen demand(COD)removal rate for actual wastewater treatment.Conversely,the nonradical species-dominated system can considerably improve the biodegradability of wastewater(biochemical oxygen demand(BOD)/COD=0.997).The tunable hybrid reaction pathways will expand the targeted applications of AOPs.