高活性Cu-MnO_(2)类氧化物纳米酶降解罗丹明B  

Rhodamine B degradation by highly active Cu-MnO_(2) oxidase-like nanoenzyme

作　　者：谢碧梅 郑燕宁 王迎波[1] 孙建华[1] 杨崎峰 廖丹葵[1] XIE Bimei;ZHENG Yanning;WANG Yingbo;SUN Jianhua;YANG Qifeng;LIAO Dankui(Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology,School of Chemistry and Chemical Engineering,Guangxi University,Nanning 530004,Guangxi,China;Guangxi Bossco Environmental Protection Technology Co.,Ltd.,Nanning 530007,Guangxi,China)

机构地区：[1]广西大学化学化工学院广西石化资源加工及工程强化技术重点实验室,广西南宁530004 [2]广西博世科环保科技股份有限公司,广西南宁530007

出　　处：《精细化工》2023年第12期2752-2761,共10页Fine Chemicals

基　　金：国家自然科学基金项目(52162004);广西石化资源加工及过程强化技术重点实验室主任项目(2020Z003);广西博世科环保科技股份有限公司国家企业技术中心开放基金(GXU-BFY-2020-007)。

摘　　要：采用一步水热法制备了高活性铜掺杂二氧化锰(Cu-MnO_(2))类氧化物纳米酶(简称为类氧化物酶),采用XRD、SEM、EDS、N_(2)吸附-脱附、XPS对其进行了表征,探究了Cu-MnO_(2)催化降解罗丹明B(RhB)的效果。结果表明,铜掺杂后Cu-MnO_(2)产生了协同效应,增强了Cu-MnO_(2)的类氧化物酶催化活性,当溶液pH=3.0、RhB初始质量浓度为50 mg/L、Cu-MnO_(2)-10%(10%为CuCl_(2)·2H_(2)O物质的量占KMnO_(4)物质的量的百分数)用量为0.01 g时,30℃下,30 min内可完全降解RhB,并且催化剂使用5次后RhB降解率仍达75%。此外,对环丙沙星、氧氟沙星、四环素和对苯二酚难降解的污染物的降解率分别为88.86%、90.47%、92.62%和90.99%。Cu-MnO_(2)类氧化物酶催化降解RhB的机理研究表明,富含氧空位的Cu-MnO_(2)中存在丰富的空穴,有利于吸附和催化溶解氧生成大量的单线态氧(^(1)O_(2))和少量的超氧自由基(O_(2)^(·-))等活性氧物种,可用于快速降解有机污染物。Highly active copper-doped manganese dioxide(Cu-MnO_(2))oxidase-like nanozyme(abbreviated as oxidase-like enzyme)was prepared by one-step hydrothermal method and characterized by XRD,SEM,EDS,N2 adsorption-desorption and XPS.And its catalytic performance on Rhodamine B(RhB)degradation was further investigated.The results showed that the improved catalytic activity of Cu-MnO_(2) was attributed to the synergistic effect of MnO_(2) and doped copper.RhB could be fully degraded within 30 min at 30℃under the conditions of solution pH 3.0,initial RhB mass concentration 50 mg/L,and Cu-MnO_(2)-10%(10%is the percentage of amount of substance of CuCl_(2)·2H2O and KMnO_(4))dosage 0.01 g,while the degradation rate of RhB was still maintained 75%even when the catalyst was recycled 5 times.In addition,the degradation rates of ciprofloxacin,ofloxacin,tetracycline,and hydroquinone were 88.86%,90.47%,92.62%and 90.99%,respectively.The mechanism study of RhB degradation catalyzed by Cu-MnO_(2) oxidase-like enzyme revealed that there were abundant holes in oxygen vacancy rich Cu-MnO_(2),which was beneficial for adsorbing and catalyzing dissolved oxygen to produce a large amount of singlet oxygen(^(1)O_(2))and a small number of superoxide radicals(O_(2)^(·-))and other reactive oxygen species for the rapid degradation of organic pollutants.

关 键 词：类氧化物酶 铜掺杂 MnO_(2) 降解 罗丹明B 水处理技术 

分 类 号：X7034[环境科学与工程—环境工程] TQ426.97[化学工程]