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Article(id=1241116652000039615, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1723132800000, receivedDateStr=2024-08-09, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773834868669, onlineDateStr=2026-03-18, pubDate=1742400000000, pubDateStr=2025-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773834868669, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773834868669, creator=13701087609, updateTime=1773834868669, updator=13701087609, issue=Issue{id=1241116641321350143, tenantId=1146029695717560320, journalId=1234093305789726721, year='2025', volume='45', issue='3', pageStart='1185', pageEnd='1776', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773834866123, creator=13701087609, updateTime=1773881366030, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241311676130193619, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241311676130193620, tenantId=1146029695717560320, journalId=1234093305789726721, issueId=1241116641321350143, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1251, endPage=1259, ext={EN=ArticleExt(id=1241116653782618872, articleId=1241116652000039615, tenantId=1146029695717560320, journalId=1234093305789726721, language=EN, title=Catalytic ozonation of 2,3-dimethylpyrazine using CN-doped Mn3O4, columnId=1234106386360103680, journalTitle=China Environmental Science, columnName=Water Pollution Control, runingTitle=null, highlight=null, articleAbstract=

A CN-supported Mn3O4（Mn3O4-CN）composite was synthesized as a catalyst for the catalytic ozonation of 2,3-dimethylpyrazine degradation in wastewater. The catalytic efficiencies of 2, 3-dimethylpyrazine were investigated under various ozone dosages, catalyst dosages, pH and temperature conditions. The results showed that under the conditions of an ozone dosage of 3mg/L, a catalyst dosage of 0.02g/L, pH =7 and a temperature of 10℃, the degradation rate of pollutants reached 100% within 20 min. Scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and other characterization methods were used to analyze the properties of the prepared Mn3O4-CN. It was confirmed that Mn3O4 and CN were successfully bonded, and the valence states of Mn were mostly +2 and +3. The reactive oxygen species analysis demonstrated that the surface hydroxyl groups and oxygen vacancies were identified as the main active sites, and ⋅OH was the main active oxygen species generated in the reaction system. The cyclic experiments showed that the Mn3O4-CN has good stability and reusability.

, correspAuthors=Da WANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Yi CHEN, Yin-ning HE, Da WANG, Shuang SONG, Jun MA), CN=ArticleExt(id=1241116659465900247, articleId=1241116652000039615, tenantId=1146029695717560320, journalId=1234093305789726721, language=CN, title=碳氮掺杂Mn3O4催化臭氧氧化降解水中2,3-二甲基吡嗪, columnId=1234106386565624579, journalTitle=中国环境科学, columnName=水污染与控制, runingTitle=null, highlight=null, articleAbstract=

合成了碳氮负载Mn3O4(Mn3O4-CN)复合材料作为臭氧催化剂用于降解废水中的2，3-二甲基吡嗪，考察了不同臭氧投量催化剂投量、pH值与温度下催化臭氧氧化水中2，3-二甲基吡嗪的效果.结果表明，在臭氧投量为3mg/L，催化剂投量为0.02g/L，pH =7，温度为10℃的条件下，20min内污染物的降解率达到100%.采用扫描电镜，X射线光电子能谱，X射线衍射等手段对材料进行表征分析，证实Mn3O4-CN中Mn3O4与CN发生键合，Mn价态为+2价与+3价的混合，证明Mn3O4-CN表面羟基基团与氧空位是主要活性位点，•OH是主要活性氧物种;循环实验表明Mn3O4-CN具有良好的稳定性与重复利用性.

, correspAuthors=汪达, authorNote=null, correspAuthorsNote=
* 责任作者，副教授，
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陈怡(2002-)，女，浙江绍兴人，浙江工业大学硕士研究生，主要从事水污染控制研究..

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陈怡(2002-)，女，浙江绍兴人，浙江工业大学硕士研究生，主要从事水污染控制研究..

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陈怡(2002-)，女，浙江绍兴人，浙江工业大学硕士研究生，主要从事水污染控制研究..

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碳氮掺杂Mn3O4催化臭氧氧化降解水中2,3-二甲基吡嗪
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陈怡 1 , 何银宁 1 , 汪达 1, * , 宋爽 1 , 马军 2
中国环境科学 | 水污染与控制 2025,45(3): 1251-1259
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中国环境科学 | 水污染与控制 2025, 45(3): 1251-1259
碳氮掺杂Mn3O4催化臭氧氧化降解水中2,3-二甲基吡嗪
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陈怡1 , 何银宁1, 汪达1, * , 宋爽1, 马军2
作者信息
  • 1.浙江工业大学环境学院，浙江省工业污染微生物控制技术重点实验室，浙江 杭州 310032
  • 2.哈尔滨工业大学环境学院，城市水资源与水环境国家重点实验室，黑龙江 哈尔滨 150006

    • 陈怡(2002-)，女，浙江绍兴人，浙江工业大学硕士研究生，主要从事水污染控制研究..

通讯作者:

* 责任作者，副教授，
Catalytic ozonation of 2,3-dimethylpyrazine using CN-doped Mn3O4
Yi CHEN1 , Yin-ning HE1, Da WANG1, * , Shuang SONG1, Jun MA2
Affiliations
  • 1.Key Laboratory of Microbial Technology for Industrial Pollution Control of Zhejiang Province, College of Environment, Zhejiang University of Technology, Hangzhou 310032, China
  • 2.State Key Laboratory of Urban Water Resource and Environment, School of Environment, Harbin Institute of Technology, Harbin 150006, China
出版时间: 2025-03-20
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摘要
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合成了碳氮负载Mn3O4(Mn3O4-CN)复合材料作为臭氧催化剂用于降解废水中的2，3-二甲基吡嗪，考察了不同臭氧投量催化剂投量、pH值与温度下催化臭氧氧化水中2，3-二甲基吡嗪的效果.结果表明，在臭氧投量为3mg/L，催化剂投量为0.02g/L，pH =7，温度为10℃的条件下，20min内污染物的降解率达到100%.采用扫描电镜，X射线光电子能谱，X射线衍射等手段对材料进行表征分析，证实Mn3O4-CN中Mn3O4与CN发生键合，Mn价态为+2价与+3价的混合，证明Mn3O4-CN表面羟基基团与氧空位是主要活性位点，•OH是主要活性氧物种;循环实验表明Mn3O4-CN具有良好的稳定性与重复利用性.

臭氧催化氧化  /  吡嗪  /  水处理  /  锰氧化物

A CN-supported Mn3O4（Mn3O4-CN）composite was synthesized as a catalyst for the catalytic ozonation of 2,3-dimethylpyrazine degradation in wastewater. The catalytic efficiencies of 2, 3-dimethylpyrazine were investigated under various ozone dosages, catalyst dosages, pH and temperature conditions. The results showed that under the conditions of an ozone dosage of 3mg/L, a catalyst dosage of 0.02g/L, pH =7 and a temperature of 10℃, the degradation rate of pollutants reached 100% within 20 min. Scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction and other characterization methods were used to analyze the properties of the prepared Mn3O4-CN. It was confirmed that Mn3O4 and CN were successfully bonded, and the valence states of Mn were mostly +2 and +3. The reactive oxygen species analysis demonstrated that the surface hydroxyl groups and oxygen vacancies were identified as the main active sites, and ⋅OH was the main active oxygen species generated in the reaction system. The cyclic experiments showed that the Mn3O4-CN has good stability and reusability.

catalytic ozonation  /  pyrazines  /  water treatment  /  manganese oxide
陈怡, 何银宁, 汪达, 宋爽, 马军. 碳氮掺杂Mn3O4催化臭氧氧化降解水中2,3-二甲基吡嗪. 中国环境科学, 2025 , 45 (3) : 1251 -1259 .
Yi CHEN, Yin-ning HE, Da WANG, Shuang SONG, Jun MA. Catalytic ozonation of 2,3-dimethylpyrazine using CN-doped Mn3O4[J]. China Environmental Science, 2025 , 45 (3) : 1251 -1259 .
正文
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吡嗪类物质作为一种被广泛运用在医药、农业、食品等领域的六元杂环化合物，可通过糖与氨基酸的反应生成[1]，该类物质存在于天然的各种动物、植物和微生物中，种类繁多.然而吡嗪类及其衍生物通常具有较为严重的嗅味，即便废水中含有低浓度的吡嗪类物质也会产生较为强烈的嗅味[2].2，3-二甲基吡嗪(2，3-DMP)作为吡嗪类的代表，具有较大的皮肤刺激性和眼睛损伤性，且在水中频繁被检出.目前关于吡嗪类物质处理的研究较少，传统水处理工艺难以有效降解吡嗪[2].因此，急需开发高效降解吡嗪类物质的技术方法.
臭氧氧化技术能够有效处理难降解污染物，已被应用于嗅味物质的处理[3].但由于单独臭氧氧化对污染物具有选择性，不能有效降解难降解污染物.此外，低浓度的臭氧降解效率低，而较高浓度的臭氧虽然氧化效果好，但容易产生氧化副产物，对人体健康危害较大.与传统臭氧氧化技术相比，非均相催化臭氧氧化(HCO)具有更高的反应速率以及臭氧利用率，且适用范围广，氧化能力强，无二次污染[4]，因此可以选择合适的催化剂来有效提高在HCO体系中对难降解有机污染物的降解效率.目前金属氧化物有铁基催化剂(Fe3O4[5]，FeO[6])、锰基催化剂(MnO2)[7]和钙基催化剂(CaO[8])已被广泛用作HCO催化剂.然而，金属氧化物依旧存在需要解决的问题，由于温度与制备方法的不同，催化剂容易团聚烧结；且催化剂活性位点暴露不均匀，导致活性位点容易失活；M(n+m)+难以还原回Mn+(M，金属物种)导致催化材料稳定性较弱，并容易出现金属组分浸出等问题[9].除金属氧化物外，非金属碳基材料表面因具有丰富的官能团与缺陷结构，如活性碳(AC)、氮掺杂石墨烯(N-rGO)和石墨氮化碳(g-C3N4)等，也被广泛用作HCO催化剂和催化载体材料[10].其中，CN材料由于N的加入，其缺陷结构产生和电子传递性能都得到了显著的提高，且CN材料合成便利，环境友好，成本较低，因此被广泛作为催化材料进行研究[11].
但由于臭氧存在强氧化性，且碳基材料官能团不稳定、容易被消耗，表面容易被氧化，导致催化剂活性降低[12].因此，将金属/金属氧化物分散在催化载体上制得的负载型催化剂已逐渐成为商用催化材料的制备趋势[13].这些复合材料不仅克服了金属/金属氧化物催化剂普遍存在的团聚问题，同时还稳定了非金属材料的表面官能团和结构缺陷，产生协同效应.
本文合成了CN掺杂Mn3O4复合材料(Mn3O4-CN)，选取2，3-二甲基吡嗪(2，3-DMP)作为目标污染物，系统考察了臭氧催化氧化2，3-DMP的效果，并通过X射线光电子能谱(XPS)等一系列表征方法探究催化剂结构组成及其催化降解污染物的效能与机理.
1　材料与方法
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1.1　试剂
高锰酸钾(KMnO4)，硫代硫酸钠(Na2S2O3)，双氰胺，靛蓝二磺酸钠，5，5-二甲基-1-吡咯啉-N-氧化物(DMPO)，2，2，6，6-四甲基哌啶(TEMP)，叔丁醇(TBA)，糠醇(FFA)，对苯醌(p-BQ)，氢氧化钠(NaOH)，高氯酸(HClO4)，2，3-DMP均购于上海阿拉丁试剂有限公司.
1.2　催化剂的制备
1.2.1　二氧化锰(MnO2)的合成
MnO2由KMnO4与Na2S2O3反应制得.具体制备过程如下：向60℃持续搅拌的KMnO4溶液中(0.2mol/L，500mL)缓慢滴加NaS2O3溶液(0.376mol/L，100mL).直至NaS2O3溶液滴完后，陈化静置2h.使用离心机分离沉淀物并用超纯水洗涤，在110℃的烘箱中干燥过夜，最后将样品转移至管式炉中，以3℃/min的升温速率升至450℃，于氩气条件下煅烧3h，所得的产物即为MnO2.
1.2.2　Mn3O4-CN的合成
将双氰胺作为氮源，与制备得到的MnO2按照物质的量比1：4的比例用研钵充分混合，放置在石英舟中，以5℃/min的升温速率升温至550℃煅烧4h，冷却至常温，所得的产物即为Mn3O4-CN.
1.3　臭氧催化氧化实验方法
采用静态实验进行非均相催化臭氧氧化降解反应.臭氧由高纯度氧气(99.9%)通入臭氧发生器(北京同林公司)生成，通入水中后形成臭氧水溶液，在通入臭氧30min后，使用紫外分光光度仪(T6，中国北京普析公司)在260nm的波长下测量臭氧浓度，制得高浓度臭氧水储备液.降解实验在在自制100mL玻璃反应器里进行，先在反应器内加入2，3-DMP溶液与催化材料，随后加入一定体积的高浓度臭氧水后即刻开始反应.催化反应开始后，经一定时间间隔采集两份水样.一份采用靛蓝法在610nm下测量吸光度来测定残余臭氧浓度.另一份水样采用0.22µm PTFE膜滤去催化剂，并迅速加入20µL Na2S2O3(12.5g/L)对猝灭臭氧，使用高效液相色谱法(2695，美国Waters公司)测定溶液中剩余的2，3-DMP污染物浓度，测量条件如下：流动相为甲醇与水的混合物(60：40，体积比)，流速1mL/min，柱温25℃，进样量20µL，检测器波长设置为276nm.
1.4　催化材料的表征
采用X射线衍射仪(XRD)测定样品的晶型；扫描电子显微镜(SEM)测定样品的形貌；氮吸附法测定催化剂的比表面积(BET)和孔容，X射线光电子能谱(XPS)测定样品的元素价态；傅里叶变换红外光谱(FT-IR)测定样品表面官能团；电子顺磁共振(EPR)测定反应体系中ROS的种类.
2　结果与讨论
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2.1　催化剂材料表征
图1为Mn3O4-CN催化剂的XRD谱图，样品27.8°的衍射峰对应CN结构，其余衍射峰与JCPDS(24-0734)标准卡一一对应，均属于Mn3O4的特征峰，无其他杂峰出现，证明制备过程中，Mn3O4-CN材料中的MnO2完全被还原为Mn3O4.Mn3O4-CN材料的特征衍射峰形状较为尖锐，说明催化剂的结晶性较好.
由图2可见，Mn3O4-CN主要呈珊瑚状，形状致密，放射状的分支结构能够提供更多的活性位点，长度在100~250nm，纳米级粒径的复合材料通常具有较大的比表面积，有利于催化剂与体系中其他组分的充分接触，有效提升污染物的降解效率.
材料的比表面积以及其孔隙体积采用N2吸脱附法进行分析.如图3所示，Mn3O4-CN的吸附与脱附曲线形成了一个滞后环，属于典型的H3型滞后环，这意味着材料中存在着大量介孔结构，可显著提高催化活性位点的暴露量，更好的催化降解污染物[14].Mn3O4-CN的吸附等温线类型属于Ⅳ型，该材料的总比表面积为13.1m2/g，孔隙率为0.1478cm3/g，平均孔径为19.2694nm.催化剂的元素组成采用XPS进行分析，如图4所示，检测到C 1s、O 1s、Mn 2p、Mn 3s、N 1s的特征峰，意味着Mn3O4-CN材料中主要存在C，N，O，Mn4种元素.
XPS常被用于对催化剂表面组成分析、催化活性成分确定、催化机理研究以及催化剂失效分析及失效机理研究等[15].图4(a)是C 1s的谱图，对其进行分峰拟合，拟合峰对应于C=C/C—C(284.8eV)和C—O—C(286.1eV)和C-O(288.8eV)[16].图4(b)中N 1s的398.2eV特征峰对应于末端氨基官能团(C=N—H)，而结合能为400.3eV的特征峰则对应Mn-N峰，证明N的成功掺杂[17].图4(c)为O 1s谱图，3个拟合峰分别对应晶格氧(OL)，表面吸附氧(OS)与吸附的分子水(OW)，其结合能分别为529.9eV，531.2eV与532.8eV[18]，表面吸附氧吸附的OH基团可作为活性位点，进一步促使臭氧分解形成•OH降解污染物.从Mn 2p图中(图4(d))可以看出，其特征峰分别为640.9eV，644.5eV和652eV，依次对应于Mn 2p3/2，卫星峰以及Mn 2p1/2[19].
为了进一步确定Mn3O4-CN中锰的存在形态，对Mn 3s(图4 (e))图进行分析，Mn 3s图中两个特征峰之间的结合能差值(∆Es)与Mn的平均氧化态(AOS)线性相关，当Mn的价态为+2价时，∆Es约为6.1，而当Mn的价态为+4价时，∆Es则约为4.4.因此，在多价态混合的锰氧化物中，可通过量取Mn 3s图中的∆Es值，通过式(1)计算Mn的AOS[20]，计算得到该材料的AOS为2.31，表明材料中Mn2+存在较多，与Mn 2p所显示的结果相对应，低价态的Mn的形成意味着Mn与其周边空间结构上的氧原子呈现不饱和配位状态，即Mn原子周边的O原子少于理论数，在材料结构上表现为氧空位的存在，因此认为Mn3O4-CN材料中存在较多氧空位[18].此外，由于Mn从高价态向低价态转变，Mn金属外围的电子数也随之增多，成为富电子的Mn位点.Mn3O4-CN材料中主要存在Mn的价态主要为+2价与+3价，这与Mn3O4的特征相吻合.
式中：AOS代表Mn的平均氧化态；∆Es代表Mn 3s图中两个特征峰之间的结合能差值.
Mn3O4-CN的FT-IR结果如图5所示，3422cm−1的峰为O—H基团，证明材料表面羟基化结构基团的存在，有利于提升催化剂的臭氧吸附能力与分解能力.而1434~1500cm−1的特征峰归结于C=N与C=C的拉伸振动与表面羟基的弯曲振动[21].609.9cm−1的峰是由于Mn—O的变形振动.此外，还在FTIR光谱中观察到了493.4cm−1的伸缩振动峰，这是由于Mn-N峰存在的结果，与XPS的结果相对应.
以上表征结果表明，Mn3O4-CN材料中存在Mn，C，O，N等元素，锰氧化物以Mn3O4为单一晶相存在，Mn的主要价态为+2价与+3价，且Mn3O4-CN材料中存在Mn—N键，证明Mn3O4与CN的紧密键合.Mn—N键形成后，电子更容易通过N传导给Mn，进一步佐证形成了富电子Mn位点，有利于臭氧分解形成活性氧物种[21].
2.2　催化臭氧氧化降解2，3-DMP的研究
2.2.1　催化剂优异的降解性能
本研究考察了催化剂在HCO体系与纯臭氧体系下对2，3-DMP的降解效率，实验条件为：臭氧初始浓度3mg/L，污染物初始浓度5µmol/L，催化剂投加量0.1g/L，反应温度10℃，反应溶液pH值7.如图6(a)所示，Mn3O4-CN对2，3-DMP几乎没有吸附(低于5%)，与单独臭氧的2，3-DMP去除率之和也远远小于加入催化剂后2，3-DMP的去除率，可见Mn3O4-CN作为催化剂对污染物降解起到的关键作用.在单独臭氧氧化体系中，30min反应时间后对污染物的降解效率仅为36.7%，说明臭氧直接氧化对污染物的降解作用有限，也确认了2，3-DMP为臭氧难降解污染物.在HCO体系中，由于Mn3O4-CN的存在，仅需20min便可将2，3-DMP完全降解，证明了Mn3O4-CN高效的分解臭氧能力和ROS生成能力.因此，Mn3O4-CN对臭氧催化降解污染物有显著作用.
为了进一步探究催化剂引发的降解速率变化，对图6(a)中的实验数据采用式(2)进行一级动力学方程拟合，由图可知，直接臭氧氧化和HCO反应动力学都遵循典型的二段式反应.在直接臭氧氧化体系中，第一段臭氧分解反应速率为0.3568min−1；加入催化剂后臭氧催化氧化的速率明显提升，反应速率为1.0319min−1，反应速率增加约3倍，可能是因为反应初始溶液中存在微量其他可引发臭氧分解的物质.当此类物质被消耗后，HCO反应的第二段反应速率是直接臭氧氧化的110倍，证明臭氧在Mn3O4-CN表面被快速分解并产生ROS，强化了2，3-DMP的降解[22].
式中：Ct和C0分别代表2，3-DMP在0和t时刻的浓度，µmol/L；k代表污染物降解的反应速率常数，min−1，t代表反应的时刻，min.
2.2.2　不同条件影响下
Mn3O4-CN的催化效能为了进一步探究催化剂使用的最佳条件，分别对臭氧投量，催化剂投量、pH值、温度等条件下Mn3O4-CN催化臭氧降解2，3-DMP的效能开展了研究，本实验的非变量条件如下：臭氧投量为3mg/L，2，3-DMP初始浓度为5µmol/L，Mn3O4-CN投量为0.02g/L，pH=7，温度为10℃.
图7(a)为不同臭氧投量(1mg/L，3mg/L，5mg/L)下2，3-DMP的降解效能.在反应30min后，投加1mg/L，3mg/L，5mg/L臭氧时2，3-DMP的降解效率分别为18.9%，39.8%，49.7%，而在加入Mn3O4-CN的HCO体系中，1mg/L臭氧投量下2，3-DMP的降解效率就达到了85.7%，在投加3mg/L臭氧时，5min后2，3-DMP降解率就达到了94.7%，20min后2，3-DMP便完全降解.在进一步投加5mg/L臭氧时，2，3-DMP在5min后即被完全降解，这说明Mn3O4-CN催化剂的加入可显著提高臭氧对污染物的降解.随着臭氧浓度的逐渐提高，催化降解污染物的降解率也随之提高.这不仅仅是因为臭氧可以直接与污染物发生反应，也是因为臭氧分解产生了更多的ROS，进而与污染物间接发生反应导致降解效率的提高[23].从观察加入催化剂的HCO体系可知，臭氧投量从3mg/L提高至5mg/L对于降解效率的提高不甚明显，综合其他条件考虑，选取3mg/L的臭氧投量作为Mn3O4-CN在本体系中催化降解污染物的最优值.
如图7(b)所示，未添加催化剂与0.01g/L投量的2，3-DMP降解效率分别为36.7%与83.5%，而催化剂投量在增加至0.02g/L时，降解效率显著提高.进一步增加至0.03g/L时，污染物在1min时便完全分解.催化剂投量的增加可以增加反应体系内催化臭氧的活性位总量，增加活性位与臭氧接触产生•OH的概率，更能有效降解污染物.但过量的催化剂可能会导致体系内短时间形成过量•OH，发生自猝灭而被自消耗[24].为了避免这种现象，选择0.02g/L的催化剂投量作为最优值.
pH值对2，3-DMP降解的影响如图7(c)所示.在pH= 3时，直接臭氧氧化和HCO的降解效率分别为12.4%与47.1%，在pH= 5时，降解效率达到了24.6%与62.9%，而当pH值增加到9时，纯臭氧体系效率显著提升至94.8%，添加催化剂的HCO体系在1min时降解效率便达到了100%.由此可见，pH值低于4时，臭氧的自分解被抑制[25]，随着溶液pH值的升高，体系对2，3-DMP的降解效率也逐渐提高.这是由于OH−作为O3链式反应的引发剂，见式(3)~(5)[26]：
O2•−作为O3在生成•OH过程中的中间产物，能够引发产生更多的•OH.因此pH值越高，OH−浓度增加，有利于上述反应的发生，能够高效地作用于污染物使其分解.
温度对2，3-DMP降解的影响如图7(d)所示.在纯臭氧体系中，不同温度的初始条件(T=10℃、20℃、30℃)，降解效率分别为36.7%，56.6%，70.5%.由此可见，温度越高，体系对2，3-DMP的降解效果越好.高温有利于臭氧分解产生大量•OH作用于污染物，促使反应高效进行[27].在有催化剂的HCO体系中，随着温度的升高，污染物分别在20min，5min，1min内降解完毕.总体而言，在加入催化剂后体系中温度因素对降解效率影响不大，说明当低温的条件时，加入催化剂能够获得更好的实验效果，也佐证了Mn3O4-CN可以适应各种温度条件，在实际应用中具有广泛的适用性，是极具应用前景的催化剂.
2.3　催化剂稳定性分析
Mn3O4-CN的重复利用循环降解2，3-DMP的效能如图8所示.第2，3，4次循环实验相较前一次降解效率分别下降了1.7%，2.6%和1.6%，第三次效能降低略微明显，可能是在收集过程中造成了催化剂损失，但四次循环后2，3-DMP的降解率依旧稳定在90%以上，说明Mn3O4-CN的臭氧催化活性十分稳定，因此在实际应用中，Mn3O4-CN催化剂具有潜在的稳定性优势.
2.4　催化机理与ROS分析
由前文的物理化学表征分析可知，Mn-N键将Mn3O4与CN紧密键合，且Mn-N键能够促进阳离子-π反应进行电子转移[28].此外，Mn3O4-CN材料中Mn活性中心的周围存在大量氧空位，导致Mn周围电子密度增加，成为富电子中心，向臭氧直接提供电子，臭氧得到电子后进一步形成活性氧物种(ROS)对污染物进行降解[21].
在臭氧催化过程中，产生最主要的ROS为•OH、1O2和O2•−[25]，为了明确体系中所存在的活性氧物种，开展自由基淬灭实验.采用叔丁醇(TBA)，对苯醌(p-BQ)与糠醇(FFA)作为自由基淬灭剂，实验结果如图9所示.TBA是一种极强的自由基抑制剂，既不与臭氧发生反应且可以与自由基反应生成惰性物质，从而抑制•OH的生成[29].在加入0.5mmol/L的5mL TBA时，反应30min后HCO体系中2，3-DMP的降解效率从100%降至26.6%，证明体系中2，3-DMP的降解主要由•OH贡献.p-BQ和FFA分别用来淬灭体系中的O2•−与1O2，在加入两种淬灭剂后2，3-DMP降解效率几乎完全被抑制.考虑到p-BQ和FFA也能够直接与臭氧进行反应，消耗臭氧，因此很难通过p-BQ和FFA的淬灭实验来确定体系中1O2和O2•-的生成[30].
为了进一步验证体系中是否存在•OH、1O2和O2•−,采用EPR进行检测，结果如图10所示.在图10(a)中可以发现，加入催化剂后能够明显检测到DMPO-OH加成产物的信号，而O3体系中未检测到相关信号，说明HCO体系中产生了大量的⋅OH.在图10(b)中，两种体系中产生的EPR信号基本相同，且没有观察到较为明显的峰型，说明并未产生超氧自由基.此外，在图10(c)中的O3/Mn3O4-CN体系中清晰显示峰强度为1：1：1的EPR信号，表明体系中还存在着1O2[31].1O2对于体系中2，3-DMP污染物的降解确切贡献未知，但结合抑制实验可知，HCO体系中主导2，3-DMP降解的ROS为⋅OH[32].
综上所述，Mn3O4-CN材料中的Mn以+2价与+3价存在，且Mn位点的周围存在大量氧空位，进而导致Mn周围电子密度增加，成为富电子中心. Mn3O4-CN材料中的Mn-N结构增强了电子在材料内部以及与臭氧间的传递能力，使得材料表面的臭氧可有效得到电子并被分解生成⋅OH，最终引发2，3-DMP的高效稳定降解[21].
3　结论
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3.1　将MnO2与双氰胺一同煅烧生成Mn3O4-CN，粒径在100~250nm之间，比表面积为13.1m2/g，Mn价态为+2价和+3价，表面存在大量氧空位与富电子Mn位点.
3.2　加入Mn3O4-CN催化剂的HCO体系中2，3-DMP的降解效率显著提升，第二段反应速率增加了110倍.在臭氧浓度为3mg/L，温度为10℃，pH=7的条件下，20min便可将2，3-DMP完全降解.随着臭氧浓度、催化剂投量以及pH值的增加，Mn3O4-CN催化臭氧降解2，3-DMP的效率也逐步增加.
3.3　通过自由基淬灭实验和EPR分析，发现•OH是Mn3O4-CN催化臭氧产生的主要ROS.Mn3O4-CN表面的氧空位和富电子Mn位点是引发臭氧分解的主要活性位点.
3.4　Mn3O4-CN经过4次循环利用实验后，催化活性并没有发生明显下降，对2，3-DMP的降解效率稳定在90%以上，具有潜在的应用优势.
基金
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  • 浙江省自然科学基金重点项目(LZ24B070002)
  • 浙江省大学生科技创新活动计划暨新苗人才计划(2023R403016)
文献
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2025年第45卷第3期
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  • 接收时间：2024-08-09
  • 首发时间：2026-03-18
  • 出版时间：2025-03-20
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  • 收稿日期：2024-08-09
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浙江省自然科学基金重点项目(LZ24B070002)
浙江省大学生科技创新活动计划暨新苗人才计划(2023R403016)
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    1.浙江工业大学环境学院，浙江省工业污染微生物控制技术重点实验室，浙江 杭州 310032
    2.哈尔滨工业大学环境学院，城市水资源与水环境国家重点实验室，黑龙江 哈尔滨 150006

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2种不同金属材料的力学参数
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species		 占总种数比例
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total species (%)		 属
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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