电化学技术在水处理中的应用

电化学技术在水处理中的应用摘要：电化学水处理技术是一种绿色的水处理技术，近年来以其独特的技术优点获得广泛的关注与研究。常见的电化学水处理技术有很多种，本文作者基于自身研究基础及研究兴趣，重点关注电催化氧化技术和电化学水垢去除技术，对相关技术的基本原理、关键影响因素、核心技术模块、技术瓶颈以及未来发展方向进行详细阐述，以期为相关技术领域的发展贡献微薄之力。关键词：水处理；电化学；催化氧化；除垢Abstract:Electrochemicaltechnologyisakindofgreenwatertreatmenttechnologywithenvironmental-friendliness.Inrecentyears,ithasattractedextensiveattentionandresearchduetoitsuniquetechnicalsuperiority.Therehavebeenmanyavarietyofmatureelectrochemicalwastewatertreatmenttechnology.Basedonourowninvestigationbaseandresearchinterests,theauthorsfocusonelectrocatalyticoxidationandelectrochemicalscaleremovaltechnology.Thosetechnologiesareelaboratedintermsoftheirbasicprinciple,keyinfluentialfactors,thecoretechnologymodule,technicalbottlenecksandthedirectionoffuturedevelopment,soastomakecontributionfortheprogressofrelatedtechnicalfields.Keywords:Wastewatertreatment;Electrochemistry;Catalyticoxidation;Descaling1、概述电化学水处理技术是一种绿色的水处理技术，无需化学药剂添加，处理废水高效，设备及操作简单，反应过程温和，并且可以与其它技术灵活配合，受到越来越多科研机构与企业的关注与重视ADDINEN.CITEADDINEN.CITE.DATA[1-5]。电化学水处理技术相比传统水处理技术具有独特的优势：（1）清洁。反应物为电子，无化学添加，无二次污染。（2）灵活。电极的形状、大小可精准控制；反应器类型灵活多变，水处理场地无硬性要求，可单独使用，也可与其它技术联合使用。（3）简便。所需设备简单，操作简单，控制电流或电压即可；条件简单，在常温常压下即可处理，并且处理过程中的“垃圾”极少，后处理简单。（4）温和可控。由于不需要高压、高温等苛刻条件，反应较为温和，人力需求很低，便于自动化控制。上述技术优势使得电化学水处理技术近年来逐渐成为水污染领域的研究热点ADDINEN.CITEADDINEN.CITE.DATA[1,3,5,6]。目前常见的电化学水处理技术包括：电催化氧化技术、电化学水垢去除技术、电气浮/电絮凝技术ADDINEN.CITEADDINEN.CITE.DATA[7,8]、电化学消毒技术ADDINEN.CITEADDINEN.CITE.DATA[9-11]、电渗析技术ADDINEN.CITE<EndNote><Cite><Author>朱茂森</Author><Year>2012</Year><RecNum>8818</RecNum><DisplayText>[12]</DisplayText><record><rec-number>8818</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1376275966">8818</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>朱茂森</author><author>夏春梅</author><author>胡筱敏</author></authors></contributors><titles><title>用于电渗析处理酸洗废水的Ti/SnO_2-Sb_2O_3/PbO_2电极的制备与表征</title><secondary-title>安全与环境学报</secondary-title></titles><periodical><full-title>安全与环境学报</full-title></periodical><number>06</number><keywords><keyword>环境工程学</keyword><keyword>电极</keyword><keyword>氧化物涂层</keyword><keyword>电渗析</keyword><keyword>酸洗废水</keyword></keywords><dates><year>2012</year></dates><isbn>1009-6094</isbn><urls></urls></record></Cite></EndNote>[12]、微生物燃料电池技术ADDINEN.CITEADDINEN.CITE.DATA[13-15]等。限于文章篇幅、作者研究基础及研究兴趣，本文将重点阐述电催化氧化技术和电化学水垢去除技术的相关情况。2、电催化氧化技术2.1技术原理与技术困境 电催化氧化处理有机物技术是非常典型的高级氧化技术，其技术原理如图1所示ADDINEN.CITEADDINEN.CITE.DATA[16-18]。如图1所示，电催化氧化技术的核心点在于使得阳极表面产生的强氧化性物质（尤其是羟基自由基）与溶液中的有机物分子进行充分的接触与反应，由此使得有机物分子被逐步氧化分解，直至形成二氧化碳和水ADDINEN.CITE<EndNote><Cite><Author>Chaplin</Author><Year>2014</Year><RecNum>20204</RecNum><DisplayText>[19]</DisplayText><record><rec-number>20204</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1409791188">20204</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chaplin,B.P.</author></authors></contributors><auth-address>Chaplin,BP UnivIllinois,DeptChemEngn,810SClintonAve,Chicago,IL60607USA UnivIllinois,DeptChemEngn,810SClintonAve,Chicago,IL60607USA UnivIllinois,DeptChemEngn,Chicago,IL60607USA</auth-address><titles><title>Criticalreviewofelectrochemicaladvancedoxidationprocessesforwatertreatmentapplications</title><secondary-title>EnvironmentalScience-Processes&Impacts</secondary-title><alt-title>EnvironSci-ProcImp</alt-title></titles><periodical><full-title>EnvironmentalScience-Processes&Impacts</full-title><abbr-1>EnvironSci-ProcImp</abbr-1></periodical><alt-periodical><full-title>EnvironmentalScience-Processes&Impacts</full-title><abbr-1>EnvironSci-ProcImp</abbr-1></alt-periodical><pages>1182-1203</pages><volume>16</volume><number>6</number><keywords><keyword>boron-dopeddiamond</keyword><keyword>thin-filmelectrodes</keyword><keyword>reverse-osmosisconcentrate</keyword><keyword>highovervoltageanodes</keyword><keyword>industrialwaste-water</keyword><keyword>tindioxideelectrodes</keyword><keyword>naturalorganic-matter</keyword><keyword>aqueousphenolwastes</keyword><keyword>leaddioxide</keyword><keyword>hydroxylradicals</keyword></keywords><dates><year>2014</year></dates><isbn>2050-7887</isbn><accession-num>WOS:000336841600002</accession-num><urls><related-urls><url><GotoISI>://WOS:000336841600002</url></related-urls></urls><electronic-resource-num>Doi10.1039/C3em00679d</electronic-resource-num><language>English</language></record></Cite></EndNote>[19]。近年来，电催化氧化技术除受到较多科研人员的关注与研究，在工程实践中也得到一定程度的应用ADDINEN.CITEADDINEN.CITE.DATA[2-4,20-23]，但是表现出一些问题：（1）催化效率较低；（2）传质效果较差；（3）单位能耗较高。上述问题所对应的技术瓶颈为：（1）如何提高电极材料的使用效率？（2）如何优化电子转移与物质转移？3）如何提高反应系统能量利用率，降低能耗？图1电催化氧化技术原理示意图造成上述问题的根本缺陷在于电催化氧化过程中电子利用效率低，解决该问题成为推动技术实际应用的重中之重。电催化氧化体系是一个复合系统，主要包括阳极、阴极、电源、电解槽和其它配套设备等。为提高全过程的电子利用效率，需要从系统各组成部分来综合考虑：（i）电极（尤其是阳极）是电催化氧化技术的核心部件，是产生催化能力的源泉ADDINEN.CITEADDINEN.CITE.DATA[24,25]，因此，研发出性能优越的阳极材料能够有效改善或解决技术瓶颈（1）~（3）。（ii）反应器是完成物质转化的核心单元，理想的反应器设计是提高电流效率、增强传质过程的有效手段ADDINEN.CITEADDINEN.CITE.DATA[26,27]。因此，设计出高效的电催化反应器可以解决或改善技术瓶颈（2）与瓶颈（3）。（iii）电能是电催化氧化技术的能量来源，恰当的供电方式可以有效地降低能耗、提高电流效率，并且优化处理效果ADDINEN.CITE<EndNote><Cite><Author>雷佳妮</Author><Year>2019</Year><RecNum>23685</RecNum><DisplayText>[28]</DisplayText><record><rec-number>23685</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1578710632">23685</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">雷佳妮</style></author><author><styleface="normal"font="default"charset="134"size="100%">袁孟孟</style></author><author><styleface="normal"font="default"charset="134"size="100%">郭华</style></author><author><styleface="normal"font="default"charset="134"size="100%">杨鸿辉</style></author><author><styleface="normal"font="default"charset="134"size="100%">徐浩</style></author><author><styleface="normal"font="default"charset="134"size="100%">杨柳</style></author></authors></contributors><titles><title><styleface="normal"font="default"charset="134"size="100%">电化学氧化技术供电方式研究进展</style></title><secondary-title><styleface="normal"font="default"charset="134"size="100%">工业水处理</style></secondary-title></titles><periodical><full-title>工业水处理</full-title></periodical><pages><styleface="normal"font="default"size="100%">7</style><styleface="normal"font="default"charset="134"size="100%">-12</style></pages><volume>39</volume><number>12</number><section>7</section><dates><year>2019</year></dates><urls></urls><electronic-resource-num>10.11894/iwt.2018-1107</electronic-resource-num></record></Cite></EndNote>[28]。针对瓶颈（3），找寻合适的供电方式十分关键。基于此，目前文献报道的解决方法都集中于阳极改性、电催化体系优化、电催化参数优化、供电方式优化等方面，以此来强化电催化氧化技术的传质过程，提高溶液本体中有机物分子向阳极/溶液界面区域的传质效率，提高羟基自由基的利用效率，进而全过程的电子利用效率。2.2电催化阳极2.2.1阳极性能要求电极材料是电催化氧化技术的灵魂，而阳极材料比阴极材料更为重要，这主要归因于阳极表面及其附近溶液区域是电催化氧化反应的主要区域。理想的阳极材料应具有三个特点：高催化活性、高稳定性和低制备成本。高催化活性是电极可使用性的根本和前提，高稳定性意味着设备运行成本和维护成本的节约，而低制备成本则是对珍贵物质资源和能源消耗的控制，也是电化学氧化技术工业化应用的前提。通常而言，如一种未成熟应用的阳极材料具有其中两个较为突出的特点，则这种材料就具有一定的研究价值。2.2.2阳极材料的种类适用于电催化氧化技术的阳极通常为不溶性阳极。传统的不溶性阳极材料主要包括石墨电极、贵金属电极和钛基体金属氧化物电极。图2所示典型阳极材料的发展简史。意大利DeNora公司于1968年将荷兰学者H.Beer研发出钛基混合氧化钌涂层阳极实现工业化生产与应用，进而拉开DSA（DimensionalStableAnode）电极的序幕，成为20世纪电化学工业最重要的发明之一，对电化学领域（尤其是水处理领域）具有划时代的贡献ADDINEN.CITEADDINEN.CITE.DATA[24,29,30]。图2典型阳极材料发展简史近年来，掺硼金刚石电极（Borondopeddiamond,BDD）作为一种新型功能电极材料，引起较多科研工作者的关注。BDD电极具有许多其它电极材料所不可比拟的优势，如较强的抗中毒及抗污染能力、较宽的电化学电势窗口、较小的背景电流和较好的电化学稳定性。目前，BDD电极已经有报道被用于废水处理ADDINEN.CITEADDINEN.CITE.DATA[31-33]。尽管BDD电极具有非常优异的综合性能，但是由于其制备工艺的复杂性及相关设备的成本较高，导致BDD电极难以大尺寸生产且成本相比于钛基金属氧化物电极而言较高，极大的限制其应用范围。相比于石墨电极不稳定、贵金属电极和BDD电极的价格昂贵，DSA电极以其价格相对低廉、易于功能化、制备方法简单等优点受到极大的关注与研究ADDINEN.CITEADDINEN.CITE.DATA[29,34]。2.2.3DSA阳极改性如前所述，为强化电催化氧化技术中的传质过程，大量研究人员采用多种技术手段对DSA阳极进行改性，重点是：1）提升阳极表面羟基自由基（尤其是游离态羟基自由基）的产生量，2）制备表面多孔的立体电极，以此增大电极与溶液接触面积，进而提高电催化氧化的效果以及电极的稳定性。（1）使用新基体传统钛基体电极是使用钛板、钛网或钛棒作为基体。近年来兴起的二氧化钛纳米管阵列（TiO2nanotubes，TiO2-NTs）的阳极氧化制备ADDINEN.CITE<EndNote><Cite><Author>Xu</Author><Year>2011</Year><RecNum>8558</RecNum><DisplayText>[35,36]</DisplayText><record><rec-number>8558</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366798856">8558</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xu,Hao</author><author>Zhang,Qian</author><author>Zheng,Chunli</author><author>Yan,Wei</author><author>Chu,Wei</author></authors></contributors><titles><title>ApplicationofultrasonicwavetocleanthesurfaceoftheTiO2nanotubespreparedbytheelectrochemicalanodization</title><secondary-title>AppliedSurfaceScience</secondary-title></titles><periodical><full-title>AppliedSurfaceScience</full-title></periodical><pages>8478-8480</pages><volume>257</volume><number>20</number><section>8478</section><dates><year>2011</year></dates><isbn>01694332</isbn><urls></urls><electronic-resource-num>10.1016/j.apsusc.2011.04.135</electronic-resource-num></record></Cite><Cite><Author>Zhang</Author><Year>2012</Year><RecNum>8561</RecNum><record><rec-number>8561</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366798991">8561</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Zhang,Qian</author><author>Xu,Hao</author><author>Yan,Wei</author></authors></contributors><titles><title>HighlyOrderedTiO2NanotubeArrays:RecentAdvancesinFabricationandEnvironmentalApplications—AReview</title><secondary-title>NanoscienceandNanotechnologyLetters</secondary-title></titles><periodical><full-title>NanoscienceandNanotechnologyLetters</full-title><abbr-1>NanosciNanotechLet</abbr-1></periodical><pages>505-519</pages><volume>4</volume><number>5</number><section>505</section><dates><year>2012</year></dates><isbn>19414900 19414919</isbn><urls></urls><electronic-resource-num>10.1166/nnl.2012.1345</electronic-resource-num></record></Cite></EndNote>[35,36]，为钛基体电极提供一种新的基体材料。赵国华ADDINEN.CITEADDINEN.CITE.DATA[37-40]等人以TiO2-NTs作为基体，将Sb-SnO2活性层以真空抽气施加负压的方式加入TiO2-NTs中，使得新电极在稳定性和催化能力方面有较大的提高。徐浩ADDINEN.CITE<EndNote><Cite><Author>Hao</Author><Year>2011</Year><RecNum>8562</RecNum><DisplayText>[41]</DisplayText><record><rec-number>8562</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366799246">8562</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>XuHao</author><author>ZhangQian</author><author>YanWei</author><author>ChuW</author></authors></contributors><titles><title>ACompositeSb-dopedSnO2ElectrodeBasedontheTiO2NanotubesPreparedbyHydrothermalSynthesis</title><secondary-title>InternationalJournalofElectrochemicalScience</secondary-title></titles><periodical><full-title>InternationalJournalofElectrochemicalScience</full-title><abbr-1>IntJElectrochemSc</abbr-1></periodical><pages>6639-6652</pages><volume>6</volume><section>6639</section><dates><year>2011</year></dates><urls></urls></record></Cite></EndNote>[41]等人以水热法加压方式完成上述过程（过程如图3所示），除提高新电极稳定性外，还使得新电极具有一定程度的光电响应能力。造成此现象的原因在于：TiO2-NTs所起作用类似于建筑地基上的桩，其一端紧紧连结钛基体，另一端又可被Sb-SnO2涂层所填充并覆盖，使得基体与涂层的结合力大大增强。类似的，PbO2电极也可采用TiO2-NTs为基体。WuADDINEN.CITE<EndNote><Cite><Author>Jia</Author><Year>2015</Year><RecNum>23477</RecNum><DisplayText>[42]</DisplayText><record><rec-number>23477</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1467273714">23477</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>WuJia</author><author>XuHao</author><author>YanWei</author></authors></contributors><titles><title>Fabricationandcharacterizationofβ-PbO2α-PbO2Sb-SnO2TiO2nanotubearrayselectrodeanditsapplicationinelectrochemicaldegradationofAcidRedG</title><secondary-title>RscAdvances</secondary-title></titles><periodical><full-title>RscAdvances</full-title><abbr-1>RscAdv</abbr-1></periodical><pages>19284-19293</pages><volume>5</volume><section>19284</section><dates><year>2015</year></dates><urls></urls><electronic-resource-num>10.1039/C4RA16613B 10.1039/c4ra16613b</electronic-resource-num></record></Cite></EndNote>[42]等在TiO2-NTs上添加多个中间层，成功制备出具有较高催化活性与稳定性的TiO2/Sb–SnO2/α-PbO2/β-PbO2电极。经过测试，该电极的强化寿命高达815h，并对酸性红G具有较好的催化氧化能力。图3传统刷涂法与以TiO2-NTs为基体时的Sb-SnO2电极制备过程对比图ADDINEN.CITE<EndNote><Cite><Author>Hao</Author><Year>2011</Year><RecNum>8562</RecNum><DisplayText>[41]</DisplayText><record><rec-number>8562</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366799246">8562</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>XuHao</author><author>ZhangQian</author><author>YanWei</author><author>ChuW</author></authors></contributors><titles><title>ACompositeSb-dopedSnO2ElectrodeBasedontheTiO2NanotubesPreparedbyHydrothermalSynthesis</title><secondary-title>InternationalJournalofElectrochemicalScience</secondary-title></titles><periodical><full-title>InternationalJournalofElectrochemicalScience</full-title><abbr-1>IntJElectrochemSc</abbr-1></periodical><pages>6639-6652</pages><volume>6</volume><section>6639</section><dates><year>2011</year></dates><urls></urls></record></Cite></EndNote>[41]（2）加入中间层钛基体金属氧化物电极失效的机制包括：氧化物层溶解/溶蚀、氧化物层脱落以及活性层钝化ADDINEN.CITE<EndNote><Cite><Author>Hao</Author><Year>2015</Year><RecNum>22704</RecNum><DisplayText>[43,44]</DisplayText><record><rec-number>22704</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1448414181">22704</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>XuHao</author><author>YanWei</author><author>YangHonghui</author></authors></contributors><titles><title>SurfaceAnalysisofTi/Sb-SnO2/PbO2ElectrodeafterLongTimeElectrolysis</title><secondary-title>RareMetalMaterialsandEngineering</secondary-title></titles><periodical><full-title>RareMetalMaterialsandEngineering</full-title><abbr-1>RareMetalMatEng</abbr-1></periodical><pages>2637-2641</pages><volume>44</volume><number>11</number><section>2637</section><dates><year>2015</year></dates><urls></urls></record></Cite><Cite><Author>徐浩</Author><Year>2014</Year><RecNum>9152</RecNum><record><rec-number>9152</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1393130653">9152</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">徐浩</style></author><author><styleface="normal"font="default"charset="134"size="100%">邵丹</style></author><author><styleface="normal"font="default"charset="134"size="100%">杨鸿辉</style></author><author><styleface="normal"font="default"charset="134"size="100%">延卫</style></author></authors></contributors><titles><title>Ti_Sb_SnO2电极电解后的表面状态变化研究</title><secondary-title><styleface="normal"font="default"charset="134"size="100%">西安交通大学学报</style></secondary-title></titles><periodical><full-title>西安交通大学学报</full-title></periodical><pages>93-98</pages><volume>48</volume><number>2</number><section>93</section><dates><year>2014</year></dates><urls></urls></record></Cite></EndNote>[43,44]。而在钛基体和表面活性层之间引入中间层能够有效保护钛基体与涂层之间这一重要界面，避免出现氧化物层脱落以及活性层钝化的现象。常见中间层有贵金属（Pt为代表）、铂族氧化物（RuO2，IrO2）、金属氧化物（Sb-SnO2、α-PbO2及MnO2等）。徐浩ADDINEN.CITE<EndNote><Cite><Author>徐浩</Author><Year>2012</Year><RecNum>8565</RecNum><DisplayText>[45]</DisplayText><record><rec-number>8565</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366799652">8565</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author><styleface="normal"font="default"charset="134"size="100%">徐浩</style></author><author><styleface="normal"font="default"charset="134"size="100%">延卫</style></author><author><styleface="normal"font="default"charset="134"size="100%">常乐</style></author></authors></contributors><titles><title>Pb3O4层引入对钛基PbO_2电极强化寿命的影响</title><secondary-title><styleface="normal"font="default"charset="134"size="100%">稀有金属材料与工程</style></secondary-title></titles><periodical><full-title>稀有金属材料与工程</full-title></periodical><pages>462-466</pages><volume>41</volume><number>3</number><section>462</section><dates><year>2012</year></dates><urls></urls></record></Cite></EndNote>[45]等以Ti/Sb-SnO2/PbO2电极为基础，在Sb-SnO2层与PbO2层之间嵌入Pb3O4过渡层，有效削弱了涂层间的内应力，同时提高了电极的抗侵蚀能力，使得Ti/SnO2-Sb2O5/Pb3O4/PbO2电极的稳定性有了明显的增强，其强化寿命由原来的100.5h提高至970.0h。（3）颗粒掺杂颗粒掺杂是指将活性颗粒或惰性颗粒加入二氧化铅电极的电沉积液中，利用电化学共沉积过程，使得颗粒被裹挟进入二氧化铅层中，使得完整镀层被分割为多个小区域，减少电极表面层的内应力，提高电极稳定性，其过程如图4所示。图4颗粒掺杂改性二氧化铅电极过程示意图ADDINEN.CITE<EndNote><Cite><Author>Hua</Author><Year>2020</Year><RecNum>23687</RecNum><DisplayText>[46]</DisplayText><record><rec-number>23687</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1593048216">23687</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>GuoHua</author><author>XuZhicheng</author><author>QiaoDan</author><author>WangLiangtian</author><author>XuHao</author><author>YanWei</author></authors></contributors><titles><title>Fabricationandcharacterizationoftitanium-basedleaddioxideelectrodebyelectrochemicaldepositionwithTi4O7particles</title><secondary-title>WaterEnvironmentResearch</secondary-title></titles><periodical><full-title>WaterEnvironmentResearch</full-title><abbr-1>WaterEnvironRes</abbr-1></periodical><pages>1-9</pages><dates><year>2020</year></dates><urls></urls><electronic-resource-num>/10.1002/wer.1339</electronic-resource-num></record></Cite></EndNote>[46]所谓活性颗粒，即本身具有功能性，并能通过掺杂方式赋予复合电极以相应的功能。徐浩ADDINEN.CITE<EndNote><Cite><Author>Hao</Author><Year>2013</Year><RecNum>8564</RecNum><DisplayText>[47]</DisplayText><record><rec-number>8564</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1366799467">8564</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>XuHao</author><author>ZhangQian</author><author>YanWei</author><author>ChuW</author><author>ZhangLongfei</author></authors></contributors><titles><title>PreparationandCharacterizationofPbO2ElectrodesDopedwithTiO2andItsDegradationEffectonAzoDyeWastewater</title><secondary-title>InternationalJournalofElectrochemicalScience</secondary-title></titles><periodical><full-title>InternationalJournalofElectrochemicalScience</full-title><abbr-1>IntJElectrochemSc</abbr-1></periodical><pages>5382-5395</pages><volume>8</volume><section>5382</section><dates><year>2013</year></dates><urls></urls></record></Cite></EndNote>[47]等采用共沉积的方式将P25-TiO2颗粒掺杂到PbO2活性层中，制备出了具有光电性质的TiO2-PbO2电极，并且其稳定性也有了一定程度提高。所谓惰性颗粒，即颗粒掺入无法使得复合电极有性质上的增加，仅能改善二氧化铅的原始性能ADDINEN.CITEADDINEN.CITE.DATA[48]。姚颖悟课题组ADDINEN.CITEADDINEN.CITE.DATA[49-52]采用共沉积的方式将CeO2、ZrO2颗粒掺杂到PbO2层中，研究这些金属氧化物粒子对电极性能的影响。结果证明CeO2、ZrO2颗粒的掺杂可以有效提高电极的析氧过电位与强化寿命。（4）元素掺杂元素掺杂是将某种或某几种选定的元素加入到电极刷涂液或是电沉积液中，通过热分解或电沉积的方式，使得元素进入金属氧化物活性层，进而使得电极性质发生改变。以Sb-SnO2阳极为例，有研究者使用稀土元素（Eu，Gd等）ADDINEN.CITEADDINEN.CITE.DATA[53,54]，CdADDINEN.CITE<EndNote><Cite><Author>Sun</Author><Year>2014</Year><RecNum>9220</RecNum><DisplayText>[55]</DisplayText><record><rec-number>9220</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1393462817">9220</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Peng</author><author>Zhou,Xin</author><author>Wang,Chen</author><author>Wang,Biao</author><author>Xu,Xiumei</author><author>Lu,Geyu</author></authors></contributors><titles><title>One-stepsynthesisandgassensingpropertiesofhierarchicalCd-dopedSnO2nanostructures</title><secondary-title>SensorsandActuatorsB:Chemical</secondary-title></titles><periodical><full-title>SensorsandActuatorsB:Chemical</full-title></periodical><pages>32-39</pages><volume>190</volume><dates><year>2014</year></dates><isbn>09254005</isbn><urls></urls><electronic-resource-num>10.1016/j.snb.2013.08.045</electronic-resource-num></record></Cite></EndNote>[55]、FeADDINEN.CITE<EndNote><Cite><Author>Xu</Author><Year>2012</Year><RecNum>9955</RecNum><DisplayText>[56]</DisplayText><record><rec-number>9955</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1397177293">9955</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xu,D.</author><author>Lu,C.H.</author><author>Zhang,D.P.</author><author>Song,J.B.</author><author>Ni,Y.R.</author><author>Xu,Z.Z.</author></authors></contributors><auth-address>Xu,D NanjingUnivTechnol,CollMatSci&Engn,StateKeyLabMatOrientChemEngn,Nanjing210009,Jiangsu,PeoplesRChina NanjingUnivTechnol,CollMatSci&Engn,StateKeyLabMatOrientChemEngn,Nanjing210009,Jiangsu,PeoplesRChina NanjingUnivTechnol,CollMatSci&Engn,StateKeyLabMatOrientChemEngn,Nanjing210009,Jiangsu,PeoplesRChina</auth-address><titles><title>Preparationandphotocatalyticactivitiesofalpha-Fe2O3/Sb-dopedSnO2(ATO)nanocomposites</title><secondary-title>MaterialSciencesandTechnology,Pts1&2</secondary-title><alt-title>AdvMaterRes-Switz</alt-title></titles><alt-periodical><full-title>ProgressinMaterialsandProcesses,Pts1-3</full-title><abbr-1>AdvMaterRes-Switz</abbr-1></alt-periodical><pages>722-727</pages><volume>560-561</volume><keywords><keyword>alpha-fe2o3/sb-dopedsno2</keyword><keyword>nanocomposites</keyword><keyword>photocatalyticactivitie</keyword></keywords><dates><year>2012</year></dates><isbn>1022-6680</isbn><accession-num>WOS:000317994200122</accession-num><urls><related-urls><url><GotoISI>://WOS:000317994200122</url></related-urls></urls><electronic-resource-num>DOI10.4028//AMR.560-561.722</electronic-resource-num><language>English</language></record></Cite></EndNote>[56]、Bi、NiADDINEN.CITE<EndNote><Cite><Author>NanjanaguduSubbaRao</Author><Year>2018</Year><RecNum>23627</RecNum><DisplayText>[57]</DisplayText><record><rec-number>23627</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1562980885">23627</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>NanjanaguduSubbaRao,Anantha</author><author>ThimmappaVenkatarangaiah,Venkatesha</author></authors></contributors><titles><title>PreparationandcharacterizationofTi/Sb-SnO2/Ni-Sb-SnO2anode;applicationinelectrochemicaldegradationofAcidRedIdye</title><secondary-title>MaterialsToday:Proceedings</secondary-title></titles><periodical><full-title>MaterialsToday:Proceedings</full-title></periodical><pages>25006-25015</pages><volume>5</volume><number>11</number><section>25006</section><dates><year>2018</year></dates><isbn>22147853</isbn><urls></urls><electronic-resource-num>10.1016/j.matpr.2018.10.301</electronic-resource-num></record></Cite></EndNote>[57]等能有效提升Sb-SnO2电极电催化氧化活性，但提升电极稳定性的能力十分有限。也有研究者以铂族元素（Pt，Ru，Ir）ADDINEN.CITE<EndNote><Cite><Author>Berenguer</Author><Year>2009</Year><RecNum>9177</RecNum><DisplayText>[58,59]</DisplayText><record><rec-number>9177</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1393462651">9177</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Berenguer,R.</author><author>Quijada,C.</author><author>Morallón,E.</author></authors></contributors><titles><title>ElectrochemicalcharacterizationofSnO2electrodesdopedwithRuandPt</title><secondary-title>ElectrochimicaActa</secondary-title></titles><periodical><full-title>ElectrochimicaActa</full-title></periodical><pages>5230-5238</pages><volume>54</volume><number>22</number><dates><year>2009</year></dates><isbn>00134686</isbn><urls></urls><electronic-resource-num>10.1016/j.electacta.2009.04.016</electronic-resource-num></record></Cite><Cite><Author>Fernandes</Author><Year>2014</Year><RecNum>9218</RecNum><record><rec-number>9218</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1393462810">9218</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Fernandes,A.</author><author>Santos,D.</author><author>Pacheco,M.J.</author><author>Ciríaco,L.</author><author>Lopes,A.</author></authors></contributors><titles><title>NitrogenandorganicloadremovalfromsanitarylandfillleachatesbyanodicoxidationatTi/Pt/PbO2,Ti/Pt/SnO2-Sb2O4andSi/BDD</title><secondary-title>AppliedCatalysisB:Environmental</secondary-title></titles><periodical><full-title>AppliedCatalysisB:Environmental</full-title></periodical><pages>288-294</pages><volume>148-149</volume><dates><year>2014</year></dates><isbn>09263373</isbn><urls></urls><electronic-resource-num>10.1016/j.apcatb.2013.10.060</electronic-resource-num></record></Cite></EndNote>[58,59]进行掺杂，虽能大大提升Sb-SnO2电极的寿命，但是却会使电极向析氧类电极过渡，降低电极的电化学氧化能力。对于PbO2电极，研究者发现通过电沉积法进行金属元素（如BiADDINEN.CITEADDINEN.CITE.DATA[60,61]、CeADDINEN.CITE<EndNote><Cite><Author>Yao</Author><Year>2019</Year><RecNum>23546</RecNum><DisplayText>[49]</DisplayText><record><rec-number>23546</rec-number><foreign-keys><keyapp="EN"db-id="tw00aa5s4evda7e9dt55rv9qze0t2vp9xxez"timestamp="1550479789">23546</key><keyapp="ENWeb"db-id="">0</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yao,Y.</author><author>Ren,B.</author><author>Yang,Y.</author><author>Huang,C.</author><author>Li,M.</author></authors></contributors><auth-address>HebeiUniversityofTechnology,SchoolofChemicalEngineeringandTechnology,Tianjin300130,PRChina.Electronicaddress:yaoyingwu@. HebeiUniversityofTechnology,SchoolofChemicalEngineeringandTechnology,Tianjin300130,PRChina. HebeiUniversityofTechnology,SchoolofChemicalEngineeringandTechnology,Tianjin300130,PRChina.Electronicaddress:yangyang0410@.</auth-address><titles><title>PreparationandelectrochemicaltreatmentapplicationofCe-PbO2/ZrO2compositeelectrodeinthedegradationofacridineorangebyelectrochemicaladvancedoxidationprocess</title><secondary-title>JHazardMater</secondary-title></titles><periodical><full-title>JHazardMater</full-title><abbr-1>Journalofhazardousmaterials</abbr-1></periodical><pages>141-151</pages><volume>361</volume><keywords><keyword>Acridineorange</keyword><keyword>Ce-PbO(2)/ZrO(2)compositee