【水相电催化氧还原反应（ORR）过程及基本原理概述3900字】

PAGE4水相电催化氧还原反应（ORR）过程及基本原理概述目录TOC\o"1-3"\h\u32509水相电催化氧还原反应（ORR）过程及基本原理概述 19465（一）氧还原反应的基本原理 116589（二）四电子途径ORR——燃料电池 221549（三）二电子途径ORR——制备过氧化氢 3目前所研究的氧还原反应发生环境多样，如水相ADDINEN.CITEADDINEN.CITE.DATA[1]、气固相ADDINEN.CITE<EndNote><Cite><Author>Xia</Author><Year>2019</Year><RecNum>26</RecNum><DisplayText><styleface="superscript">[2]</style></DisplayText><record><rec-number>26</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618540885">26</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Xia,Chuan</author><author>Xia,Yang</author><author>Zhu,Peng</author><author>Fan,Lei</author><author>Wang,Haotian</author></authors></contributors><titles><title>DirectelectrosynthesisofpureaqueousH2O2solutionsupto20%byweightusingasolidelectrolyte</title><secondary-title>Science</secondary-title><short-title>2</short-title></titles><periodical><full-title>Science</full-title></periodical><pages>226-+</pages><volume>366</volume><number>6462</number><dates><year>2019</year><pub-dates><date>Oct11</date></pub-dates></dates><isbn>0036-8075</isbn><accession-num>WOS:000490014700040</accession-num><urls><related-urls><url><styleface="underline"font="default"size="100%"><GotoISI>://WOS:000490014700040</style></url></related-urls></urls><electronic-resource-num>10.1126/science.aay1844</electronic-resource-num></record></Cite></EndNote>[2]等，驱动反应的条件也十分丰富，如光ADDINEN.CITE<EndNote><Cite><Author>Fan</Author><Year>2020</Year><RecNum>28</RecNum><DisplayText><styleface="superscript">[3]</style></DisplayText><record><rec-number>28</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541017">28</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Fan,Wenjun</author><author>Zhang,Bingqing</author><author>Wang,Xiaoyu</author><author>Ma,Weiguang</author><author>Li,Deng</author><author>Wang,Zhiliang</author><author>Dupuis,Michel</author><author>Shi,Jingying</author><author>Liao,Shijun</author><author>Li,Can</author></authors></contributors><titles><title>Efficienthydrogenperoxidesynthesisbymetal-freepolyterthiopheneviaphotoelectrocatalyticdioxygenreduction</title><secondary-title>Energy&EnvironmentalScience</secondary-title><short-title>3</short-title></titles><periodical><full-title>Energy&EnvironmentalScience</full-title></periodical><pages>238-245</pages><volume>13</volume><number>1</number><section>238</section><dates><year>2020</year></dates><isbn>1754-5692 1754-5706</isbn><urls></urls><electronic-resource-num>10.1039/c9ee02247c</electronic-resource-num></record></Cite></EndNote>[3]、电[1]、磁ADDINEN.CITE<EndNote><Cite><Author>Yan</Author><Year>2021</Year><RecNum>29</RecNum><DisplayText><styleface="superscript">[4]</style></DisplayText><record><rec-number>29</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541191">29</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Yan,J.</author><author>Wang,Y.</author><author>Zhang,Y.</author><author>Xia,S.</author><author>Yu,J.</author><author>Ding,B.</author></authors></contributors><auth-address>KeyLaboratoryofTextileScience&Technology,CollegeofTextile,DonghuaUniversity,Shanghai,201620,China. InnovationCenterforTextileScienceandTechnology,DonghuaUniversity,Shanghai,200051,China.</auth-address><titles><title>DirectMagneticReinforcementofElectrocatalyticORR/OERwithElectromagneticInductionofMagneticCatalysts</title><secondary-title>AdvMater</secondary-title><short-title>4</short-title></titles><periodical><full-title>AdvMater</full-title></periodical><pages>e2007525</pages><volume>33</volume><number>5</number><edition>2020/12/19</edition><keywords><keyword>bifunctionaloxygencatalysts</keyword><keyword>directmagneticenhancement</keyword><keyword>macroporouscarbonnanofibers</keyword><keyword>magneticcatalyticnanocages</keyword><keyword>rechargeableZn-airbatteries</keyword></keywords><dates><year>2021</year><pub-dates><date>Feb</date></pub-dates></dates><isbn>1521-4095(Electronic) 0935-9648(Linking)</isbn><accession-num>33336466</accession-num><urls><related-urls><url>/pubmed/33336466</url></related-urls></urls><electronic-resource-num>10.1002/adma.202007525</electronic-resource-num></record></Cite></EndNote>[4]等。本文则主要研究水相电催化氧还原。（一）氧还原反应的基本原理在电化学中，氧还原反应即为氧分子O2在电极表面获得电子被还原的反应。从式（1.1）可见虽然氧还原反应在热力学上十分有利，但通过其电极反应方程式，式（1.2）（1.3）可见，氧还原反应涉及多电子转移过程，其动力学缓慢，具有较高的过电势，表现为平衡电势附近时的反应速率较低。H2(g)+O2+2O2+4另外，根据得到电子的多少，氧还原大致可分为两种途径。O2通过四电子（4e-）途径被还原为水（H2O）。在4e-途径中，又分为直接4e-途径和（2+2）e-途径。在（2+2）e-途径中O2可经过单独一个二电子（2e-）途径还原停留在过氧化氢（H2O2）。此外，在不同的酸碱性环境中，ORR反应物、产物物种及其对应的电极电势也会有所不同。因此，氧还原反应需选择合适的催化剂，在加快反应速率的同时，提高所需产物的选择性，使得反应高效定向地向目标进行。在涂覆有催化剂的电极上发生的ORR，目前人们公认的反应机理模型为结合机理（AssociativeMechanism）和解离机理（DissociativeMechanism），见下图1.1。氧分子以不同的形式在催化剂活性位点上进行吸附，其中，只有通过结合机理才能实现2e-途径还原产生H2O2，而两种机理都可以实现4e-转移还原产生H2O。图1.1电催化ORR机理示意图ADDINEN.CITE<EndNote><Cite><Author>Guo</Author><Year>2019</Year><RecNum>30</RecNum><DisplayText><styleface="superscript">[5]</style></DisplayText><record><rec-number>30</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541220">30</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Guo,Xiangyu</author><author>Lin,Shiru</author><author>Gu,Jinxing</author><author>Zhang,Shengli</author><author>Chen,Zhongfang</author><author>Huang,Shiping</author></authors></contributors><titles><title>SimultaneouslyAchievingHighActivityandSelectivitytowardTwo-ElectronO2Electroreduction:ThePowerofSingle-AtomCatalysts</title><secondary-title>ACSCatalysis</secondary-title><short-title>5</short-title></titles><periodical><full-title>ACSCatalysis</full-title></periodical><pages>11042-11054</pages><volume>9</volume><number>12</number><section>11042</section><dates><year>2019</year></dates><isbn>2155-5435 2155-5435</isbn><urls></urls><electronic-resource-num>10.1021/acscatal.9b02778</electronic-resource-num></record></Cite></EndNote>[5]（二）四电子途径ORR——燃料电池四电子（4e-）途径ORR被研究最早，应用也最广。其中最典型的应用例子为燃料电池。燃料电池是一种将氢气、甲烷等燃料分子的化学能转变为电能的装置。由于没有热机过程，所以没有卡诺循环的限制，能量转化效率高（40-60%）。此外，与传统的发电方式相比，它在运作过程中没有硫氧化物和氮氧化物等污染物产生。以上优点使得它被认为是21世纪最有前景的发电方式之一。如图1.2所示，在燃料电池的工作环境中，阴极尽可能希望氧分子以4e-途径被还原，由此得到的电池理论输出电压高。若氧分子以2e-途径被还原，则理论输出电压大大降低。图1.2燃料电池中的氧还原反应ADDINEN.CITE<EndNote><Cite><Author>Siahrostami</Author><Year>2020</Year><RecNum>31</RecNum><DisplayText><styleface="superscript">[6]</style></DisplayText><record><rec-number>31</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541249">31</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Siahrostami,Samira</author><author>Villegas,SantiagoJimenez</author><author>BagherzadehMostaghimi,AmirHassan</author><author>Back,Seoin</author><author>Farimani,AmirBarati</author><author>Wang,Haotian</author><author>Persson,KristinAslaug</author><author>Montoya,Joseph</author></authors></contributors><titles><title>AReviewonChallengesandSuccessesinAtomic-ScaleDesignofCatalystsforElectrochemicalSynthesisofHydrogenPeroxide</title><secondary-title>ACSCatalysis</secondary-title><short-title>6</short-title></titles><periodical><full-title>ACSCatalysis</full-title></periodical><pages>7495-7511</pages><volume>10</volume><number>14</number><section>7495</section><dates><year>2020</year></dates><isbn>2155-5435 2155-5435</isbn><urls></urls><electronic-resource-num>10.1021/acscatal.0c01641</electronic-resource-num></record></Cite></EndNote>[6]目前商用燃料电池催化剂中效果最好的是铂碳（Pt/C）催化剂，但其成本高、耐久性差、Pt易受一氧化碳（CO）毒化等缺点限制了其大规模应用。据统计，催化剂的Pt成本在燃料电池中占比高达49%ADDINEN.CITE<EndNote><Cite><Author>Hu</Author><Year>2015</Year><RecNum>32</RecNum><DisplayText><styleface="superscript">[7]</style></DisplayText><record><rec-number>32</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541272">32</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Hu,Yang</author><author>Jensen,JensOluf</author><author>Zhang,Wei</author><author>Martin,Santiago</author><author>Chenitz,Régis</author><author>Pan,Chao</author><author>Xing,Wei</author><author>Bjerrum,NielsJ.</author><author>Li,Qingfeng</author></authors></contributors><titles><title>Fe3C-basedoxygenreductioncatalysts:synthesis,hollowsphericalstructuresandapplicationsinfuelcells</title><secondary-title>JournalofMaterialsChemistryA</secondary-title><short-title>7</short-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title></periodical><pages>1752-1760</pages><volume>3</volume><number>4</number><section>1752</section><dates><year>2015</year></dates><isbn>2050-7488 2050-7496</isbn><urls></urls><electronic-resource-num>10.1039/c4ta03986f</electronic-resource-num></record></Cite></EndNote>[7]。因此，研究人员发展出一系列非贵金属催化剂。其中，Fe-N-C催化剂的性能与Pt/C催化剂相媲美ADDINEN.CITE<EndNote><Cite><Author>Gao</Author><Year>2018</Year><RecNum>33</RecNum><DisplayText><styleface="superscript">[8]</style></DisplayText><record><rec-number>33</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541313">33</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Gao,Liqin</author><author>Xiao,Meiling</author><author>Jin,Zhao</author><author>Liu,Changpeng</author><author>Zhu,Jianbing</author><author>Ge,Junjie</author><author>Xing,Wei</author></authors></contributors><titles><title>CorrelatingFesourcewithFe-N-Cactivesiteconstruction:Guidanceforrationaldesignofhigh-performanceORRcatalyst</title><secondary-title>JournalofEnergyChemistry</secondary-title><short-title>8</short-title></titles><periodical><full-title>JournalofEnergyChemistry</full-title></periodical><pages>1668-1673</pages><volume>27</volume><number>6</number><section>1668</section><dates><year>2018</year></dates><isbn>20954956</isbn><urls></urls><electronic-resource-num>10.1016/j.jechem.2018.06.008</electronic-resource-num></record></Cite></EndNote>[8]。但是铁基催化剂有一致命缺点，即燃料电池2e-途径副反应产生的过氧物种会与之发生芬顿（Fenton）反应（式1.4）。由此产生的活性氧物种（ROS）会损坏催化剂和电极，从而大大降低电池寿命。FentonReaction：Fe总之，燃料电池阴极催化剂发展的关键在于提高反应活性的同时，降低ORR的2e-选择性，避免HO2-或H2O2过氧物种对催化剂或者其他电池组件产生腐蚀而缩短电池寿命。（三）二电子途径ORR——制备过氧化氢虽然二电子（2e-）途径ORR在燃料电池中被认为是不利于电池设计和工作的副反应，但研究人员发现其可以作为一种利用可再生能源产生的电能在温和条件下还原氧气生产双氧水的潜在绿色方法。目前，该领域的关注度持续上升。与4e-ORR类似，要实现O2电化学合成H2O2，关键之处同样是设计合成出高活性、高选择性的催化剂。基于图（1.1）的机理，为同时提高ORR产生H2O2的活性和选择性，所设计的催化剂活性位点应具备适当的*OOH结合能和较弱的*O吸附能（对O2分子的结合不能太强）两个条件。若*OOH结合能太强，会导致产物H2O2难以脱附，带来更高的过电位；若*OOH结合能太弱或*O吸附能太强，则*OOH易得电子被还原裂解为*O和H2O，*O进一步被还原生成H2O。只有当*OOH结合能适中，*O吸附能较低，ORR才能高效地以2e-途径进行[5]。1.二电子ORR应用价值通过电化学2e-ORR，氧气可被还原产生双氧水。双氧水作为一种重要的化工原料和潜在的能量载体ADDINEN.CITE<EndNote><Cite><Author>Fukuzumi</Author><Year>2012</Year><RecNum>34</RecNum><DisplayText><styleface="superscript">[9]</style></DisplayText><record><rec-number>34</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541366">34</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Fukuzumi,S.</author><author>Yamada,Y.</author><author>Karlin,K.D.</author></authors></contributors><auth-address>DepartmentofMaterialandLifeScience,GraduateSchoolofEngineering,OsakaUniversity,ALCA,JapanScienceandTechnologyAgency(JST),Suita,Osaka565-0871,Japan;DepartmentofBioinspiredScience,EwhaWomansUniversity,Seoul120-750,Korea.</auth-address><titles><title>HydrogenPeroxideasaSustainableEnergyCarrier:ElectrocatalyticProductionofHydrogenPeroxideandtheFuelCell</title><secondary-title>ElectrochimActa</secondary-title><short-title>9</short-title></titles><periodical><full-title>ElectrochimActa</full-title></periodical><pages>493-511</pages><volume>82</volume><edition>2013/03/05</edition><dates><year>2012</year><pub-dates><date>Nov1</date></pub-dates></dates><isbn>0013-4686(Print) 0013-4686(Linking)</isbn><accession-num>23457415</accession-num><urls><related-urls><url>/pubmed/23457415</url></related-urls></urls><custom2>PMC3584454</custom2><electronic-resource-num>10.1016/j.electacta.2012.03.132</electronic-resource-num></record></Cite></EndNote>[9]，它的应用领域十分广泛。在诸如漂白、污水处理、化学合成、冶金等领域都不乏它的身影。尤其是当其充当氧化剂时，质量氧化效率高且产物绿色无污染ADDINEN.CITE<EndNote><Cite><Author>Campos-Martin</Author><Year>2006</Year><RecNum>35</RecNum><DisplayText><styleface="superscript">[10]</style></DisplayText><record><rec-number>35</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541390">35</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Campos-Martin,J.M.</author><author>Blanco-Brieva,G.</author><author>Fierro,J.L.</author></authors></contributors><auth-address>InstitutodeCatalisisyPetroleoquimica,CSIC,MarieCurie2,Cantoblanco,28049Madrid,Spain.</auth-address><titles><title>Hydrogenperoxidesynthesis:anoutlookbeyondtheanthraquinoneprocess</title><secondary-title>AngewChemIntEdEngl</secondary-title><short-title>10</short-title></titles><periodical><full-title>AngewChemIntEdEngl</full-title></periodical><pages>6962-84</pages><volume>45</volume><number>42</number><edition>2006/10/14</edition><dates><year>2006</year><pub-dates><date>Oct27</date></pub-dates></dates><isbn>1433-7851(Print) 1433-7851(Linking)</isbn><accession-num>17039551</accession-num><urls><related-urls><url>/pubmed/17039551</url></related-urls></urls><electronic-resource-num>10.1002/anie.200503779</electronic-resource-num></record></Cite></EndNote>[10]。图1.3双氧水的应用领域[10]正因过氧化氢用途广泛，据有关数据统计，全球过氧化氢的市场需求到2024年将达年均600万吨的水平ADDINEN.CITE<EndNote><Cite><Author>Kim</Author><Year>2018</Year><RecNum>36</RecNum><DisplayText><styleface="superscript">[11]</style></DisplayText><record><rec-number>36</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541416">36</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Kim,HyoWon</author><author>Ross,MichaelB.</author><author>Kornienko,Nikolay</author><author>Zhang,Liang</author><author>Guo,Jinghua</author><author>Yang,Peidong</author><author>McCloskey,BryanD.</author></authors></contributors><titles><title>Efficienthydrogenperoxidegenerationusingreducedgrapheneoxide-basedoxygenreductionelectrocatalysts</title><secondary-title>NatureCatalysis</secondary-title><short-title>11</short-title></titles><periodical><full-title>NatureCatalysis</full-title></periodical><pages>282-290</pages><volume>1</volume><number>4</number><section>282</section><dates><year>2018</year></dates><isbn>2520-1158</isbn><urls></urls><electronic-resource-num>10.1038/s41929-018-0044-2</electronic-resource-num></record></Cite></EndNote>[11]。然而，目前H2O2的生产方式仍主要以20世纪40年代始创的传统蒽醌法（AnthraquinoneOxidation，AO）为主。AO法主要包含氢化、氧化、过氧化氢浓缩、工作液后处理四步，见图1.4。其中氢化过程需要催化剂，而双氧水在后续蒽氧化返回蒽醌的过程中产出，得到的蒽醌又可以循环利用。虽然由AO法制取双氧水的单次循环产量高，但它的缺点尤为显著，总结有如下几点：①多步合成，步骤繁琐②能耗大③存在副反应，使得蒽醌工作液及氢化催化剂无法100%循环利用④制得的双氧水需从有机相浓缩、分离⑤只适合大规模生产⑥双氧水生产后需要浓缩至70%以减少运输成本，存在一定的安全隐患ADDINEN.CITE<EndNote><Cite><Author>Jiang</Author><Year>2018</Year><RecNum>37</RecNum><DisplayText><styleface="superscript">[12]</style></DisplayText><record><rec-number>37</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541450">37</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jiang,Yuanyuan</author><author>Ni,Pengjuan</author><author>Chen,Chuanxia</author><author>Lu,Yizhong</author><author>Yang,Ping</author><author>Kong,Biao</author><author>Fisher,Adrian</author><author>Wang,Xin</author></authors></contributors><titles><title>SelectiveElectrochemicalH2 O2 ProductionthroughTwo-ElectronOxygenElectrochemistry</title><secondary-title>AdvancedEnergyMaterials</secondary-title><short-title>12</short-title></titles><periodical><full-title>AdvancedEnergyMaterials</full-title></periodical><volume>8</volume><number>31</number><section>1801909</section><dates><year>2018</year></dates><isbn>16146832</isbn><urls></urls><electronic-resource-num>10.1002/aenm.201801909</electronic-resource-num></record></Cite></EndNote>[12]。图1.4AO法制过氧化氢示意图尽管后来发展出可分散生产过氧化氢的直接合成法，即利用氢气和氧气在催化剂的作用下直接化合生产，但该法存在爆炸的危险且过氧化氢的产速和产率并不高[12]。在当今“绿色发展”的主题下，电化学ORR合成过氧化氢被视为替代传统合成的最具前景的途径之一。与传统合成法相比，电化学ORR的优势在于输入的能源可再生、反应条件温和、反应过程无污染性和危险性、原料丰富、可实现小规模原位生产。要实现高效电化学ORR合成过氧化氢，如前文分析，关键在于设计出高活性、高选择性的2e-途径催化剂。2.催化剂评价准则理想的2e-ORR电催化剂应具备下列这些条件：（1）制备成本低：成本低是催化剂能大规模应用的关键前提。（2）导电性好：催化剂的导电性影响电子向反应物分子传递的效率，优越的导电性是理想催化剂的必要条件。（3）催化活性高：理想催化剂能大幅降低反应能垒，过电位小，Tafel斜率较小，电子传输动力学迅速。另外，极限电流密度接近2e-转移理论最大值，由式（2.1）可得，在一般测试转速1600rpm时，2e-转移电流密度理论最大值为2.85mA/cm2。（4）2e-选择性高：副反应程度低，反应转移电子数接近2、法拉第效率高。（5）稳定性好：催化剂活性位点不易受环境或副产物等影响，如在宽pH范围内催化剂活性保持良好或是经长时间催化反应后催化剂活性无大幅度衰减。3.二电子ORR催化剂研究进展（1）贵金属催化剂金属铂（Pt）最早因其出色的4e-ORR性能被广泛关注。然而，作为4e-ORR的副反应，2e-ORR因能原位绿色生产双氧水，关注度逐年上升。因此，研究人员对Pt催化剂进行调控改性，大大提高了其2e-选择性，发展出一系列Pt基2e-催化剂。对ORR机理的认识正是人们在对Pt基催化剂的研究中逐渐深入完善。铂（Pt）基催化剂图1.1阐明了2e-ORR的关键中间体为*OOH。若催化活性位点与*OOH结合太强，则不利于产物H2O2的脱附。因此，Dahn等人认为催化剂纳米颗粒均匀分散能增大H2O2的脱附空间，进而提高2e-选择性。Inaba和Compton等人的工作证实了该观点。Inaba将Pt分散在导电碳上，得到Pt/C催化剂，经比例调控，实现了1MHClO4酸性环境中67%的H2O2选择性ADDINEN.CITE<EndNote><Cite><Author>Bonakdarpour</Author><Year>2008</Year><RecNum>7</RecNum><DisplayText><styleface="superscript">[13]</style></DisplayText><record><rec-number>7</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618453651">7</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Bonakdarpour,Arman</author><author>Dahn,TaraR.</author><author>Atanasoski,R.T.</author><author>Debe,M.K.</author><author>Dahn,J.R.</author></authors></contributors><titles><title>H[sub2]O[sub2]ReleaseduringOxygenReductionReactiononPtNanoparticles</title><secondary-title>ElectrochemicalandSolid-StateLetters</secondary-title><short-title>13</short-title></titles><periodical><full-title>ElectrochemicalandSolid-StateLetters</full-title></periodical><pages>B208</pages><volume>11</volume><number>11</number><dates><year>2008</year></dates><publisher>TheElectrochemicalSociety</publisher><isbn>1099-0062</isbn><urls><related-urls><url>/10.1149/1.2978090</url></related-urls></urls><electronic-resource-num>10.1149/1.2978090</electronic-resource-num></record></Cite></EndNote>[13]。Compton等人控制修饰在玻碳电极上的铂纳米颗粒的大小，发现小粒径有利于H2O2的脱附扩散，因而具备更高的2e-选择性ADDINEN.CITE<EndNote><Cite><Author>Gara</Author><Year>2013</Year><RecNum>8</RecNum><DisplayText><styleface="superscript">[14]</style></DisplayText><record><rec-number>8</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618454022">8</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Gara,Matthew</author><author>Laborda,Eduardo</author><author>Holdway,Philip</author><author>Crossley,Alison</author><author>Jones,CharlesJ.V.</author><author>Compton,RichardG.</author></authors></contributors><titles><title>Oxygenreductionatsparsearraysofplatinumnanoparticlesinaqueousacid:hydrogenperoxideasaliberatedtwoelectronintermediate</title><secondary-title>PhysicalChemistryChemicalPhysics</secondary-title><short-title>14</short-title></titles><periodical><full-title>PhysicalChemistryChemicalPhysics</full-title></periodical><pages>19487</pages><volume>15</volume><number>44</number><dates><year>2013</year></dates><publisher>RoyalSocietyofChemistry(RSC)</publisher><isbn>1463-9076</isbn><urls><related-urls><url>/10.1039/c3cp53684j</url></related-urls></urls><electronic-resource-num>10.1039/c3cp53684j</electronic-resource-num></record></Cite></EndNote>[14]。Markovic等人用杯[4]芳烃限域铂原子，实现了在0.1MHClO4酸性环境中高效2e-ORR，比Pt（111）晶面过电位降低300mVADDINEN.CITE<EndNote><Cite><Author>Genorio</Author><Year>2010</Year><RecNum>9</RecNum><DisplayText><styleface="superscript">[15]</style></DisplayText><record><rec-number>9</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618454276">9</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Genorio,Bostjan</author><author>Strmcnik,Dusan</author><author>Subbaraman,Ram</author><author>Tripkovic,Dusan</author><author>Karapetrov,Goran</author><author>Stamenkovic,VojislavR.</author><author>Pejovnik,Stane</author><author>Marković,NenadM.</author></authors></contributors><titles><title>Selectivecatalystsforthehydrogenoxidationandoxygenreductionreactionsbypatterningofplatinumwithcalix[4]arenemolecules</title><secondary-title>NatureMaterials</secondary-title><short-title>15</short-title></titles><periodical><full-title>NatureMaterials</full-title></periodical><pages>998-1003</pages><volume>9</volume><number>12</number><dates><year>2010</year></dates><publisher>SpringerScienceandBusinessMediaLLC</publisher><isbn>1476-1122</isbn><urls><related-urls><url>/10.1038/nmat2883</url></related-urls></urls><electronic-resource-num>10.1038/nmat2883</electronic-resource-num></record></Cite></EndNote>[15]。此外，还有利用TiN、TiC等载体分散铂原子的研究，均能实现较高的H2O2选择性ADDINEN.CITEADDINEN.CITE.DATA[16,17]。贵金属合金催化剂金（Au）、银（Ag）、汞（Hg）等金属与*O的结合能力较弱，从机理上分析，该类金属更倾向于2e-ORR生成H2O2。然而，这类金属吸附O2的能力弱，其ORR动力学极其缓慢，过电位大ADDINEN.CITE<EndNote><Cite><Author>Jirkovský</Author><Year>2011</Year><RecNum>12</RecNum><DisplayText><styleface="superscript">[18]</style></DisplayText><record><rec-number>12</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618454863">12</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Jirkovský,JakubS.</author><author>Panas,Itai</author><author>Ahlberg,Elisabet</author><author>Halasa,Matej</author><author>Romani,Simon</author><author>Schiffrin,DavidJ.</author></authors></contributors><titles><title>SingleAtomHot-SpotsatAu–PdNanoalloysforElectrocatalyticH2O2Production</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title><short-title>18</short-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>19432-19441</pages><volume>133</volume><number>48</number><dates><year>2011</year></dates><publisher>AmericanChemicalSociety(ACS)</publisher><isbn>0002-7863</isbn><urls><related-urls><url>/10.1021/ja206477z</url></related-urls></urls><electronic-resource-num>10.1021/ja206477z</electronic-resource-num></record></Cite></EndNote>[18]。因此，将*O结合能强弱的金属制成合金，成为实现2e-ORR高活性和选择性的新策略。图1.7不同金属*O结合能-催化活性火山曲线ADDINEN.CITE<EndNote><Cite><Author>Wang</Author><Year>2020</Year><RecNum>38</RecNum><DisplayText><styleface="superscript">[19]</style></DisplayText><record><rec-number>38</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618541487">38</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Wang,K.</author><author>Huang,J.</author><author>Chen,H.</author><author>Wang,Y.</author><author>Song,S.</author></authors></contributors><auth-address>TheKeyLabofLow-carbonChemistry&EnergyConservationofGuangdongProvince,SchoolofMaterialsScienceandEngineering,SunYat-senUniversity,Guangzhou510275,P.R.China.stsssq@.</auth-address><titles><title>Recentadvancesinelectrochemical2eoxygenreductionreactionforon-sitehydrogenperoxideproductionandbeyond</title><secondary-title>ChemCommun(Camb)</secondary-title><short-title>19</short-title></titles><periodical><full-title>ChemCommun(Camb)</full-title></periodical><pages>12109-12121</pages><volume>56</volume><number>81</number><edition>2020/09/23</edition><dates><year>2020</year><pub-dates><date>Oct18</date></pub-dates></dates><isbn>1364-548X(Electronic) 1359-7345(Linking)</isbn><accession-num>32959823</accession-num><urls><related-urls><url>/pubmed/32959823</url></related-urls></urls><electronic-resource-num>10.1039/d0cc05156j</electronic-resource-num></record></Cite></EndNote>[19]Jirkovsky等人利用碳负载Au0.92Pd0.08纳米颗粒（Au0.92Pd0.08/C）提高了二电子ORR活性的同时，实现了95%的选择性[18]。Rossmeisl等人先通过计算预测利用Hg和Pt制成合金能大幅提高其2e-选择性。随后，实验表明Pt-Hg合金在0.2-0.4Vvs.RHE的电位下H2O2选择性达到96%ADDINEN.CITE<EndNote><Cite><Author>Siahrostami</Author><Year>2013</Year><RecNum>13</RecNum><DisplayText><styleface="superscript">[20]</style></DisplayText><record><rec-number>13</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618455630">13</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Siahrostami,Samira</author><author>Verdaguer-Casadevall,Arnau</author><author>Karamad,Mohammadreza</author><author>Deiana,Davide</author><author>Malacrida,Paolo</author><author>Wickman,Björn</author><author>Escudero-Escribano,María</author><author>Paoli,ElisaA.</author><author>Frydendal,Rasmus</author><author>Hansen,ThomasW.</author><author>Chorkendorff,Ib</author><author>Stephens,IfanE.L.</author><author>Rossmeisl,Jan</author></authors></contributors><titles><title>EnablingdirectH2O2productionthroughrationalelectrocatalystdesign</title><secondary-title>NatureMaterials</secondary-title><short-title>20</short-title></titles><periodical><full-title>NatureMaterials</full-title></periodical><pages>1137-1143</pages><volume>12</volume><number>12</number><dates><year>2013</year></dates><publisher>SpringerScienceandBusinessMediaLLC</publisher><isbn>1476-1122</isbn><urls><related-urls><url>/10.1038/nmat3795</url></related-urls></urls><electronic-resource-num>10.1038/nmat3795</electronic-resource-num></record></Cite></EndNote>[20]。受此启发，Stephen等人进行了关于Hg合金的研究，发现Pd-Hg位于火山图的顶端ADDINEN.CITE<EndNote><Cite><Author>Verdaguer-Casadevall</Author><Year>2014</Year><RecNum>14</RecNum><DisplayText><styleface="superscript">[21]</style></DisplayText><record><rec-number>14</rec-number><foreign-keys><keyapp="EN"db-id="erpe0sdt5z0zd2eztp7vz0rz5ras0vv5rwsw"timestamp="1618455909">14</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Verdaguer-Casadevall,Arnau</author><author>Deiana,Davide</author><author>Karamad,Mohammadreza</author><author>Siahrostami,Samira</author><author>Malacrida,Paolo</author><author>Hansen,ThomasW.</author><author>Rossmeisl,Jan</author><author>Chorkendorff,Ib</author><author>Stephens,IfanE.L.</author></authors></contributors><titles><title>TrendsintheElectrochemicalSynthesisofH2O2:EnhancingActivityandSelectivitybyElectrocatalyti