【《CeO2及其复合物的形貌控制与合成机理研究文献综述》6700字】

图1-3是在纳米尺度的Kirkendall效应下空心纳米结构的形成过程ADDINEN.CITEADDINEN.CITE.DATA[12,36]。2017年，Sun等人ADDINEN.CITE<EndNote><Cite><Author>Sun</Author><Year>2017</Year><RecNum>1127</RecNum><DisplayText><styleface="superscript">[37]</style></DisplayText><record><rec-number>1127</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619029889"guid="7971537b-ab87-4e77-b635-baf9fb4b489b">1127</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Yugang</author><author>Zuo,Xiaobing</author><author>Sankaranarayanan,SubramanianK.R.S.</author><author>Peng,Sheng</author><author>Narayanan,Badri</author><author>Kamath,Ganesh</author></authors></contributors><titles><title>Quantitative3Devolutionofcolloidalnanoparticleoxidationinsolution</title><secondary-title>Science</secondary-title></titles><periodical><full-title>Science</full-title></periodical><pages>303-307</pages><volume>356</volume><number>6335</number><dates><year>2017</year></dates><urls><related-urls><url>/content/sci/356/6335/303.full.pdf</url></related-urls></urls><electronic-resource-num>10.1126/science.aaf6792</electronic-resource-num></record></Cite></EndNote>[37]首先同时基于时间分辨小角和广角X射线散射，在Kirkendall过程中直接观察到纳米颗粒中间体三维形貌的变化。这一发现为深入理解Kirkendall效应提供了强有力的工具。图1-SEQ图1-\*ARABIC4Kirkendall效应制备空心纳米结构示意图Figure1-4SchematicdiagramofhollownanostructurespreparedbyKirkendalleffectLi等人利用Kirkendall效应制备了空心结构的CeO2-ZrO2固溶体。首先，制备了球形或立方形的CeO2并分别作为模板。当Zr4+离子被引入该体系中时，与CeO2发生反应并掺杂其中，形成Ce1−xZrxO2固溶体。ADDINEN.CITE<EndNote><Cite><Author>Liang</Author><Year>2008</Year><RecNum>1128</RecNum><DisplayText><styleface="superscript">[38]</style></DisplayText><record><rec-number>1128</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619102507"guid="a3ca522d-6eec-4465-8874-eee3d4a695bf">1128</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Liang,Xin</author><author>Wang,Xun</author><author>Zhuang,Yuan</author><author>Xu,Biao</author><author>Kuang,Simin</author><author>Li,Yadong</author></authors></contributors><titles><title>FormationofCeO2−ZrO2SolidSolutionNanocageswithControllableStructuresviaKirkendallEffect</title><secondary-title>JournaloftheAmericanChemicalSociety</secondary-title></titles><periodical><full-title>JournaloftheAmericanChemicalSociety</full-title></periodical><pages>2736-2737</pages><volume>130</volume><number>9</number><dates><year>2008</year><pub-dates><date>2008/03/01</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>0002-7863</isbn><urls><related-urls><url>/10.1021/ja7109629</url></related-urls></urls><electronic-resource-num>10.1021/ja7109629</electronic-resource-num></record></Cite></EndNote>[38]同时，基于Kirkendall效应，形成足够多的孔洞，最终凝聚形成空心结构。同样，基于Kirkendall效应，Zr掺杂的CeO2纳米管也可以被制得。Lee等人基于水热法，将NaOH与Ce3+在少量ZrO2粉末共混，生成ZrxCe1−x(OH)3纳米棒。随后，Zr4+离子对Ce3+/Ce4+离子的扩散起催化作用。由于Ce4+的扩散速率高于Ce3+，随着内部Ce3+的氧化形成了Ce净向外流动，导致了从棒状氢氧化物向Zr掺杂CeO2纳米管转变和分解。ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2009</Year><RecNum>1129</RecNum><DisplayText><styleface="superscript">[39]</style></DisplayText><record><rec-number>1129</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619109187"guid="61f8b64c-051d-4f61-9ca7-e18eb101dd1a">1129</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Ying-Chen</author><author>Chen,Kuei-Bo</author><author>Lee,Chi-Shen</author><author>Lin,M.C.</author></authors></contributors><titles><title>DirectSynthesisofZr-DopedCeriaNanotubes</title><secondary-title>TheJournalofPhysicalChemistryC</secondary-title></titles><periodical><full-title>TheJournalofPhysicalChemistryC</full-title></periodical><pages>5031-5034</pages><volume>113</volume><number>13</number><dates><year>2009</year><pub-dates><date>2009/04/02</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>1932-7447</isbn><urls><related-urls><url>/10.1021/jp810492s</url></related-urls></urls><electronic-resource-num>10.1021/jp810492s</electronic-resource-num></record></Cite></EndNote>[39]再者，Ag纳米线也可被用于制备Ag掺杂CeO2纳米管。Mendoza-Anaya等人首先采用溶胶-凝胶法在PVP修饰的Ag纳米线上涂覆CeO2纳米颗粒。然后在空气中加热烧结。因此，当Ag向外扩散速率超过了壳层材料（CeO2）向内扩散时，界面出现了Kirkendall效应。随着Ag的逐渐排空，其内部空腔逐渐扩大，最终形成空腔较大的Ag/CeO2纳米管。ADDINEN.CITE<EndNote><Cite><Author>Mondragón-Galicia</Author><Year>2011</Year><RecNum>1130</RecNum><DisplayText><styleface="superscript">[40]</style></DisplayText><record><rec-number>1130</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619109674"guid="f2425dab-6f5c-4a32-ba39-b9fdd0ec5583">1130</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Mondragón-Galicia,G.</author><author>Pérez-Hernández,R.</author><author>Gutiérrez-Wing,C.E.</author><author>Mendoza-Anaya,D.</author></authors></contributors><titles><title>Anovelsynthesismethodtoproducesilver-dopedCeO2nanotubesbasedonAgnanowiretemplates</title><secondary-title>PhysicalChemistryChemicalPhysics</secondary-title></titles><periodical><full-title>PhysicalChemistryChemicalPhysics</full-title></periodical><pages>16756-16761</pages><volume>13</volume><number>37</number><dates><year>2011</year></dates><publisher>TheRoyalSocietyofChemistry</publisher><isbn>1463-9076</isbn><work-type>10.1039/C1CP21017C</work-type><urls><related-urls><url>/10.1039/C1CP21017C</url></related-urls></urls><electronic-resource-num>10.1039/C1CP21017C</electronic-resource-num></record></Cite></EndNote>[40]除了固体前驱体与传入分子之间的物理扩散外，另一种方式是基于模板化合物的物质转化，涉及置换反应中不同的扩散速率。离子交换法，通过用不同的离子替换晶格内的阳离子/阴离子来改变材料成分，同时伴随着纳米尺度的Kirkendall效应来创造空洞。Sun等人以Ce(OH)CO3纳米棒为模板和前驱体，制备了CeO2纳米管。在氢氧化钠溶液中，Ce(OH)CO3解离缓慢并且释放出Ce3+、OH-和CO32−离子。随后通过快速的界面离子交换反应在原纳米棒上沉淀生成不溶性的Ce(OH)3壳层。生成的Ce(OH)3壳层将内部部分与溶液分离，因此只能由通过壳层的Ce3+和OH-才能实现以下转化。由于Ce3+离子比OH-离子小得多，Ce3+从Ce(OH)CO3向外扩散的速度要快于OH-离子向内扩散的速度。因此，形成了小段的Kirkendall空洞来补偿Ce3+离子的净流出。随着时间的延长，这些空洞逐渐扩大并聚集，形成单一的大空腔。同时，在碱性环境下，Ce(OH)3氧化为Ce(OH)4。在煅烧处理后，生成CeO2纳米管。ADDINEN.CITE<EndNote><Cite><Author>Chen</Author><Year>2009</Year><RecNum>1131</RecNum><DisplayText><styleface="superscript">[41]</style></DisplayText><record><rec-number>1131</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619116671"guid="378a6a49-79d8-4101-8b5b-5d611380732f">1131</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Chen,Guozhu</author><author>Sun,Sixiu</author><author>Sun,Xun</author><author>Fan,Weiliu</author><author>You,Ting</author></authors></contributors><titles><title>Formation of CeO2 Nanotubes from Ce(OH)CO3NanorodsthroughKirkendallDiffusion</title><secondary-title>InorganicChemistry</secondary-title></titles><periodical><full-title>InorganicChemistry</full-title></periodical><pages>1334-1338</pages><volume>48</volume><number>4</number><dates><year>2009</year><pub-dates><date>2009/02/16</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>0020-1669</isbn><urls><related-urls><url>/10.1021/ic801714z</url></related-urls></urls><electronic-resource-num>10.1021/ic801714z</electronic-resource-num></record></Cite></EndNote>[41]Pan等人开发了一种制备CeO2纳米管的方法。首先，Ce(OH)3纳米颗粒汇聚成纳米棒。其次，Ce(OH)3作为中间体转化为CeO2并在纳米棒表面形成壳层，而纳米棒内部主要成分为Ce(OH)3。接着，溶解的Ce3+在溶液中被氧化，向外扩散，并优先沉积于纳米棒表面。因此，在合适的时间和温度下，可以得到CeO2纳米管ADDINEN.CITE<EndNote><Cite><Author>Pan</Author><Year>2008</Year><RecNum>1132</RecNum><DisplayText><styleface="superscript">[42]</style></DisplayText><record><rec-number>1132</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619119283"guid="f3570abf-b76c-4edf-9b2e-30622f336b54">1132</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Pan,Chengsi</author><author>Zhang,Dengsong</author><author>Shi,Liyi</author><author>Fang,Jianhui</author></authors></contributors><titles><title>Template-FreeSynthesis,ControlledConversion,andCOOxidationPropertiesofCeO2Nanorods,Nanotubes,Nanowires,andNanocubes</title><secondary-title>EuropeanJournalofInorganicChemistry</secondary-title></titles><periodical><full-title>EuropeanJournalofInorganicChemistry</full-title></periodical><pages>2429-2436</pages><volume>2008</volume><number>15</number><dates><year>2008</year></dates><isbn>1434-1948</isbn><urls><related-urls><url>/doi/abs/10.1002/ejic.200800047</url></related-urls></urls><electronic-resource-num>/10.1002/ejic.200800047</electronic-resource-num></record></Cite></EndNote>[42]。Kirkendall效应在控制固溶体的尺寸、形状和组成方面存在巨大的潜力，但应特别注意的是，利用柯肯达尔效应制备中空纳米结构时，原子或离子的扩散速率与正常的溶液传输过程或表面反应过程导致的柯肯达尔效应被区分。（三）电化学置换法电化学置换反应在自然界中广泛存在，其主要是由于金属元素的活泼性不同，在活性较高的金属模板和活性相对较低的金属盐之间进行置换反应。在反应过程中，金属模板原子被氧化溶解至溶液，从而牺牲了模板，同时惰性金属离子在模板表面被还原，形成空心结构。基于这一机制，为构建中空结构的提供了一种可能的方法。Xia等人首次利用电化学置换法合成了尺寸分布窄、形状均匀、腔体大、壳层结晶良好的纳米级空心贵金属结构ADDINEN.CITE<EndNote><Cite><Author>Sun</Author><Year>2002</Year><RecNum>1133</RecNum><DisplayText><styleface="superscript">[43]</style></DisplayText><record><rec-number>1133</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619174235"guid="b5484969-6011-4c55-8b50-026d960d4f70">1133</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Sun,Yugang</author><author>Mayers,BrianT.</author><author>Xia,Younan</author></authors></contributors><titles><title>Template-EngagedReplacementReaction: AOne-StepApproachtotheLarge-ScaleSynthesisofMetalNanostructureswithHollowInteriors</title><secondary-title>NanoLetters</secondary-title></titles><periodical><full-title>NanoLetters</full-title></periodical><pages>481-485</pages><volume>2</volume><number>5</number><dates><year>2002</year><pub-dates><date>2002/05/01</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>1530-6984</isbn><urls><related-urls><url>/10.1021/nl025531v</url></related-urls></urls><electronic-resource-num>10.1021/nl025531v</electronic-resource-num></record></Cite></EndNote>[43]。由此，通过电化学置换反应制备的不同形貌金属空心结构继承了模板的形状，且壳体的厚度也由模板决定。同样，电化学置换反应也能应用于氧化物体系。不同与金属体系的是，氧化还原反应发生在可变价金属离子对之间，使氧化物中的高价离子与溶液中的低价离子交换。Peter等人ADDINEN.CITE<EndNote><Cite><Author>Ramani</Author><Year>2017</Year><RecNum>1134</RecNum><DisplayText><styleface="superscript">[44]</style></DisplayText><record><rec-number>1134</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619189403"guid="91627a46-30a0-402d-9ff3-d9a889f8d9d0">1134</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Ramani,Swetha</author><author>Sarkar,Sumanta</author><author>Vemuri,Vamseedhara</author><author>Peter,SebastianC.</author></authors></contributors><titles><title>ChemicallydesignedCeO2nanoboxesboostthecatalyticactivityofPtnanoparticlestowardelectro-oxidationofformicacid</title><secondary-title>JournalofMaterialsChemistryA</secondary-title></titles><periodical><full-title>JournalofMaterialsChemistryA</full-title><abbr-1>JMaterChemA</abbr-1></periodical><pages>11572-11576</pages><volume>5</volume><number>23</number><dates><year>2017</year></dates><publisher>TheRoyalSocietyofChemistry</publisher><isbn>2050-7488</isbn><work-type>10.1039/C6TA06339J</work-type><urls><related-urls><url>/10.1039/C6TA06339J</url></related-urls></urls><electronic-resource-num>10.1039/C6TA06339J</electronic-resource-num></record></Cite></EndNote>[44]报道了一种CeO2纳米盒负载Pt的方案，该方案使用Cu2O纳米立方体作为模板，用Ce4+和Pt4+依次取代Cu+。首先，Cu2O纳米立方体被分散于含Ce4+的溶液中并发生电置换，形成CeO2壳层得到Cu2O@CeO2核壳立方体。随后，Cu+电还原K2PtCl6形成Pt纳米颗粒，并进一步溶解了Cu2O，形成空心的CeO2纳米盒。Lee等人ADDINEN.CITE<EndNote><Cite><Author>Lee</Author><Year>2016</Year><RecNum>1135</RecNum><DisplayText><styleface="superscript">[45]</style></DisplayText><record><rec-number>1135</rec-number><foreign-keys><keyapp="EN"db-id="swdx0aa0w2f2the2fs6pzdeaxvz9wawrttwz"timestamp="1619202739"guid="c1960012-e47f-4d8c-92d7-43a2769e1f7f">1135</key></foreign-keys><ref-typename="JournalArticle">17</ref-type><contributors><authors><author>Lee,Dong-Gyu</author><author>Kim,SooMin</author><author>Kim,SunMi</author><author>Lee,SiWoo</author><author>Park,JeongYoung</author><author>An,Kwangjin</author><author>Lee,InSu</author></authors></contributors><titles><title>PostsynthesisModulationoftheCatalyticInterfaceinsideaHollowNanoreactor:ExploitationoftheBidirectionalBehaviorofMixed-ValentMn3O4PhaseintheGalvanicReplacementReaction</title><secondary-title>ChemistryofMaterials</secondary-title></titles><periodical><full-title>ChemistryofMaterials</full-title></periodical><pages>9049-9055</pages><volume>28</volume><number>24</number><dates><year>2016</year><pub-dates><date>2016/12/27</date></pub-dates></dates><publisher>AmericanChemicalSociety</publisher><isbn>0897-4756</isbn><urls><related-urls><url>/10.1021/acs.chemmater.6b04097</url></related-urls></urls><electronic-resource-num>10.1021/acs.chemmater.6b04097</electronic-resource-num></record></Cite></EndNote>[45]基于其先前的研究，以Mn3O4@SiO2空心球为原料，在不添加还原剂的情况下，通过电替代反应在内腔的Mn3O4上沉积Pt、Pd、Ir和Rh纳米颗粒。随后，将前者形成的纳米结构浸入70℃的Ce3+水溶液中，使得Mn3O4固体与Ce3+离子在溶液中发生电化学置换反应来沉积CeO2。在整个过程中，混合价Mn3O4在电化学置换反应中既引起贵金属离子的还原，又引起低价Ce3+离子的氧化。因此，在纳米反应器中形成的CeO2继承原Mn3O4的空心结构形态。虽然通过电置换反应能制备不同形状、不同尺寸、可控制孔隙率和可调节腔体的空心结构。但需要指出的是，电置换反应法相对不易控制。其次，该方法目前仅限于贵金属、一些过渡金属氧化物或硫化物的制备，且模板的选择也较为狭窄。再者，电置换过程中总是伴随着合金与脱合金、掺杂与脱掺杂过程，形成的壳层或框架结构不稳易破碎塌陷。参考文献[1] 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