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1、化学学报ACTACHIMICASINICA综述ReviewDOI:10.6023/A14080602对氨基苯硫酚分子的表面增强拉曼光谱及等离激元光催化反应赵刘斌a黄逸凡a吴德印*,a任斌*,a,b(a厦门大学化学化工学院固体表面物理化学国家重点实验室厦门361005)(b厦门大学能源材料协同创新中心厦门361005)摘要对氨基苯硫酚(PATP)是表面增强拉曼光谱(SERS)研究中最重要的探针分子之一.PATP吸附体系具有非常特征且异常强的SERS信号,但人们对其SERS信号的理解仍存在较大争议.本文结合文
2、献,总结了我们为了理解PATP分子异常的SERS光谱所开展的系统的理论和实验工作.首先介绍PATP的SERS增强机理方面开展的理论工作,研究表明PATP分子的异常SERS信号不是来自PATP分子本身,而是来自其表面催化偶联反应产物二巯基偶氮苯(DMAB).通过实验和DMAB合成两个方面,验证了DMAB是异常SERS信号的根源.其次总结了各种实验条件对PATP转化为DMAB的影响,并从实验和理论两个角度探讨PATP的表面催化偶联反应机理.最后,通过对PATP体系的SERS和等离激元增强化学反应的总结,展望表面
3、等离激元增强化学反应的未来发展方向.关键词对氨基苯硫酚(PATP);表面增强拉曼光谱;表面等离激元共振;光催化反应;密度泛函理论Surface-enhancedRamanSpectroscopyandPlasmon-AssistedPhotocatalysisofp-AminothiophenolZhao,LiubinaHuang,YifanaWu,Deyin*,aRen,Bin*,a,b(aStateKeyLaboratoryofPhysicalChemistryofSolidSurfacesandDep
4、artmentofChemistry,CollegeofChemistryandChemicalEngineering,XiamenUniversity,Xiamen361005)(bInnovationCenterofChemistryforEnergeticMaterials,XiamenUniversity,Xiamen361005)Abstractp-Aminothiophenol(PATP)isoneofthemostimportantprobemoleculesinsurface-enhance
5、dRamanspectros-copy(SERS).AdsorbedPATPexhibitsveryuniqueandabnormallyintenseSERSsignals.However,theunderstandingto-wardtheabnormalSERSsignalsisstillindebate.Inthisreview,weoverviewourtheoreticalandexperimentalstudiestounderstandtheabnormalSERSofPATP.Wefirs
6、tintroducethetheoreticalinvestigationontheSERSenhancementmecha-nismofPATP.ThetheoreticalstudyshowsthattheabnormalSERSsignalsofPATParenotfromPATPitselfbutarisefromitssurfacecatalyticcouplingproductp,p'-dimercaptoazobenzene(DMAB).Theassumptionissupportedbyca
7、refullyde-signedexperimentsofPATPandtheSERSsignalofthesynthesizedDMABmolecule.Then,wesummarizetheexperimentalfactorsthatinfluencethephotochemicalconversionofPATPtoDMABonthesurfacesofmetalnanostructures.Wethenex-plorethereactionmechanismsforthesurfacecataly
8、ticcouplingreactionofPATPinbothexperimentalandtheoreticalas-pects.Finally,weproposedthefurtherdirectionofsurfaceplasmonenhancedchemicalreactiononthebasisofoursystem-aticallystudiesofSERSandplasmonphotocatalys
