以循环伏安方法在玻碳载体上制备纳米级厚度的过渡金属 (Pt,Pd ,Rh ,Ru)和合金 (PtPd ,PtRu)薄膜电极 ,并运用原位FTIR反射光谱研究了CO的吸附过程 .发现所制备的纳米薄膜电极均具有异常红外效应 ,即与本体金属电极相比较 ,吸附在纳米薄膜电极上的CO分子的红外吸收被显著增强 ,并且红外谱峰方向倒反 .本文的结果进一步证明异常红外效应是一种新的、普遍的现象 ,主要取决于过渡金属或合金膜的结构和厚度 .对异常红外效应的深入认识 ,不仅将推动红外反射光谱及界面电化学理论的发展 ,而且将在表面和界面分析中得到广泛应用 .
孙世刚
,
郑明森
,
卢国强
,
蔡丽蓉
,
陈声培
,
肖晓银
. 酸性溶液中过渡金属及合金纳米薄膜电极的异常红外效应研究[J]. 电化学, 2000
, 6(1)
: 25
-30
.
DOI: 10.61558/2993-074X.1368
The adsorption of CO on electrodes of nanometer thin films of transition metals (Pt, Pd, Rh, Ru) and alloys (PtPd, PtRu) prepared under cyclic voltammetric conditions has been studied by in situ FTIR spectroscopy. The abnormal infrared effects (AIREs) have been explored as a novel and general phenomenon. The AIREs consist mainly in the inversion of the direction of IR band and the significant enhancement of IR absorption by adsorbed CO species. It was revealed that the enhanced IR absoroption of adsorbed species in AIREs depends strongly on the nature of metal or alloy, and on the structure and the thickness of the thin film. The investigation of AIREs will contribute not only to develop the theory of reflectance IR spectroscopy as well as interfacial electrochemistry, but also to increase the determining sensitivity in applications of interfacial and surface analysis.
[1] JacobsPW ,WindSJ,etal.Nanometersizeplatinumparticlearray :catalyticandsurfacechemicalproper ties[J].Surf.Sci.,1997,372 :2 49.
[2 ] ChenShengpei,SunShigang ,HuangTaisan .TheStructureandtheElectroanalyticActivityofElectrodeofPlatinizedPlatinumSupportedonGlassyCarbon[J].ChineseScienceBulletin .1995 ,40 (5 ) :377.
[3] LuGQ ,SunSG ,ChenSP ,etal.NovelpropertiesofdispersedPtandPdthinlayersupportedonGCforCOadsorptionstudiedusinginsituMS_FTIRspectroscopy[J].J.ElectroanalChem ,1997,42 1:19.
[4 ] SunSG ,YangDF ,TianZW .InsituFTIRStudiesontheAdsorptionandOxidationofn_propanolandiso propanolataPlatinumElectrode[J].J .ElectroanalChem ,1990 ,2 89:177.
[5 ] LuGQ ,SunSG ,etal.InsituFTIRspectroscopicstudiesofadsorptionofCO ,SCN-andPoly(o_phenylenediamine)onelectrodesofnanometerthinfilmsofPt,PdandRh———Theabnormalinfraredeffects(AIREs) .Langmuir,1999,inpress .
[6 ] HartsteinA ,KirtlyJR ,etal.Enhancementoftheinfraredabsorptionfrommolecularmonolayerswiththinmetaloverlayers[J].Phys.Rev .Lett.1980 ,45 :2 0 1.
[7] OsawaM .Dynamicprocessesineletrochemicalreactionsstudiedbysurface_enhancedinfraredabsorptionspec troscopy (SEIRAS) [J].Bull.Chem .Soc.Jpn .,1997,70 :2 86 1.
[8] SunShi_Gang ,CaiWen_Bin ,etal.EffectsofsurfacestructureofAufilmonIRabsorptionenhancementforCOadsorption———Acombinedstudyofcyclicvoltammetry ,scanningtunnelingmicroscopyandsurfaceen hancedIRspectroscopy[J].J.Phys .Chem .B .1999,10 3:2 46 0 .