Self Assembled Films of Porphyrins with Amine Groups at Different Positions Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity 英文参考文献.docVIP

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Self Assembled Films of Porphyrins with Amine Groups at Different Positions Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity 英文参考文献.doc

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Self Assembled Films of Porphyrins with Amine Groups at Different Positions Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity 英文参考文献

Molecules 2012, 17, 7824-7842; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Self Assembled Films of Porphyrins with Amine Groups at Different Positions: Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity Koodlur Sannegowda Lokesh ?, Michel De Keersmaecker and Annemie Adriaens * Department of Analytical Chemistry, Ghent University, Krijgslaan 281-S12, 9000 Ghent, Belgium; E-Mails: lokeshsk@ (K.S.L.); michel.dekeersmaecker@ugent.be (M.D.K.) ? Current address: Faculty of Science and Technology, Shinshu University, Tokida, Ueda, Nagano 386-8567, Japan. * Author to whom correspondence should be addressed; E-Mail: annemie.adriaens@ugent.be; Tel.: +32-9-264-4826; Fax: +32-9-264-4960. Received: 28 April 2012; in revised form: 8 June 2012 / Accepted: 12 June 2012 / Published: 26 June 2012 Abstract: Self-assembled molecular films of two cobalt porphyrins with amine groups at different positions—(5,10,15,20-tetrakis-(2-aminophenyl) porphyrin-cobalt(II), [Co(II) (T(o-NH2)PP)] and (5,10,15,20-tetrakis-(4-aminophenyl) porphyrin-cobalt(II), [Co(II)(T(p-NH2)PP)]—were formed on a gold substrate. The functionalized surfaces were characterized using Raman spectroscopy, atomic force microscopy and electrochemical methods. Both modified gold surfaces completely mask the charge transfer of a [Fe(CN)6]3?/4? redox couple in solution, indicating the layer is highly resistive in behavior. Electrochemical impedance spectroscopy analyses revealed that the porphyrin film with amine groups at ortho positions shows a higher charge-transfer resistance with a better protective behavior compared to the para position modified surface. Raman, AFM and EIS data suggests that an ortho amine positioned molecule forms a more compact layer compared to the para-positioned molecule. This can be explained in terms of their orientatio