Experimental and theoretical study of the activity of substituted metallophthalocyanines for nitrite electro-oxidation

被引:50
作者
Caro, CA [1 ]
Bedioui, F
Páez, MA
Cárdenas-Jiron, GI
Zagal, JH
机构
[1] Univ Santiago Chile, Fac Quim & Biol, Dept Quim Mat, Santiago, Chile
[2] Univ Santiago Chile, Fac Quim & Biol, Dept Ciencias Quim, Lab Quim Theor, Santiago, Chile
[3] Ecole Natl Super Chim Paris, CNRS, UMR 7575,ENSCP, Lab Electrochim & Chim Analyt, F-75231 Paris 05, France
关键词
D O I
10.1149/1.1631822
中图分类号
O646 [电化学、电解、磁化学];
学科分类号
081704 ;
摘要
The electrocatalytic activity of various metallophthalocyanines (M-Pc) adsorbed on an ordinary pyrolytic graphite electrode for the oxidation of nitrite has been investigated in aqueous phosphate buffer solution (pH 7.3). A comparison of Pcs of different metals, shows that the activity is influenced by the nature of the central metal but not very significantly. However, the effect of substituents on the periphery of the Pc ligand is more pronounced. Electron-donor substituents of the Pc ligand enhance this activity. At a density functional theoretical level, we found that the calculated condensed Fukui function, associated to a nucleophilic attack, gives a reasonable explanation for the location of the reaction site in the case of the set of M-Pcs. Indeed, for Cr-Pc, Mn-Pc, Fe-Pc, and Co-Pc, the Fukui function predicts that the preferred reactive sites are located on the central metal whereas for Ni-Pc, Cu-Pc, and Zn-Pc it predicts that the reactive sites are located on the ligand, in agreement with the experimental trends observed. (C) 2003 The Electrochemical Society.
引用
收藏
页码:E32 / E39
页数:8
相关论文
共 42 条
[21]  
Lever ABP, 1999, J PORPHYR PHTHALOCYA, V3, P488, DOI 10.1002/(SICI)1099-1409(199908/10)3:6/7<488::AID-JPP167>3.3.CO
[22]  
2-B
[23]  
LEVER ABP, 1982, ADV CHEM SER, V201, P237
[24]   SUBSTITUTED COBALT PHTHALOCYANINE COMPLEXES AS CARRIERS FOR NITRITE-SENSITIVE ELECTRODES [J].
LI, JZ ;
PANG, XY ;
YU, RQ .
ANALYTICA CHIMICA ACTA, 1994, 297 (03) :437-442
[25]   Nitrite reduction by myoglobin in surfactant films [J].
Lin, R ;
Bayachou, M ;
Greaves, J ;
Farmer, PJ .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (51) :12689-12690
[26]  
MARLETTA MA, 1992, FRONTIERS MOL TOXICO, P46
[27]   Electroreduction of nitrite by hemin, myoglobin and hemoglobin in surfactant films [J].
Mimica, D ;
Zagal, JH ;
Bedioui, F .
JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 2001, 497 (1-2) :106-113
[28]   Detection and determination of nitrate and nitrite: a review [J].
Moorcroft, MJ ;
Davis, J ;
Compton, RG .
TALANTA, 2001, 54 (05) :785-803
[29]   ELECTROCRYSTALLIZATION OF METALLOPHTHALOCYANINES - EFFECTS OF SUBSTITUENTS ON THE OXIDATION POTENTIAL AND CRYSTALLIZATION [J].
ORIHASHI, Y ;
OHNO, H ;
TSUCHIDA, E ;
MATSUDA, H ;
NAKANISHI, H ;
KATO, M .
MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 1988, 160 :139-&
[30]   DENSITY FUNCTIONAL-APPROACH TO THE FRONTIER-ELECTRON THEORY OF CHEMICAL-REACTIVITY [J].
PARR, RG ;
YANG, WT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (14) :4049-4050