Interfaces and devices based on supramolecular porphyrins

Author(s)

Herbert Winnischofer

• Document type: Doctoral Thesis
• Press: São Paulo.
• Institution: Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ)
• Defense date: 2004-12-15

Examining board members

Koiti Araki; Lúcio Angnes; Marco Aurélio de Paoli; Osvaldo Antonio Serra; Roberto Manuel Torresi

• Advisor: Koiti Araki

Abstract

A full characterization of the morphologic, conduction, photoelectrochemical and electrocatalytic properties of supramolecular porphyrin films containing ruthenium polypyridyl or ruthenium clusters, is described. Techniques, such as scanning probe microscopy, cyclic voltammetry, electrochemical impedance spectroscopy, UV-vis spectroelectrochemistry, rotating disk electrode voltammetry, and combined electrochemical/photoelectrochemical experiments were employed. Semi-empirical calculations were utilized in order to obtain more information on the interpretations. The preparation method of film deposition has a special effect on the material packing. Consequently, the conduction and photoelectrochemical properties are also affected. For example, the electronic diffusion coefficient (DeCm2) differs by up to 104 times depending on the packing characteristics of the same porphyrin material. The conduction process is limited by a redox mechanism involving the ruthenium centers and is mediated by &#960;* orbitals of the porphyrin or polypyridine species. The photocurrent intensity as a function of the incident &#955; depends on the electron transport mechanism involved and this can be tuned by the nature and the degree of electronic coupling between the porphyrin rings, in the film. This kind of films also exhibits electrocatalytic activities for the oxidation of substrates with interests in the environmental, food and medical areas, such as nitrite, sulfite, and ascorbic acid. The efficiency of these materials are also high, with kf > 104 mol-1dm3s-1. An exponential relationship of the heterogeneous electron transfer kinetic constant with the E1/2 of the redox center was found, as predicted by the Marcus equation. The cobalt porphyrin containing four ruthenium clusters behaves as an efficient catalyst for the 4-electron reduction of O2, at pH <5. The mechanism does not involve the bis-coordination of O2 to two metallic centers, but electronic effects from the ruthenium clusters should be activating the metalloporphyrin center, promoting the multi-electronic transfer and preventing the formation of reactive species, such as OH· e O2-. A FIA cell was built in order to provide a quantitative analysis of sulfite, and it exhibited high sampling frequency, reproducibility, as confirmed by the low detection limit (0.1 &#181;mol.dm-3). The FIA system was adapted and employed with a supramolecular porphyrin film as logic gates and they exhibited a unique behavior, operating the three basic functions (AND, OR and NOT) in a single integrated chemical system. (AU)