Thiol-derivatized metalloporphyrins. Monomolecular films for the electrocatalytic reduction of dioxygen at gold electrodes

Journal Article · Mon Nov 01 00:00:00 EST 1993 · Langmuir; (United States)

DOI:https://doi.org/10.1021/la00035a006· OSTI ID:5565867

Zak, J; Yuan, H; Ho, M; Woo, L K; Porter, M D ^[1]

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1. Ames Lab. - USDOE, IA (United States) Iowa State Univ., Ames, IA (United States)

This paper describes preliminary results in the design, construction, and characterization of cobalt (II) porphyrins derivatized with alkanethiol appendages. The use of the thiol appendages leads to the formation of a chemisorbed monolayer of the corresponding thiolate at gold electrodes. Our findings suggest that this approach may serve as a beginning for fabricating electrocatalytic monolayers with a preselected architecture through the manipulation of the number and location of the appendages. Voltammetric data indicate that monolayers from both I(Co) and II(Co) catalyze the two-electron reduction of O[sub 2] to H[sub 2]O[sub 2]. The monolayer from I(Co), however, has a lower electrocatalytic activity. Infrared, X-ray photoelectron, and visible spectroscopic data are presented that argue the difference in reactivity arises from a difference in interfacial architecture. The results from attempts to metalate monolayers from I(H[sub z]) and II(H[sub z]) support this interpretation. Findings are also reported that indicate the preparation of mixed monolayers (e.g., two-component monolayers from I(Co) and CH[sub 3](CH[sub z])[sub 3]SH) may prove valuable to this area of research. 20 refs., 3 figs.

• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 5565867
• Journal Information: Langmuir; (United States), Vol. 9:11; ISSN 0743-7463
• Country of Publication: United States
• Language: English

Related Subjects

30 DIRECT ENERGY CONVERSION
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COBALT COMPLEXES
DERIVATIZATION
ELECTROCATALYSTS
FABRICATION
OXYGEN
REDUCTION
ELECTRODES
FUEL CELLS
GOLD
HYDROGEN PEROXIDE
INFRARED SPECTRA
PORPHYRINS
THIN FILMS
THIOLS
VOLTAMETRY
X-RAY SPECTROSCOPY
CARBOXYLIC ACIDS
CATALYSTS
CHEMICAL REACTIONS
COMPLEXES
DIRECT ENERGY CONVERTERS
ELECTROCHEMICAL CELLS
ELEMENTS
FILMS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN COMPOUNDS
METALS
NONMETALS
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
SPECTRA
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
300503* - Fuel Cells- Materials
Components
& Auxiliaries
400102 - Chemical & Spectral Procedures
400400 - Electrochemistry
400201 - Chemical & Physicochemical Properties