Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 113, Issue 21, Pages 9359-9367Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp803725x
Keywords
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Funding
- Natural Science Foundation of China [20775060, 20875077]
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Self-assembled monolayers (SAMs) of thiol-derivatized tetraphenylporphyrin (SH-TPP) and cobalt tetraphenylporphyrin (SH-CoTPP) have been prepared to examine the structure and direct electron transfer (ET) on a gold electrode in an aqueous solution. The cyclic voltammetry peaks of the porphyrin were obviously observed in aqueous solution. An interesting phenomenon was that direct ET cannot occur in phosphate-buffered solutions when a highly oriented and tightly packed monolayer is in existence, but the relatively low-density SH-TPP SAMs exhibited good electrochemical response. The electron transfer rate constants were obtained from the impedance spectra (Cole-Cole plot), upon application of different biasing potentials to the modified electrode. We propose a new kinetic model of the ET processes of SAMs of thiol-derivatized porphyrin and apply the density functional theory (DFT) to study the ET of porphyrin molecules on Au surfaces.
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