Synthesis and Electrocatalytic Water Oxidation by Electrode-Bound Helical Peptide Chromophore鈥揅atalyst Assemblies

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• 作者：Derek M. Ryan ; Michael K. Coggins ; Javier J. Concepcion ; Dennis L. Ashford ; Zhen Fang ; Leila Alibabaei ; Da Ma ; Thomas J. Meyer ; Marcey L. Waters
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：August 4, 2014
• 年：2014
• 卷：53
• 期：15
• 页码：8120-8128
• 全文大小：447K
• ISSN：1520-510X

文摘

Artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells requires the assembly of a chromophore and catalyst in close proximity on the surface of a transparent, high band gap oxide semiconductor for integrated light absorption and catalysis. While there are a number of approaches to assemble mixtures of chromophores and catalysts on a surface for use in artificial photosynthesis based on dye-sensitized photoelectrosynthesis cells, the synthesis of discrete surface-bound chromophore鈥揷atalyst conjugates is a challenging task with few examples to date. Herein, a versatile synthetic approach and electrochemical characterization of a series of oligoproline-based light-harvesting chromophore鈥搘ater-oxidation catalyst assemblies is described. This approach combines solid-phase peptide synthesis for systematic variation of the backbone, copper(I)-catalyzed azide鈥揳lkyne cycloaddition (CuAAC) as an orthogonal approach to install the chromophore, and assembly of the water-oxidation catalyst in the final step. Importantly, the catalyst was found to be incompatible with the conditions both for amide bond formation and for the CuAAC reaction. The modular nature of the synthesis with late-stage assembly of the catalyst allows for systematic variation in the spatial arrangement of light-harvesting chromophore and water-oxidation catalyst and the role of intrastrand distance on chromophore鈥揷atalyst assembly properties. Controlled potential electrolysis experiments verified that the surface-bound assemblies function as water-oxidation electrocatalysts, and electrochemical kinetics data demonstrate that the assemblies exhibit greater than 10-fold rate enhancements compared to the homogeneous catalyst alone.