Noncovalent Immobilization of Pentamethylcyclopentadienyl Iridium Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation

Autor: Ana M. Geer, Chang Liu, Charles B. Musgrave III, Christopher Webber, Grayson Johnson, Hua Zhou, Cheng-Jun Sun, Diane A. Dickie, William A. Goddard III, Sen Zhang, T. Brent Gunnoe
Jazyk: angličtina
Rok vydání: 2021
Předmět:
Zdroj: Small Science, Vol 1, Iss 11, Pp n/a-n/a (2021)
Druh dokumentu: article
ISSN: 2688-4046
DOI: 10.1002/smsc.202100037
Popis: The attachment of molecular catalysts to conductive supports for the preparation of solid‐state anodes is important for the development of devices for electrocatalytic water oxidation. The preparation and characterization of three molecular cyclopentadienyl iridium(III) complexes, Cp*Ir(1‐pyrenyl(2‐pyridyl)ethanolate‐κO,κN)Cl (1) (Cp* = pentamethylcyclopentadienyl), Cp*Ir(diphenyl(2‐pyridyl)methanolate‐κO,κN)Cl (2), and [Cp*Ir(4‐(1‐pyrenyl)‐2,2′‐bipyridine)Cl]Cl (3), as precursors for electrochemical water oxidation catalysts, are reported. These complexes contain aromatic groups that can be attached via noncovalent π‐stacking to ordered mesoporous carbon (OMC). The resulting iridium‐based OMC materials (Ir‐1, Ir‐2, and Ir‐3) were tested for electrocatalytic water oxidation leading to turnover frequencies (TOFs) of 0.9–1.6 s−1 at an overpotential of 300 mV under acidic conditions. The stability of the materials is demonstrated by electrochemical cycling and X‐ray absorption spectroscopy analysis before and after catalysis. Theoretical studies on the interactions between the molecular complexes and the OMC support provide insight onto the noncovalent binding and are in agreement with the experimental loadings.
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