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

Geer, Ana M. and Liu, Chang and Musgrave, Charles B., III and Webber, Christopher and Johnson, Grayson and Zhou, Hua and Sun, Cheng-Jun and Dickie, Diane A. and Goddard, William A., III and Zhang, Sen and Gunnoe, T. Brent (2021) Noncovalent Immobilization of Pentamethylcyclopentadienyl Iridium Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation. Small Science, 1 (11). Art. No. 2100037. ISSN 2688-4046. doi:10.1002/smsc.202100037.

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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.

Item Type:Article
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URLURL TypeDescription Image
Geer, Ana M.0000-0003-1115-6759
Musgrave, Charles B., III0000-0002-3432-0817
Dickie, Diane A.0000-0003-0939-3309
Goddard, William A., III0000-0003-0097-5716
Zhang, Sen0000-0002-1716-3741
Gunnoe, T. Brent0000-0001-5714-3887
Additional Information:© 2021 The Authors. Small Science published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. Issue Online: 15 November 2021; Version of Record online: 06 August 2021; Manuscript revised: 01 June 2021; Manuscript received: 20 March 2021. A.M.G. and C.L. contributed equally to this work. This work was primarily supported by the US. National Science Foundation (CBET-1805022). This research used the PHI Versaprobe III XPS facility within the Nanoscale Materials Characterization Facility (NMCF) at the University of Virginia, supported by NSF MRI-1626201. This research used the resources of the Advanced Photon Source, an Office of Science User Facility operated for the USA. Department of Energy (DOE) Office of Science by the Argonne National Laboratory, and was supported by the USA. DOE under contract no. DE–AC02-06CH11357. The authors declare no conflict of interest. Data Availability Statement: The data that support the findings of this study are available from the corresponding author upon reasonable request.
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Subject Keywords:electrocatalysis; iridium molecular complexes; noncovalent immobilization; ordered mesoporous carbon; water oxidation
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Issue or Number:11
Record Number:CaltechAUTHORS:20210831-210007797
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Official Citation:Geer, A.M., Liu, C., Musgrave, C.B., III, Webber, C., Johnson, G., Zhou, H., Sun, C., Dickie, D.A., Goddard, W.A., III, Zhang, S. and Gunnoe, T.B. (2021), Noncovalent Immobilization of Pentamethylcyclopentadienyl Iridium Complexes on Ordered Mesoporous Carbon for Electrocatalytic Water Oxidation. Small Sci., 1: 2100037.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:110668
Deposited By: Tony Diaz
Deposited On:31 Aug 2021 21:08
Last Modified:18 Nov 2021 22:19

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