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Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor

Materna, Kelly L. and Rudshteyn, Benjamin and Brennan, Bradley J. and Kane, Morgan H. and Bloomfield, Aaron J. and Huang, Daria L. and Shopov, Dimitar Y. and Batista, Victor S. and Crabtree, Robert H. and Brudvig, Gary W. (2016) Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor. ACS Catalysis, 6 (8). pp. 5371-5377. ISSN 2155-5435. doi:10.1021/acscatal.6b01101.

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A pentamethylcyclopentadienyl (Cp*) iridium water-oxidation precatalyst was modified to include a silatrane functional group for covalent attachment to metal oxide semiconductor surfaces. The heterogenized catalyst was found to perform electrochemically driven water oxidation at an overpotential of 462 mV with a turnover number of 304 and turnover frequency of 0.035 s^(–1) in a 0.1 M KNO3 electrolyte at pH 5.8. Computational modeling of the experimental IR spectra suggests that the catalyst retains its Cp* group during the first hour of catalysis and likely remains monomeric.

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Additional Information:© 2016 American Chemical Society. Received: April 18, 2016; Revised: July 4, 2016; Published: July 8, 2016. This material is based upon work supported as part of the Argonne-Northwestern Solar Energy Research (ANSER) Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-SC0001059. Additional funding was provided by a generous donation from the TomKat Charitable Trust. V.S.B. acknowledges high performance computing time from NERSC and the high performance computing facilities at Yale and Shanghai Jiao Tong University. B.R. acknowledges support from the National Science Foundation Graduate Research Fellowship under Grant DGE-1122492. We thank Subhajyoti Chaudhuri and the group of Charles A. Schmuttenmaer for helpful discussions. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001059
TomKat Charitable TrustUNSPECIFIED
NSF Graduate Research FellowshipDGE-1122492
Subject Keywords:alternative energy; electrocatalysis; iridium; metal oxide; silatrane; surface binding; water oxidation
Issue or Number:8
Record Number:CaltechAUTHORS:20160831-131102505
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Official Citation:Heterogenized Iridium Water-Oxidation Catalyst from a Silatrane Precursor Kelly L. Materna, Benjamin Rudshteyn, Bradley J. Brennan, Morgan H. Kane, Aaron J. Bloomfield, Daria L. Huang, Dimitar Y. Shopov, Victor S. Batista, Robert H. Crabtree, and Gary W. Brudvig ACS Catalysis 2016 6 (8), 5371-5377 DOI: 10.1021/acscatal.6b01101
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70076
Deposited By: Tony Diaz
Deposited On:31 Aug 2016 22:08
Last Modified:11 Nov 2021 04:23

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