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001     904166
005     20240712112826.0
024 7 _ |a 10.1021/acscatal.1c01395
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037 _ _ |a FZJ-2021-05736
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100 1 _ |a Geer, Ana M.
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245 _ _ |a Electrocatalytic Water Oxidation by a Trinuclear Copper(II) Complex
260 _ _ |a Washington, DC
|c 2021
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520 _ _ |a We report a trinuclear copper(II) complex, [(DAM)Cu3(μ3-O)][Cl]4 (1, DAM = dodecaaza macrotetracycle), as a homogeneous electrocatalyst for water oxidation to dioxygen in phosphate-buffered solutions at pH 7.0, 8.1, and 11.5. Electrocatalytic water oxidation at pH 7 occurs at an overpotential of 550 mV with a turnover frequency of ∼19 s–1 at 1.5 V vs NHE. Controlled potential electrolysis (CPE) experiments at pH 11.5 over 3 h at 1.2 V and at pH 8.1 for 40 min at 1.37 V vs NHE confirm the evolution of dioxygen with Faradaic efficiencies of 81% and 45%, respectively. Rinse tests conducted after CPE studies provide evidence for the homogeneous nature of the catalysis. The linear dependence of the current density on the catalyst concentration indicates a likely first-order dependence on the Cu precatalyst 1, while kinetic isotope studies (H2O versus D2O) point to involvement of a proton in or preceding the rate-determining step. Rotating ring-disk electrode measurements at pH 8.1 and 11.2 show no evidence of H2O2 formation and support selectivity to form dioxygen. Freeze-quench electron paramagnetic resonance studies during electrolysis provide evidence for the formation of a molecular copper intermediate. Experimental and computational studies support a key role of the phosphate as an acceptor base. Moreover, density functional theory calculations highlight the importance of second-sphere interactions and the role of the nitrogen-based ligands to facilitate proton transfer processes.
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700 1 _ |a Musgrave III, Charles
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700 1 _ |a Webber, Christopher
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700 1 _ |a Nielsen, Robert J.
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700 1 _ |a McKeown, Bradley A.
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700 1 _ |a Liu, Chang
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700 1 _ |a Schleker, P. Philipp M.
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700 1 _ |a Jakes, Peter
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700 1 _ |a Jia, Xiaofan
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700 1 _ |a Dickie, Diane A.
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700 1 _ |a Granwehr, Josef
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700 1 _ |a Zhang, Sen
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700 1 _ |a Machan, Charles W.
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700 1 _ |a Goddard, William A.
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700 1 _ |a Gunnoe, T. Brent
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773 _ _ |a 10.1021/acscatal.1c01395
|g Vol. 11, no. 12, p. 7223 - 7240
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|t ACS catalysis
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|y 2021
|x 2155-5435
856 4 _ |y Restricted
|u https://juser.fz-juelich.de/record/904166/files/acscatal.1c01395.pdf
856 4 _ |y Published on 2021-06-04. Available in OpenAccess from 2022-06-04.
|u https://juser.fz-juelich.de/record/904166/files/final%20manuscript.pdf
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