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@ARTICLE{Geer:904166,
      author       = {Geer, Ana M. and Musgrave III, Charles and Webber,
                      Christopher and Nielsen, Robert J. and McKeown, Bradley A.
                      and Liu, Chang and Schleker, P. Philipp M. and Jakes, Peter
                      and Jia, Xiaofan and Dickie, Diane A. and Granwehr, Josef
                      and Zhang, Sen and Machan, Charles W. and Goddard, William
                      A. and Gunnoe, T. Brent},
      title        = {{E}lectrocatalytic {W}ater {O}xidation by a {T}rinuclear
                      {C}opper({II}) {C}omplex},
      journal      = {ACS catalysis},
      volume       = {11},
      number       = {12},
      issn         = {2155-5435},
      address      = {Washington, DC},
      publisher    = {ACS},
      reportid     = {FZJ-2021-05736},
      pages        = {7223 - 7240},
      year         = {2021},
      abstract     = {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.},
      cin          = {IEK-9},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-9-20110218},
      pnm          = {1223 - Batteries in Application (POF4-122)},
      pid          = {G:(DE-HGF)POF4-1223},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000664333800044},
      doi          = {10.1021/acscatal.1c01395},
      url          = {https://juser.fz-juelich.de/record/904166},
}