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@ARTICLE{Zhu:1005447,
      author       = {Zhu, Xinwei and Huang, Jun and Eikerling, Michael},
      title        = {p{H} {E}ffects in a {M}odel {E}lectrocatalytic {R}eaction
                      {D}isentangled},
      journal      = {JACS Au},
      volume       = {3},
      number       = {4},
      issn         = {2691-3704},
      address      = {Washington, DC},
      publisher    = {ACS Publications},
      reportid     = {FZJ-2023-01478},
      pages        = {1052–1064},
      year         = {2023},
      abstract     = {Varying the solution pH not only changes the reactant
                      concentrations in bulk solution but also the local reaction
                      environment (LRE) that is shaped furthermore by macroscopic
                      mass transport and microscopic electric double layer (EDL)
                      effects. Understanding ubiquitous pH effects in
                      electrocatalysis requires disentangling these interwoven
                      factors, which is a difficult, if not impossible, task
                      without physical modeling. Herein, we demonstrate how a
                      hierarchical model that integrates microkinetics,
                      double-layer charging, and macroscopic mass transport can
                      help understand pH effects of the formic acid oxidation
                      reaction (FAOR). In terms of the relation between the peak
                      activity and the solution pH, intrinsic pH effects without
                      consideration of changes in the LRE would lead to a
                      bell-shaped curve with a peak at pH = 6. Adding only
                      macroscopic mass transport, we can already reproduce
                      qualitatively the experimentally observed trapezoidal shape
                      with a plateau between pH 5 and 10 in perchlorate and
                      sulfate solutions. A quantitative agreement with
                      experimental data requires consideration of EDL effects
                      beyond Frumkin correlations. Specifically, the peculiar
                      nonmonotonic surface charging relation affects the free
                      energies of adsorbed intermediates. We further discuss pH
                      effects of FAOR in phosphate and chloride-containing
                      solutions, for which anion adsorption becomes important.
                      This study underpins the importance of a full consideration
                      of multiple interrelated factors for the interpretation of
                      pH effects in electrocatalysis.},
      cin          = {IEK-13},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-13-20190226},
      pnm          = {1212 - Materials and Interfaces (POF4-121) / 1215 -
                      Simulations, Theory, Optics, and Analytics (STOA)
                      (POF4-121)},
      pid          = {G:(DE-HGF)POF4-1212 / G:(DE-HGF)POF4-1215},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {37124300},
      UT           = {WOS:000978886200001},
      doi          = {10.1021/jacsau.2c00662},
      url          = {https://juser.fz-juelich.de/record/1005447},
}