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@ARTICLE{Huang:894409,
      author       = {Huang, Jun and Zhu, Xinwei and Eikerling, Michael},
      title        = {{T}he {R}ate-{D}etermining {T}erm of {E}lectrocatalytic
                      {R}eactions with {F}irst-{O}rder {K}inetics},
      journal      = {Electrochimica acta},
      volume       = {393},
      issn         = {0013-4686},
      address      = {New York, NY [u.a.]},
      publisher    = {Elsevier},
      reportid     = {FZJ-2021-03209},
      pages        = {139019 -},
      year         = {2021},
      abstract     = {The quest to find highly active electrocatalysts for
                      electrochemical energy conversion devices requires
                      mechanistic concepts to guide activity analysis, the most
                      commonly employed ones being the rate-determining step (RDS)
                      and the potential-determining step (PDS). Here we present a
                      generalized concept, the rate-determining term (RDT). The
                      RDT concept is not simply a semantic change but a nontrivial
                      improvement over the RDS and PDS concepts, as it
                      incorporates the detailed kinetics and thermodynamics of
                      multistep electrocatalytic reactions. The theoretical basis
                      of the RDT concept is steady-state microkinetic modelling,
                      for which we put forward a unified and compact formalism for
                      electrocatalytic reactions with first-order kinetics. The
                      new formalism allows us to write the expression for the rate
                      determining term of the reaction in general and analytical
                      form. The RDT concept is then used to derive analytical
                      expressions for the Tafel slope and the volcano plot of
                      activity that can be used in the studies of multistep
                      electrocatalytic reactions. Thereafter, the efficacy of the
                      RDT concept is demonstrated for two important case studies,
                      the oxygen evolution reaction and the carbon dioxide
                      reduction reaction. Fundamental insights into the origins of
                      the potential-dependent Tafel slope are obtained. An
                      important consequence, gleaned from this analysis, is that
                      one cannot infer a RDS from measured Tafel slopes. In
                      addition, kinetic factors are shown to exert a notable
                      influence on the slopes and apex location in volcano plots
                      of activity. The present RDT is anticipated to be a powerful
                      analytical tool for multistep electrocatalytic reactions
                      with first-order kinetics.},
      cin          = {IEK-13 / JARA-ENERGY},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-13-20190226 / $I:(DE-82)080011_20140620$},
      pnm          = {1231 - Electrochemistry for Hydrogen (POF4-123)},
      pid          = {G:(DE-HGF)POF4-1231},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000692096000013},
      doi          = {10.1016/j.electacta.2021.139019},
      url          = {https://juser.fz-juelich.de/record/894409},
}