title: Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis.
abstract: The description of the foot of the wave analysis (FOWA) applied to the electrocatalytic oxidation of water to dioxygen is reported for cases where the rate determining step is first order and second order with regard to catalyst concentration, coinciding mechanistically with the so-called water nucleophilic attack (WNA) and the interaction of two M-O units (I2M, where M represents the metal center of the catalyst), respectively. The newly adapted equations are applied to a range of relevant molecular catalysts, both in homogeneous and heterogeneous phase, and the kinetic parameters are determined, including apparent rate constants and turnover frequencies. In this respect, the application of FOWA at different catalyst concentrations allows elucidation of the reaction mechanism that operates in each case. In addition, catalytic Tafel plots are used for assessing the performance of several molecular water oxidation catalysts (WOCs) as a function of overpotential under analogous conditions, and thus can be used for benchmarking purposes. This analysis was carried out earlier for oxide-based WOCs; however, this is the first report using molecular WOCs.
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Avinguda Països Catalans 16, 43007, Tarragona, Spain.|Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel⋅lí i Domingo s/n, 43007, Tarragona, Spain.
authors.forename: Roc
authors.initials: R
authors.lastname: Matheu
authors.affiliation: Institute of Inorganic Chemistry, Georg-August-University Göttingen, 37077, Göttingen, Germany.
authors.forename: Sven
authors.initials: S
authors.lastname: Neudeck
authors.affiliation: Institute of Inorganic Chemistry, Georg-August-University Göttingen, 37077, Göttingen, Germany.|International Center for Advanced Studies of Energy Conversion, Georg-August-University, 37077, Göttingen, Germany.
authors.forename: Franc
authors.initials: F
authors.lastname: Meyer
authors.affiliation: Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193, Spain.
authors.forename: Xavier
authors.initials: X
authors.lastname: Sala
authors.affiliation: Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Avinguda Països Catalans 16, 43007, Tarragona, Spain.|Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193, Spain.
authors.forename: Antoni
authors.identifier: http://orcid.org/0000-0002-6176-5272
authors.initials: A
authors.lastname: Llobet
mesh_terms: D019985:Benchmarking; D002384:Catalysis; D007700:Kinetics; D008956:Models, Chemical; D010084:Oxidation-Reduction; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water
keywords: catalysis; foot of the wave analysis; reaction mechanisms; water oxidation; water splitting