title: Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni-Fe Oxide Water Splitting Electrocatalysts.
abstract: Mixed Ni-Fe oxides are attractive anode catalysts for efficient water splitting in solar fuels reactors. Because of conflicting past reports, the catalytically active metal redox state of the catalyst has remained under debate. Here, we report an in operando quantitative deconvolution of the charge injected into the nanostructured Ni-Fe oxyhydroxide OER catalysts or into reaction product molecules. To achieve this, we explore the oxygen evolution reaction dynamics and the individual faradaic charge efficiencies using operando differential electrochemical mass spectrometry (DEMS). We further use X-ray absorption spectroscopy (XAS) under OER conditions at the Ni and Fe K-edges of the electrocatalysts to evaluate oxidation states and local atomic structure motifs. DEMS and XAS data consistently reveal that up to 75% of the Ni centers increase their oxidation state from +2 to +3, while up to 25% arrive in the +4 state for the NiOOH catalyst under OER catalysis. The Fe centers consistently remain in the +3 state, regardless of potential and composition. For mixed Ni100-xFex catalysts, where x exceeds 9 atomic %, the faradaic efficiency of O2 sharply increases from ∼30% to 90%, suggesting that Ni atoms largely remain in the oxidation state +2 under catalytic conditions. To reconcile the apparent low level of oxidized Ni in mixed Ni-Fe catalysts, we hypothesize that a kinetic competition between the (i) metal oxidation process and the (ii) metal reduction step during O2 release may account for an insignificant accumulation of detectable high-valent metal states if the reaction rate of process (ii) outweighs that of (i). We conclude that a discussion of the superior catalytic OER activity of Ni-FeOOH electrocatalysts in terms of surface catalysis and redox-inactive metal sites likely represents an oversimplification that fails to capture essential aspects of the synergisms at highly active Ni-Fe sites.
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Mikaela
authors.initials: M
authors.lastname: Görlin
authors.affiliation: Free University of Berlin , Department of Physics, Arnimallee 14, 14195 Berlin, Germany.
authors.forename: Petko
authors.initials: P
authors.lastname: Chernev
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Jorge
authors.initials: J
authors.lastname: Ferreira de Araújo
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Reier
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Sören
authors.initials: S
authors.lastname: Dresp
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Benjamin
authors.initials: B
authors.lastname: Paul
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Ralph
authors.initials: R
authors.lastname: Krähnert
authors.affiliation: Free University of Berlin , Department of Physics, Arnimallee 14, 14195 Berlin, Germany.
authors.forename: Holger
authors.initials: H
authors.lastname: Dau
authors.affiliation: Technical University Berlin , Department of Chemistry, Chemical Engineering Division, Straße des 17. Juni 124, 10623 Berlin, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Strasser