Cooperative Fe sites on transition metal (oxy)hydroxides drive high oxygen evolution activity in base.

Autor: Ou Y; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA.; School of Chemistry and Chemical Engineering, Chongqing University, 400044, Chongqing, China., Twight LP; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA., Samanta B; Department of Materials Science and Engineering, Technion-Israel Institute of Technology, Haifa, 3200003, Israel., Liu L; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA.; School of Materials Science and Engineering, Chongqing University, 400044, Chongqing, China., Biswas S; Department of Materials Science and Engineering, Technion-Israel Institute of Technology, Haifa, 3200003, Israel., Fehrs JL; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA., Sagui NA; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA., Villalobos J; Nachwuchsgruppe Gestaltung des Sauerstoffentwicklungsmechanismus, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109, Berlin, Germany., Morales-Santelices J; Nachwuchsgruppe Gestaltung des Sauerstoffentwicklungsmechanismus, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109, Berlin, Germany., Antipin D; Nachwuchsgruppe Gestaltung des Sauerstoffentwicklungsmechanismus, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109, Berlin, Germany., Risch M; Nachwuchsgruppe Gestaltung des Sauerstoffentwicklungsmechanismus, Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, 14109, Berlin, Germany., Toroker MC; Department of Materials Science and Engineering, Technion-Israel Institute of Technology, Haifa, 3200003, Israel. maytalc@technion.ac.il.; The Nancy and Stephen Grand Technion Energy Program, Haifa, Israel. maytalc@technion.ac.il., Boettcher SW; Department of Chemistry and Biochemistry and the Oregon Center for Electrochemistry, University of Oregon, Eugene, Oregon, 97403, USA. swb@uoregon.edu.
Jazyk: angličtina
Zdroj: Nature communications [Nat Commun] 2023 Nov 24; Vol. 14 (1), pp. 7688. Date of Electronic Publication: 2023 Nov 24.
DOI: 10.1038/s41467-023-43305-z
Abstrakt: Fe-containing transition-metal (oxy)hydroxides are highly active oxygen-evolution reaction (OER) electrocatalysts in alkaline media and ubiquitously form across many materials systems. The complexity and dynamics of the Fe sites within the (oxy)hydroxide have slowed understanding of how and where the Fe-based active sites form-information critical for designing catalysts and electrolytes with higher activity and stability. We show that where/how Fe species in the electrolyte incorporate into host Ni or Co (oxy)hydroxides depends on the electrochemical history and structural properties of the host material. Substantially less Fe is incorporated from Fe-spiked electrolyte into Ni (oxy)hydroxide at anodic potentials, past the nominally Ni 2+/3+ redox wave, compared to during potential cycling. The Fe adsorbed under constant anodic potentials leads to impressively high per-Fe OER turn-over frequency (TOF Fe ) of ~40 s -1 at 350 mV overpotential which we attribute to under-coordinated "surface" Fe. By systematically controlling the concentration of surface Fe, we find TOF Fe increases linearly with the Fe concentration. This suggests a changing OER mechanism with increased Fe concentration, consistent with a mechanism involving cooperative Fe sites in FeO x clusters.
(© 2023. The Author(s).)
Databáze: MEDLINE
Externí odkaz: