Indexado en

Documentos y archivos

Licencia y uso

Citaciones

Altmetrics

Grant support

K.L.S. and J.R. acknowledge the Danish National Research Foundation Centre for High-Entropy Alloy Catalysis (CHEAC) DNRF-149. B.M. acknowledges the EPSRC and horizon project EP/W033232/1 for funding as well as an Edward Steers grant from the British Association of Spectroscopists and Schmidt Futures. D.N.-C., L.J., and J.R.G.-M. are thankful for the support of the Spanish Ministerio de Ciencia e Innovacion through a Severo Ochoa Excellence Accreditation 2020-2023 (CEX2019-000925-S, MIC/AEI); through the project PID2021-124796OB-I00; and the Generalitat de Catalunya (2021-SGR-1154). ICIQ is supported by the Ministerio de Ciencia e Innovacion through the Severo Ochoa Excellence Accreditations CEX2019-000925-S (MCIN/AEI) and by the CERCA Programme/Generalitat de Catalunya. We acknowledge Diamond Light Source for time on Beamline B18 under Proposal SP30396. J.R.D. acknowledges Horizon 2020 for funding through the SUN2CHEM project (884444). I.E.L.S., R.R.R., and S.B.S. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (grant agreement no. 866402). S.B.S. thanks Energy 4 Future, Iberdrola Espana.

Análisis de autorías institucional

Compartir

Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates

Publicado en:Journal Of The American Chemical Society. 146 (13): 8915-8927 - 2024-03-22 146(13), DOI: 10.1021/jacs.3c11651

Autores: Moss, Benjamin; Svane, Katrine Louise; Nieto-Castro, David; Rao, Reshma R; Scott, Soren B; Tseng, Cindy; Sachs, Michael; Pennathur, Anuj; Liang, Caiwu; Oldham, Louise I; Mazzolini, Eva; Jurado, Lole; Sankar, Gopinathan; Parry, Stephen; Celorrio, Veronica; Dawlaty, Jahan M; Rossmeisl, Jan; Galan-Mascaros, J R; Stephens, Ifan E L; Durrant, James R

Afiliaciones

Resumen

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple overlapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (similar to 0.34 eV/monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O-2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O-2 evolution onset coincide due to weaker binding and destabilization (similar to 0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

Palabras clave