Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting

Autor: Friebel, D, Louie, MW, Bajdich, M, Sanwald, KE, Cai, Y, Wise, AM, Cheng, MJ, Sokaras, D, Weng, TC, Alonso-Mori, R, Davis, RC, Bargar, JR, Nørskov, JK, Nilsson, A, Bell, AT
Rok vydání: 2015
Předmět:
Zdroj: Journal of the American Chemical Society, vol 137, iss 3
Friebel, D; Louie, MW; Bajdich, M; Sanwald, KE; Cai, Y; Wise, AM; et al.(2015). Identification of highly active Fe sites in (Ni,Fe)OOH for electrocatalytic water splitting. Journal of the American Chemical Society, 137(3), 1305-1313. doi: 10.1021/ja511559d. UC Berkeley: Retrieved from: http://www.escholarship.org/uc/item/6k0041j4
DOI: 10.1021/ja511559d.
Popis: © 2015 American Chemical Society. Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni1-xFexOOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe3+ in Ni1-xFexOOH occupies octahedral sites with unusually short Fe-O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni1-xFexOOH are not active sites for the oxidation of water. (Graph Presented).
Databáze: OpenAIRE