Intermediate Sr2Co1.5Fe0.5O6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

Ede, Sivasankara Rao; Collins, Candyce N.; Posada, Carlos D.; George, Gibin; Wu, Hui; Ratcliff, William D.; Lin, Yulin; Wen, Jianguo; Han, Shubo; Luo, Zhiping

doi:10.1021/acscatal.1c00465

Title: Intermediate Sr₂Co_1.5Fe_0.5O_6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

Journal Article · Tue Mar 23 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c00465· OSTI ID:1829826

Ede, Sivasankara Rao ^[1]; Collins, Candyce N. ^[1]; Posada, Carlos D. ^[1]; George, Gibin ^[1]; Wu, Hui ^[2]; Ratcliff, William D. ^[3]; Lin, Yulin ^[4];

^[4]; Han, Shubo ^[1];

^[1]

Fayetteville State University, Fayetteville, NC (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Maryland, College Park, MD (United States)
Argonne National Lab. (ANL), Lemont, IL (United States). Center for Nanoscale Materials

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr₂Co_1.5Fe_0.5O_6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm^-2 and Tafel slope of 44.8 mV dec^-1. High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr₂Co_1.5Fe_0.5O_6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr₂Co_1.5Fe_0.5O_6-δ oxide as a better catalyst for its enhanced OER activity.

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Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; DMR 1827731; DMR 1508249

OSTI ID:: 1829826

Journal Information:: ACS Catalysis, Vol. 11, Issue 7; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Intermediate Sr2Co1.5Fe0.5O6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

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Title: Intermediate Sr₂Co_1.5Fe_0.5O_6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation