MgCo₂O₄, CoCr₂O₄, and Co₂TiO₄ were selected, where only Co³⁺ in the center of octahedron (Oh), Co²⁺ in the center of tetrahedron (Td), and Co²⁺ in the center of Oh can be active sites as model electrocatalysts for the oxygen evolution reaction. Co³⁺(Oh) sites are the best geometrical configuration; Co²⁺(Oh) sites exhibit better electrochemical activity than Co²⁺(Td).

Abstract

MgCo₂O₄, CoCr₂O₄, and Co₂TiO₄ were selected, where only Co³⁺ in the center of octahedron (Oh), Co²⁺ in the center of tetrahedron (Td), and Co²⁺ in the center of Oh, can be active sites for the oxygen evolution reaction (OER). Co³⁺(Oh) sites are the best geometrical configuration for OER. Co²⁺(Oh) sites exhibit better activity than Co²⁺(Td). Calculations demonstrate the conversion of O* into OOH* is the rate-determining step for Co³⁺(Oh) and Co²⁺(Td). For Co²⁺(Oh), it is thermodynamically favorable for the formation of OOH* but difficult for the desorption of O₂. Co³⁺(Oh) needs to increase the lowest Gibbs free energy over Co²⁺(Oh) and Co²⁺(Td), which contributes to the best activity. The coexistence of Co³⁺(Oh) and Co²⁺(Td) in Co₃O₄ can promote the formation of OOH* and decrease the free-energy barrier. This work screens out the optimal geometrical configuration of cobalt cations for OER and gives a valuable principle to design efficient electrocatalysts.

Conflict of interest

The authors declare no conflict of interest.

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Volume59, Issue12

March 16, 2020

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Optimal Geometrical Configuration of Cobalt Cations in Spinel Oxides to Promote Oxygen Evolution Reaction

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Optimal Geometrical Configuration of Cobalt Cations in Spinel Oxides to Promote Oxygen Evolution Reaction

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