Engineering Electrocatalytic Activity in Nanosized Perovskite Cobaltite Through Surface Spin-state Transition

Overview

Journal Nat Commun

Specialty Biology

Date 2016 May 18

PMID 27187067

Citations 34

Authors

Shiming Zhou

Xianbing Miao

Xu Zhao

Chao Ma

Yuhao Qiu

Zhenpeng Hu

Jiyin Zhao

Lei Shi

Jie Zeng

Affiliations

Soon will be listed here.

Abstract

The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg(∼1.2) configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity.

Citing Articles

A Review of Surface Reconstruction and Transformation of 3d Transition-Metal (oxy)Hydroxides and Spinel-Type Oxides during the Oxygen Evolution Reaction.

He B, Bai F, Jain P, Li T Small. 2025; 21(10):e2411479.

PMID: 39916593 PMC: 11899548. DOI: 10.1002/smll.202411479.

Spin effects in regulating the adsorption characteristics of metal ions.

Gao C, Zhen S, Wang Y, Wang L, Cao Y, Zhan J Chem Sci. 2025; 16(5):2429-2436.

PMID: 39790990 PMC: 11708777. DOI: 10.1039/d4sc06477a.

Tracking the correlation between spintronic structure and oxygen evolution reaction mechanism of cobalt-ruthenium-based electrocatalyst.

Wang C, Deng C, Zhai P, Shi X, Liu W, Jin D Nat Commun. 2025; 16(1):215.

PMID: 39747255 PMC: 11697232. DOI: 10.1038/s41467-024-55688-8.

Deciphering Water Oxidation Catalysts: The Dominant Role of Surface Chemistry over Reconstruction Degree in Activity Promotion.

An L, Li J, Sun Y, Zhu J, Seow J, Zhang H Nanomicro Lett. 2024; 17(1):70.

PMID: 39589691 PMC: 11599692. DOI: 10.1007/s40820-024-01562-7.

Spin-dependent electrocatalysis.

Chen Z, Li X, Ma H, Zhang Y, Peng J, Ma T Natl Sci Rev. 2024; 11(9):nwae314.

PMID: 39363911 PMC: 11448474. DOI: 10.1093/nsr/nwae314.

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