Issue 11, 2019

Optimized Co2+(Td)–O–Fe3+(Oh) electronic states in a spinel electrocatalyst for highly efficient oxygen evolution reaction performance

Abstract

Electronic configuration is crucial for enhancing the catalytic activities of spinels for the oxygen evolution reaction (OER). However, controlling the electronic spin state of materials is still a challenge. In this work, we synthesized Fe-doped meso-Co3O4via a nanocasting method. The merit of our method lies in high spin state Fe3+ (t2g3eg2) being controllably introduced into an octahedral site to regulate the valence states and configure the eg electron of Co3+. The introduced Fe3+ prefers to occupy octahedral sites due to its lower formation energy. Then, Fe3+ doping enlarges the Co3+–O distance and decreases the lattice symmetry, leading to the splitting of the d-orbital in Co3+. Our density functional theory (DFT) calculations reveal that spin state optimized Co3+(Oh) acts preferentially as an active site. Furthermore, CoFe-7.5 (Co2.775Fe0.225O4), with its maximum Fe3+(Oh) content, exhibits the best OER activity. Our work indicates that the introduction of Fe3+ enables an improvement in the electrocatalytic performance of Co3O4 by regulating the spin state of Co3+.

Graphical abstract: Optimized Co2+(Td)–O–Fe3+(Oh) electronic states in a spinel electrocatalyst for highly efficient oxygen evolution reaction performance

Supplementary files

Article information

Article type
Research Article
Submitted
12 Jul 2019
Accepted
24 Sep 2019
First published
25 Sep 2019

Inorg. Chem. Front., 2019,6, 3295-3301

Optimized Co2+(Td)–O–Fe3+(Oh) electronic states in a spinel electrocatalyst for highly efficient oxygen evolution reaction performance

X. Gao, J. Liu, Y. Sun, X. Wang, Z. Geng, F. Shi, X. Wang, W. Zhang, S. Feng, Y. Wang and K. Huang, Inorg. Chem. Front., 2019, 6, 3295 DOI: 10.1039/C9QI00852G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements