Modulating the electronic structures of cobalt-organic frameworks for efficient electrocatalytic oxygen evolution

Yongchao Hao; Zhongyuan Guo; Huiya Cheng; Chenghao Yao; Shuling Cheng; Lizhi Yi; Hao Li

doi:10.1016/j.jcis.2023.07.151

Modulating the electronic structures of cobalt-organic frameworks for efficient electrocatalytic oxygen evolution

J Colloid Interface Sci. 2023 Nov 15;650(Pt B):1949-1957. doi: 10.1016/j.jcis.2023.07.151. Epub 2023 Jul 25.

Authors

Yongchao Hao¹, Zhongyuan Guo², Huiya Cheng³, Chenghao Yao⁴, Shuling Cheng³, Lizhi Yi³, Hao Li⁵

Affiliations

¹ Guangdong Provincial Key Laboratory of Distributed Energy Systems, School of Chemical Engineering and Energy Technology, Dongguan University of Technology, Dongguan 523808, China. Electronic address: haoyc@dgut.edu.cn.
² College of Environmental and Resource Sciences, Zhejiang University, Hangzhou 310058, China; Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan.
³ Guangdong Provincial Key Laboratory of Distributed Energy Systems, School of Chemical Engineering and Energy Technology, Dongguan University of Technology, Dongguan 523808, China.
⁴ Guangdong Provincial Key Laboratory of Distributed Energy Systems, School of Chemical Engineering and Energy Technology, Dongguan University of Technology, Dongguan 523808, China; School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.
⁵ Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan. Electronic address: li.hao.b8@tohoku.ac.jp.

PMID: 37517194
DOI: 10.1016/j.jcis.2023.07.151

Abstract

The oxygen evolution reaction (OER) is a key process in various energy storage/generation technologies. Tuning the electronic structures of catalysts is an effective approach to improve the catalyst's activity. In this work, we synthesized Ce-doped cobalt-organic frameworks with benzene-1, 4-dicarboxylic acid (BDC) as the ligand as efficient OER electrocatalysts (denoted as Co₃Ce₁ BDC) with excellent stability and improved catalytic performance. The introduced Ce in Co₃Ce₁ BDC changes the surface configuration and tunes electronic structures of the active Co site, leading to enhanced interaction between intermediates and catalysts. Besides, the specific surface area, reaction kinetics, charge transfer efficiency, and turnover frequency are also improved in the presence of Ce. As a result, the Co₃Ce₁ BDC demonstrated excellent performance with a low overpotential of 285 mV at a current of 10 mA·cm^-2, a preferable Tafel slope of 56.1 mV·dec^-1, and an excellent durability in 1 M KOH, indicating the potential for practical applications in water splitting and other energy storage technologies wherein the OER plays a critical role. Comprehensive theoretical calculations and modeling further identified the key role of Ce in modulating the electronic structure and OER activity of cobalt-organic frameworks. Most importantly, this work provides a new strategy to the development of efficient cobalt-organic framework catalysts in OER-related applications.

Keywords: Cerium-doping; Cobalt-organic frameworks; Density functional theory; Electronic state modulation; Oxygen evolution reaction.