Tuning Co2+ active sites over Co3O4 for boosting electrocatalytic oxygen evolution in neutral media

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis Pub Date : 2025-05-02 DOI:10.1016/j.mcat.2025.115165

Juan Zhang , Lian Duan , Junshan Lin , Ruiling Du , Gen Chen , Qing Kang , Ning Zhang

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引用次数: 0

Abstract

Electrochemical water splitting is a promising hydrogen production technology, with the oxygen evolution reaction (OER) as the key step. This study focuses on enhancing the OER activity under neutral conditions using acid-treated Co₃O₄ (A-Co₃O₄) as a viable alternative to noble metal electrocatalysts. We synthesized acid-treated Co₃O₄ with a tunable Co²⁺/Co³⁺ atomic ratio from 0.63 to 1.69. The A-Co₃O₄ exhibited an overpotential of only 438 mV at a current density of 10 mA cm^–² with sustained activity for over 70 h. In-situ Raman spectroscopy analysis indicated that Co²⁺ sites were conducive to forming highly oxidative γ-CoOOH and stabilizing the CoOOH phase under OER conditions. Density functional theory (DFT) calculations showed that Co²⁺ sites on the surface of Co₃O₄ significantly lower the Gibbs free energy barrier of the rate-determining step compared to Co³⁺ sites. This study proposes a simple and effective acid-treatment method to enhance the OER activity of Co₃O₄, paving the way for its application in neutral seawater electrolysis and contributing to the development of cost-effective hydrogen production technologies.

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调节Co3O4上的Co2+活性位点促进中性介质中电催化析氧

电化学水分解是一种很有前途的制氢技术，其中析氧反应是关键步骤。本研究的重点是利用酸处理的Co3O4 （a -Co3O4）作为贵金属电催化剂的可行替代品，在中性条件下提高OER活性。我们合成了Co2+/Co3+原子比在0.63 ~ 1.69之间可调的酸处理Co3O4。在电流密度为10 mA cm-2时，a - co3o4的过电位仅为438 mV，活性持续时间超过70 h。原位拉曼光谱分析表明，在OER条件下，Co2+位点有利于形成高度氧化的γ-CoOOH并稳定CoOOH相。密度泛函理论（DFT）计算表明，与Co3+位点相比，Co3O4表面的Co2+位点显著降低了速率决定步骤的吉布斯自由能垒。本研究提出了一种简单有效的酸处理方法来提高Co3O4的OER活性，为其在中性海水电解中的应用铺平了道路，并有助于开发具有成本效益的制氢技术。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Molecular Catalysis Chemical Engineering-Process Chemistry and Technology

CiteScore

6.90

自引率

10.90%

发文量

700

审稿时长

40 days

期刊介绍： Molecular Catalysis publishes full papers that are original, rigorous, and scholarly contributions examining the molecular and atomic aspects of catalytic activation and reaction mechanisms. The fields covered are: Heterogeneous catalysis including immobilized molecular catalysts Homogeneous catalysis including organocatalysis, organometallic catalysis and biocatalysis Photo- and electrochemistry Theoretical aspects of catalysis analyzed by computational methods