强钴―氧键合作用提升缺陷型Co<sub>2</sub>MnO<sub>4</sub>酸性析氧反应稳定性

引用本文: 谢静宜, 吕千喜, 乔韦珍, 卜辰宇, 张昱声, 翟雪君, 吕仁庆, 柴永明, 董斌. 强钴―氧键合作用提升缺陷型Co₂MnO₄酸性析氧反应稳定性[J]. 物理化学学报, 2024, 40(3): 230502. doi: 10.3866/PKU.WHXB202305021 shu

Citation: Jingyi Xie, Qianxi Lü, Weizhen Qiao, Chenyu Bu, Yusheng Zhang, Xuejun Zhai, Renqing Lü, Yongming Chai, Bin Dong. Enhancing Cobalt―Oxygen Bond to Stabilize Defective Co₂MnO₄ in Acidic Oxygen Evolution[J]. Acta Physico-Chimica Sinica, 2024, 40(3): 230502. doi: 10.3866/PKU.WHXB202305021 shu

强钴―氧键合作用提升缺陷型Co₂MnO₄酸性析氧反应稳定性

中国石油大学(华东)化学化工学院, 重质油全国重点实验室, 山东青岛 266580

通讯作者: 柴永明, ymchai@upc.edu.cn; 董斌, dongbin@upc.edu.cn

基金项目:
国家自然科学基金 52174283

中国石油大学(华东)研究生创新基金项目 22CX04023A

中央高校基本科研业务费

摘要: 通过实验和理论已经验证钴基氧化物是一种很有前景的析氧反应(OER)催化剂。然而，普通的钴基催化剂在酸性环境中非常不稳定，在酸性电解质中容易被腐蚀。因此，在目前的研究中，设计出能在强酸性条件下同时保持活性和稳定性的析氧催化剂是实现大规模工业制氢应用的一项重要挑战。因此，我们报道了通过在四氧化三钴的尖晶石晶格中引入锰(Mn)从而产生富含缺陷的催化剂(CoMn₁O)，它在酸性电解质中具有较长的使用寿命。我们利用X射线衍射(XRD)、X射线光电子能谱(XPS)、高分辨率透射电子显微镜(HRTEM)和能量色散光谱(EDS)元素图研究了晶相结构和化学价态。在引入锰后，由于局部晶体结构的改变，产生了大量的缺陷。此外，随着锰含量的增加，可以观察到Co 2p光谱的红移，这表明Co的总价逐渐增加，形成了更稳定的Co―O键。此外，当Mn与Co的比例达到1(CoMn₁O)时，目标催化剂表现出良好的OER活性，在10和50 mA∙cm⁻²时，过电位分别为415和552 mV。详细的物理表征和电化学测试表明，CoMn₁O比不含锰的Co₃O₄(CoMn₀O)能稳定4倍以上的时间。这可以归因于锰的引入调节了Co的电子密度偏向O，从而形成更稳定的Co―O键。Mn可以通过延缓Co活性位点的氧化速率来促进酸性氧的进化，并进一步提升稳定性。密度泛函理论(DFT)计算进一步分析了CoMn₁O和CoMn₀O的电子结构。与CoMn₀O相比，CoMn₁O中Co 3d的d带中心(ε_d)向费米能级(E_F)移动。这表明CoMn₁O通过加强与OER中间物的键合作用从而降低了反应能垒。本研究为设计非贵金属电催化剂实现高效稳定的酸性析氧提供有前景的策略。

关键词:

English

Enhancing Cobalt―Oxygen Bond to Stabilize Defective Co₂MnO₄ in Acidic Oxygen Evolution

State Key Laboratory of Heavy Oil Processing, College of Chemistry and Chemical Engineering, China University of Petroleum (East China), Qingdao 266580, Shandong Province, China

Corresponding author: Email: ymchai@upc.edu.cn (Y.C.); Email: dongbin@upc.edu.cn (B.D.); Tel.: +86-532-86981156 (B.D.)

Received Date: 09 May 2023
Accepted Date: 10 July 2023
Revised Date: 08 July 2023
Available Online: 15 March 2024
Fund Project:
the National Natural Science Foundation of China

Innovation Fund Project for Graduate Student of China University of Petroleum (East China)

the Fundamental Research Funds for the Central Universities

Abstract: Co-based oxides have shown promise as catalysts for the oxygen evolution reaction (OER), as evidenced by experimental and theoretical studies. However, these common Co-based catalysts suffer from poor stability in acidic environments, making them susceptible to corrosion in acid electrolytes. Consequently, developing OER catalysts that can maintain both activity and stability under strongly acidic conditions is a challenging task for large-scale industrial hydrogen production applications. To address this challenge, the incorporation of manganese (Mn) into the spinel lattice of Co₃O₄ (CoMn₁O) has been proposed, resulting in a defect-rich catalyst with improved lifetime in acidic electrolytes. The crystalline phase structures and chemical valence states were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and energy-dispersive spectroscopy (EDS) elemental maps. The introduction of Mn led to the generation of a significant number of defects due to changes in the local crystal structure. Additionally, as the amount of Mn atoms increased, a red shift was observed in the Co 2p spectrum, indicating an increase in the overall valence of Co and the formation of more stable Co―O bonds. Moreover, when the Mn-to-Co ratio reached 1 (CoMn₁O), the resulting catalyst exhibited promising OER activity, with overpotentials of 415 and 552 mV at 10 and 50 mA∙cm⁻², respectively. Detailed physical characterization and electrochemical tests demonstrated that CoMn1O exhibited over four times the stability of Mn-free Co₃O₄ (CoMn₀O). This enhanced stability can be attributed to the introduction of Mn, which promotes electron density bias of Co towards O, resulting in the formation of more stable Co―O bonds. Mn also facilitates acidic oxygen evolution by delaying the oxidation rate of the Co active sites, thereby enhancing stability. Density functional theory (DFT) calculations were further employed to analyze the electronic structures of CoMn₁O and CoMn₀O. The d-band center of Co 3d (ε_d) in CoMn₁O shifted closer to the Fermi level (E_F) compared to that of CoMn₀O, indicating a reduced reaction energy barrier for CoMn₁O and enhanced bonding interaction with OER intermediates. Overall, this work presents a promising strategy for achieving highly efficient and stable acidic oxygen evolution using noble-metal-free electrocatalysts.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

强钴―氧键合作用提升缺陷型Co₂MnO₄酸性析氧反应稳定性

通讯作者: 柴永明, ymchai@upc.edu.cn; 董斌, dongbin@upc.edu.cn

English

Enhancing Cobalt―Oxygen Bond to Stabilize Defective Co₂MnO₄ in Acidic Oxygen Evolution

Corresponding author: Email: ymchai@upc.edu.cn (Y.C.); Email: dongbin@upc.edu.cn (B.D.); Tel.: +86-532-86981156 (B.D.)

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强钴―氧键合作用提升缺陷型Co2MnO4酸性析氧反应稳定性

通讯作者: 柴永明, ymchai@upc.edu.cn; 董斌, dongbin@upc.edu.cn

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Enhancing Cobalt―Oxygen Bond to Stabilize Defective Co2MnO4 in Acidic Oxygen Evolution

Corresponding author: Email: ymchai@upc.edu.cn (Y.C.); Email: dongbin@upc.edu.cn (B.D.); Tel.: +86-532-86981156 (B.D.)

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