基于尖晶石型混合金属钴矿的高效析氧电催化性能

引用本文: 陶磊明, 郭鹏虎, 朱伟玲, 李天乐, 周贤太, 傅永庆, 余长林, 纪红兵. 基于尖晶石型混合金属钴矿的高效析氧电催化性能[J]. 催化学报, 2020, 41(12): 1855-1863. doi: 10.1016/S1872-2067(20)63638-5 shu

Citation: Leiming Tao, Penghu Guo, Weiling Zhu, Tianle Li, Xiantai Zhou, Yongqing Fu, Changlin Yu, Hongbing Ji. Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction[J]. Chinese Journal of Catalysis, 2020, 41(12): 1855-1863. doi: 10.1016/S1872-2067(20)63638-5 shu

基于尖晶石型混合金属钴矿的高效析氧电催化性能

a 广东石油化工学院理学院, 广东茂名 525000, 中国;
b 华中科技大学武汉光电国家研究中心, 湖北武汉 430074, 中国;
c 诺森比亚大学工程与环境学院, 纽卡斯尔, 英国;
d 中山大学化学学院, 精细化工研究院, 广东广州 510275, 中国
基金项目:
国家自然科学基金（21938001，21576302，21878344和201961160741）；国家自然科学基金委-中国石化股份公司石油化工联合基金（U1663220）；广东省重点研发计划（2019B110206002）；广东省教育厅特色创新项目（2018KTSCX144，2016KTSCX087）；广东珠江人才计划地方创新研究团队项目（2017BT01C102）；广东省高校珠江学者计划（2019）；广东普通高校重点项目<自然>（2019KZDXM010）；广东省基础与应用基础研究基金（2019A1515011249）；广东石油化工学院自然科学基金科研基金（2019rc019，2019rc053）；英国工程与物理科学研究委员会（EPSRC）提供资助（EP/P018998/1）；英国皇家学会和中国国家自然科学基金委员会的牛顿交流基金（IE161019）.

摘要: 尖晶石钴矿（例如ACo₂O₄，其中A=Mn，Fe，Co，Ni，Cu或Zn的阳离子取代）是一种精确调控其电子结构/性质，并因此改善相应的电催化水分解析氧（OER）性能的有前途的策略.然而，有关它的基本原理和机制尚未完全理解.为了确定尖晶石氧化物在OER中的作用，已有实验和理论报道.例如，Prabu发现Ni³⁺离子取代NiCo₂O₄的八面体位点可以显着提高OER性能；Hutchings报道OER性能提高源自Co₃O₄八面体Co³⁺的活性位；Wei研究发现MnCo₂O₄八面体位置的Mn³⁺离子是OER的活性位点.尽管多数研究没有对此给出清晰的解释，但这些研究清楚地表明，尖晶石氧化物对OER的电催化性能在很大程度上取决于过渡金属阳离子（A）的化合价态及其在尖晶石结构中的相应位点分布.本文旨在合成具有同种形貌的尖晶石ACo₂O₄混合金属有机骨架（MMOFs）材料，通过A位引入外层d电子数从5到10的过渡金属元素，如Mn，Fe，Co，Ni，Cu和Zn，系统研究催化水分解析氧机理.基于实验详细分析了不同阳离子的取代和其OER的催化行为，在获得的六种尖晶石ACo₂O₄催化剂中，FeCo₂O₄催化剂在碱性溶液中具有出色的OER性能和稳定性，其在电流密度10mA·cm^-2的超电势下164mV.催化剂的电荷传输性能与离子和空位扩散的跳跃率密切相关.我们使用密度泛函理论计算阳离子在ACo₂O₄晶体中的扩散以及扩散的活化能，并且计算过程考虑自旋的激发能.使用VASP的搜索过渡态方法（NEB-DMTS）确定离子扩散的最小能量反应路径.结果表明，尖晶石钴矿ACo₂O₄晶格中的Fe取代可以显著加速电荷转移，从而获得增强的电化学性能.由第一性原理计算Fe阳离子通过四面体-三角平面-八面体路径扩散，具有0.4eV的活化能和0.5eV的能量以形成八面体中间体.当它跳跃时，阳离子（Fe）分别在过渡态和四面体鞍点（亚稳态）下从+1.82的Bader电荷增加到+2.82和+2.83的电荷，这表明扩散的Fe在不同的位置具有的相应的价态.根据晶体场理论，通过八面体位置偏好能量（OSPE）是用于判断阳离子占据八面体或四面体的位置，其被定义为占据八面体和四面体的晶体场能量（CFSE）差.OSPE的顺序依次是Ni²⁺ > Ni³⁺ > Mn³⁺ > Fe²⁺ > Co³⁺ > Co²⁺ > Fe³⁺ > Mn²⁺ > Cu²⁺ > Zn²，由于Fe（II）、Co（II）和Ni（II）的OSPE值大于Co（III）的OSPE值，这三种阳离子在四面体可以与八面体Co（III）发生交换.对Fe（II）离子，研究发现Fe（Td）↔Co（Oh）交换很容易进行，Fe既可以占据八面体又可以占据四面体，所以FeCo₂O₄为复合尖晶石结构，可以从ACo₂O₄晶体的X射线吸收光谱法获得阳离子A的价态和分布证实.更深入研究发现尖晶石ACo₂O₄的晶体场，不仅决定A位阳离子的价态，同时影响这些尖晶石钴矿OER性能的关键因素.

关键词:

English

Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction

a School of Science, Guangdong University of Petrochemical Technology, Maoming 525000, Guangdong, China;
b Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, Hubei, China;
c Faculty of Engineering and Environment, Northumbria University, Newcastle upon Tyne, NE1 8ST, UK;
d Fine Chemical Industry Research Institute, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
Received Date: 11 March 2020
Revised Date: 14 April 2020
Fund Project:
This work was supported by the National Natural Science Foundation of China (21938001, 21576302, 21878344, 21961160741), Natural Science Foundation of China-SINOPEC Joint Fund (U1663220), Featured Innovation Project of Guangdong Education Department (2018KTSCX144, 2016KTSCX087), Guangdong Provincial Key R&D Programme (2019B110206002), the Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01C102), Scientific Research Fund of Natural Science Foundation of Guangdong University of Petrochemical Technology (2019rc019, 2019rc053), Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2019), Key Natural Science Research Projects of Guangdong Provincial Universities (2019KZDXM010), Guangdong Basic and Applied Basic Research Foundation (2019A1515011249), the UK Engineering and Physical Sciences Research Council (EPSRC) for support under grant EP/P018998/1, and Newton Mobility Grant (IE161019) through the Royal Society and the National Natural Science Foundation of China.

Abstract: Cation substitution in spinel cobaltites (e.g., ACo₂O₄, in which A=Mn, Fe, Co, Ni, Cu, or Zn) is a promising strategy to precisely modulate their electronic structure/properties and thus improve the corresponding electrochemical performance for water splitting. However, the fundamental principles and mechanisms are not fully understood. This research aims to systematically investigate the effects of cation substitution in spinel cobaltites derived from mixed-metal-organic frameworks on the oxygen evolution reaction (OER). Among the obtained ACo₂O₄ catalysts, FeCo₂O₄ showed excellent OER performance with a current density of 10 mA·cm^-2 at an overpotential of 164 mV in alkaline media. Both theoretical calculations and experimental results demonstrate that the Fe substitution in the crystal lattice of ACo₂O₄ can significantly accelerate charge transfer, thereby achieving enhanced electrochemical properties. The crystal field of spinel ACo₂O₄, which determines the valence states of cations A, is identified as the key factor to dictate the OER performance of these spinel cobaltites.

Key words:

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基于尖晶石型混合金属钴矿的高效析氧电催化性能

English

Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction

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基于尖晶石型混合金属钴矿的高效析氧电催化性能

English

Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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