催化学报

催化学报 ›› 2023, Vol. 54: 290-297.DOI: 10.1016/S1872-2067(23)64533-4

• 论文 • 上一篇    

金属有机框架衍生的阳离子调控金属硫化物增强析氧反应活性

万凯a,b, 罗江水c,*(), 刘文博a, 张婷d, Jordi Arbiold,e,*(), 张漩b, Palaniappan Subramanianb, 傅志勇a,*(), Jan Fransaerb,*()   

  1. a华南理工大学化学与化工学院, 广东省燃料电池技术重点实验室, 广东广州510641, 中国
    b鲁汶大学材料工程系, 鲁汶, 比利时
    c四川大学材料科学与工程学院, 后续能源材料与器件教育部工程研究中心, 四川成都610065, 中国
    d加泰罗尼亚纳米科学和纳米技术研究所, 巴塞罗那，西班牙
    e西班牙加泰罗尼亚研究所, 巴塞罗那, 西班牙
  • 收稿日期:2023-08-15 接受日期:2023-10-11 出版日期:2023-11-18 发布日期:2023-11-15
  • 通讯作者: *电子信箱: jiangshui.luo@scu.edu.cn (罗江水), arbiol@icrea.cat (J. Arbiol), zyfu@scut.edu.cn (傅志勇), jan.fransaer@kuleuven.be (J. Fransaer).
  • 基金资助:
    国家自然科学基金(21975081);国家自然科学基金(22178126);国家自然科学基金(22208110);国家自然科学基金(21776120);国家自然科学基金(22378270);广州市科技计划项目(2023A04J1357);中国博士后科学基金(2022M711196);四川大学后续能源材料与器件教育部工程研究中心开放课题(AEMD202204);四川省科技计划项目(2022ZYD0016);四川省科技计划项目(2023JDRC0013);呼和浩特市科技计划项目(2023-揭榜挂帅-高-3);福建省自然科学基金(2023J01254);广东省燃料电池技术重点实验室开放课题(FC202206);广东省燃料电池技术重点实验室开放课题(FC202218)

Metal-organic framework-derived cation regulation of metal sulfides for enhanced oxygen evolution activity

Kai Wana,b, Jiangshui Luoc,*(), Wenbo Liua, Ting Zhangd, Jordi Arbiold,e,*(), Xuan Zhangb, Palaniappan Subramanianb, Zhiyong Fua,*(), Jan Fransaerb,*()   

  1. aGuangdong Provincial Key Laboratory of Fuel Cell Technology, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, Guangdong, China
    bDepartment of Materials Engineering, KU Leuven, Leuven 3001, Belgium
    cEngineering Research Center of Alternative Energy Materials & Devices, Ministry of Education, College of Materials Science and Engineering, Sichuan University, Chengdu 610065, Sichuan, China
    dCatalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and BIST, Campus UAB, Bellaterra, Barcelona 08193, Catalonia, Spain
    eICREA, Pg. Lluís Companys 23, Barcelona08010, Catalonia, Spain
  • Received:2023-08-15 Accepted:2023-10-11 Online:2023-11-18 Published:2023-11-15
  • Contact: *E-mail: jiangshui.luo@scu.edu.cn (J. Luo), arbiol@icrea.cat (J. Arbiol),zyfu@scut.edu.cn (Z. Y. Fu), jan.fransaer@kuleuven.be (J. Fransaer).
  • Supported by:
    National Natural Science Foundation of China(21975081);National Natural Science Foundation of China(22178126);National Natural Science Foundation of China(22208110);National Natural Science Foundation of China(21776120);National Natural Science Foundation of China(22378270);Science and Technology Program of Guangzhou(2023A04J1357);China Postdoctoral Science Foundation(2022M711196);Open Project of Engineering Research Center of Alternative Energy Materials & Devices, Ministry of Education, Sichuan University(AEMD202204);Sichuan Science and Technology Program(2022ZYD0016);Sichuan Science and Technology Program(2023JDRC0013);Hohhot Science and Technology Program(2023-JieBangGuaShuai-Gao-3);Natural Science Foundation of Fujian Province, China(2023J01254);Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202206);Research Fund Program of Guangdong Provincial Key Laboratory of Fuel Cell Technology(FC202218)

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摘要：

析氧反应(OER)在电化学能源存储与转化技术(例如, 电解水与金属-空气电池)中扮演着至关重要的角色. OER涉及四个电子的连续转移, 动力学较为缓慢, 因此需要较高的过电位来驱动反应进行, 这严重限制了其在电化学储能和转换系统中的应用. IrO2和RuO2等贵金属基催化剂资源稀缺、价格高昂, 因此, 开发高活性、高稳定性及低成本的OER电催化剂显得尤为重要, 并且极具挑战. 杂原子掺杂是一种有效提升过渡金属化合物OER电催化剂活性的策略, 但是当前对其本征活性位点的识别及活性提升机制的研究仍然不足.

本文提出了一种阳离子掺杂策略, 通过引入金属阳离子调控多金属组分的电子结构, 优化OER中间体吸附能, 进而提升OER活性. 通过简单的一步热解硫化钴镍双金属有机框架材料前驱体, 成功制备了Ni掺杂CoS/氮掺杂介孔碳(Ni-CoS/NC)复合结构电催化剂; 并采用循环伏安法研究了其电化学行为与OER性能, 结合谱学研究结果与密度泛函理论(DFT)计算, 从原子层面揭示了OER条件下真实活性位点及掺杂型电催化剂的活性提升机制. 电化学研究结果表明, 所制备Ni-CoS/NC催化剂在1.0 mol L-1 KOH溶液中表现出较好的OER反应活性, 其在10 mA cm-2电流密度下的过电位为270 mV, Tafel斜率为37 mV dec-1. 采用X射线光电子能谱、高角度环形暗场扫描透射电子显微镜与电子能量损失谱等表征方法分析了OER前后催化剂的结构变化; 结果表明, 在OER电位下Ni-CoS/NC催化剂由金属硫化物转变为羟基氧化物CoxNi1-xOOH, CoxNii1-xOOH才是OER反应的活性位点. 理论结算结果表明, 在CoxNi1-xOOH材料中, Ni部分取代Co位点, 使两种金属之间产生强烈的电子相互作用, 导致Co位点带有更多的负电荷, Ni位点带有更多的正电荷, 从而增强了对中间物种OOH*的吸附, 提升OER活性.

综上, 金属阳离子掺杂调变金属活性中心的电子结构, 是提高电催化剂OER活性的有效策略. 过渡金属硫化物电催化剂在OER电位下发生了重构, 由晶态的金属硫化物转变为非晶态的金属羟基氧化物, 作为OER催化剂的活性位点. 本文为低成本、高性能电催化剂设计提供了一种可行的阳离子调控策略, 并且加深了对本征活性位点及活性提升机制的认识, 可为电化学能源存储与转化材料的开发提供借鉴.

关键词: 金属有机框架, 阳离子调控, 金属硫化物, 金属羟基氧化物, 析氧反应

Abstract:

Heteroatom doping serves as an important strategy to improve the oxygen evolution reaction (OER) activity of transition-metal compounds, while the investigation of intrinsic active sites and mechanisms remains insufficient. In this work, a facile cation regulation strategy is reported to boost the OER activity of metal sulfides via pyrolysis of the Ni-Co bimetallic metal-organic framework. The obtained Ni-substituted CoS nanoparticles on nitrogen-doped mesoporous carbon (Ni-CoS/NC) catalyst achieves a current density of 10 mA cm-2 at a small overpotential of 270 mV with a Tafel slope of 37 mV dec-1 in 1.0 mol L-1 KOH. Through a combination of spectroscopy study and theoretical computations, the activity origin is revealed at the atomic level. The CoxNi1-xOOH serves as the real active site for the OER generated by the Ni-CoS/NC reconstruction under oxidation potential during OER. The Ni substitution results in a strong electronic interaction between the two metals, thus generating more negatively charged Co atoms and more positively charged Ni atoms in the electrocatalyst. The metal sites with regulated electronic structure exhibit enhanced surface adsorption of OOH* and reduce the OER overpotential. Meanwhile, the conductive porous carbon scaffold facilitates electron transfer, mass diffusion, and the accessibility of active sites. This work not only provides a feasible cation regulation strategy for the design of high-performance electrocatalysts for low-cost energy storage and conversion systems, but also yields fresh insight into the activity enhancement mechanisms and intrinsic active sites.

Key words: Metal-organic framework, Cation regulation, Metal sulfide, Metal oxyhydroxide, Oxygen evolution reaction