物理化学学报 >> 2021, Vol. 37 >> Issue (7): 2009054.doi: 10.3866/PKU.WHXB202009054

所属专题: 电催化

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镍基金属有机框架衍生的双功能电催化剂用于析氢和析氧反应

闫大强1, 张林1, 陈祖鹏2, 肖卫平1,*(), 杨小飞1,*()   

  1. 1 南京林业大学理学院,材料物理与化学研究所,南京 210037
    2 南京林业大学化学工程学院,南京 210037
  • 收稿日期:2020-09-16 录用日期:2020-11-16 发布日期:2020-11-20
  • 通讯作者: 肖卫平,杨小飞 E-mail:wpxiao@njfu.edu.cn;xiaofei.yang@njfu.edu.cn
  • 基金资助:
    国家自然科学基金(21975129);江苏省自然科学基金(BK20190759);江苏省高校自然科学基金(19KJB430003);南京林业大学杰出青年基金(JC2019002)

Nickel-Based Metal-Organic Framework-Derived Bifunctional Electrocatalysts for Hydrogen and Oxygen Evolution Reactions

Daqiang Yan1, Lin Zhang1, Zupeng Chen2, Weiping Xiao1,*(), Xiaofei Yang1,*()   

  1. 1 College of Science, Institute of Materials Physics and Chemistry, Nanjing Forestry University, Nanjing 210037, China
    2 College of Chemical of Engineering, Nanjing Forestry University, Nanjing 210037, China
  • Received:2020-09-16 Accepted:2020-11-16 Published:2020-11-20
  • Contact: Weiping Xiao,Xiaofei Yang E-mail:wpxiao@njfu.edu.cn;xiaofei.yang@njfu.edu.cn
  • About author:Email: xiaofei.yang@njfu.edu.cn (X.Y.), Tel.: +86-25-85427080 (X.Y.)
    Email: wpxiao@njfu.edu.cn (W.X.)
  • Supported by:
    the National Natural Science Foundation of China(21975129);Natural Science Foundation of Jiangsu Province, China(BK20190759);Natural Science Foundation of Jiangsu Higher Education Institutions of China(19KJB430003);Science Fund for Distinguished Young Scholars, Nanjing Forestry University, China(JC2019002)

摘要:

开发高活性、低成本的析氢反应和析氧反应电催化剂对于能源的可持续发展至关重要。金属有机框架衍生的纳米材料已经成为一类非常有前景的非贵金属双功能电催化剂,但是目前对镍基金属有机框架衍生的双功能电催化剂的深入研究并不全面,其催化活性和稳定性还有待进一步提高。本文制备了一种棒状多孔碳负载镍纳米颗粒的新型电催化剂,并将其用作电催化析氢和析氧反应。实验研究结果表明该类电催化剂表现出优异的析氢和析氧反应活性和长期稳定性,在10 mA·cm−2的电流密度下,析氢反应和析氧反应的过电位分别为120和350 mV。我们认为:材料可控的纳米结构和均匀分布的活性位点共同提升了复合材料的电催化性能。

关键词: Ni基MOF, 水分解, 析氢反应, 析氧反应, 电催化剂

Abstract:

In recent years, electrochemical water splitting that involves the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has attracted widespread attention because the process is clean, environmentally friendly, and the generated oxygen/hydrogen gas can be converted into electricity in a fuel cell. However, the HER and OER kinetics are sluggish and require highly efficient electrocatalysts for enhancing the reaction rate. Currently, precious metals such as Pt and RuO2 have shown excellent HER and OER performance, respectively, but their practical applications are limited by their scarcity and high price. Therefore, the use of 3d transition metals, such as iron (Fe) and nickel (Ni), as electrocatalysts has attracted significant attention. To obtain a catalytic performance similar to that of precious metals, several methods have been explored, such as alloying 3d transition metals with precious metals, compositing a variety of transition metals, or requiring good carbon-based materials as a supporter. Metal-organic framework (MOF)-derived nanomaterials have emerged as some of the most promising non-precious metal bifunctional electrocatalysts. The MOF structure consists of metal-based units and special organic ligands, and after annealing, metal atoms can be converted into unsaturated metal-based active sites, and the organic ligands can be converted into carbon support. This could accelerate the charge transfer efficiency and can be beneficial for achieving excellent HER and OER performance. However, bifunctional electrocatalysts derived from nickel (Ni)-based MOFs have not been studied intensively, and their catalytic activity and stability remain to be improved. Herein, a Ni-MOF precursor was synthesized via a liquid-phase coordination reaction using Ni2+ and benzene-1, 3, 5-tricarboxylic acid. The obtained Ni-MOF samples were annealed under H2/Ar atmosphere at 600, 700, and 800 ℃, named Ni/C-H2-600, Ni/C-H2-700, Ni/C-Ar-700, and Ni/C-H2-800, respectively. During high-temperature annealing treatment, Ni nanoparticles were grown in situ on a rod-shaped carbon substrate to form novel hybrid architecture Ni/C nanoparticles used as a high-performance bifunctional electrocatalyst for overall water splitting. The HER overpotential of Ni/C-H2-700 was 120 mV at a current density of 10 mA∙cm−2, which is much lower than that of Ni/C-H2-600 (250 mV), Ni/C-H2-800 (348 mV), and Ni/C-Ar-700 (275 mV). Ni/C-H2-700 required an OER overpotential of 350 mV to achieve a current density of 10 mA∙cm−2, which is lower than that of Ni/C-H2-600 (370 mV), Ni/C-H2-800 (430 mV), and Ni/C-Ar-700 (380 mV). Furthermore, Ni/C-H2-700 showed the idea of HER and OER durability. Presumably, good structural properties and the abundant surface area of the carbon substrate elevated HER/OER activity owing to the synergistic advantages of accessible active sites and enhanced electronic conductivity.

Key words: Ni-based MOFs, Water splitting, Hydrogen evolution reaction, Oxygen evolution reaction, Electrocatalyst

MSC2000: 

  • O646