高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (2): 624.doi: 10.7503/cjcu20200332

• 研究论文 • 上一篇    下一篇

高效催化氧还原及氧析出反应的掺杂石墨炔的设计与理论计算

马骏1,钟洋1,张珊珊1,黄仪珺1,张利鹏1,李亚平1,孙晓明1,夏振海2   

  1. 1.北京化工大学化工资源有效利用国家重点实验室, 北京 100029
    2.北德克萨斯州大学材料科学与工程系, 丹顿 TX 76203, 美国
  • 收稿日期:2020-06-08 出版日期:2021-02-10 发布日期:2020-09-24
  • 基金资助:
    国家自然科学基金(批准号(21675007);21676015, 21520102002, 91622116, 51973174)、 国家重点研发计划项目(批准号(2018YFB1502401);2018YFA0702002, 2017YFA0206500)和牛顿学者高级基金(批准号: NAF\R1\191294)资助

Design and Theoretical Calculation of Heteroatoms Doped Graphdiyne Towards Efficiently Catalyzing Oxygen Reduction and Evolution Reactions

MA Jun1, ZHONG Yang1, ZHANG Shanshan1, HUANG Yijun1, ZHANG Lipeng1(), LI Yaping1(), SUN Xiaoming1, XIA Zhenhai2()   

  1. 1.State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China
    2.Department of Materials Science and Engineering,University of North Texas,Denton TX 76203,USA
  • Received:2020-06-08 Online:2021-02-10 Published:2020-09-24
  • Contact: ZHANG Lipeng,LI Yaping,XIA Zhenhai E-mail:zhanglp@buct.edu.cn;liyp@mail.buct.edu.cn;zhenhai.xia@unt.edu
  • Supported by:
    the National Natural Science Foundation of China(21675007);the National Key Research and Development Project, China(2018YFB1502401);the Royal Society and the Newton Fund Through the Newton Advanced Fellowship Award (No.NAF\R1\191294)

摘要:

在清洁和可再生能源的转化过程中, 氧还原反应和氧析出反应需要高效的电催化剂以克服其动力学限制. 本文设计了一系列掺杂杂原子的无金属石墨二炔, 以促进上述两类关键化学反应.为了评估电催化性能, 利用密度泛函理论研究了反应路径和吉布斯自由能变化. 计算结果表明, 掺杂剂可以优化中间体的吸附, 降低反应的过电位. 本文还得到了将催化剂性质与催化剂结构相关联的内在描述符, 该描述符可以加速开发和筛选新型电催化剂. 研究结果可为清洁能源技术(如燃料电池、 金属空气电池和电解水等)中碳基催化剂的设计提供指导.

关键词: 氧还原反应, 氧析出反应, 杂原子掺杂石墨二炔, 描述符, 密度泛函理论

Abstract:

In the process of clean and renewable energy conversion, oxygen reduction reaction and oxygen evolution reaction demand highly efficient electrocatalysts to overcome their kinetic bottlenecks. Herein, a series of metal-free graphdiyne doped with heteroatoms was designed for promoting these key chemical reactions. To evaluate electrocatalytic performance, the reaction pathways and free energies were investigated systematically with the density functional theory(DFT). The calculations indicated that the dopants can optimize the adsorption of intermediates, lowering the overpotential of the reactions. Particularly, an intrinsic descriptor was identified to correlate the catalytic properties with catalyst structures, from which rapid screening could be made for the development of new catalysts. The results may provide guidance for the construction of carbon-based catalysts in clean energy technologies(such as fuel cells, metal-air batteries, electrolyzing water and so on).

Key words: Oxygen reduction reaction, Oxygen evolution reaction, Heteroatoms doping graphdiyne, Descriptor, Density functional theory

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