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Chemical Research in Chinese Universities ›› 2022, Vol. 38 ›› Issue (5): 1226-1231.doi: 10.1007/s40242-022-2273-9

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Single Iron-dimer Catalysts on MoS2 Nanosheet for Potential Nitrogen Activation

QIAN Shengjie1, WANG Yanggang1, LI Jun1,2   

  1. 1. Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, P. R. China;
    2. Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China
  • Received:2022-09-02 Online:2022-10-01 Published:2022-10-08
  • Contact: WANG Yanggang E-mail:wangyg@sustech.edu.cn
  • Supported by:
    This work was supported by the National Natural Science Foundation of China (No.22022504), the “Pearl River” Talent Plan of Guangdong Province, China (No.2019QN01L353), the Fund of the Guangdong Provincial Key Laboratory of Catalysis, China(No.2020B121201002) and the Science and Technology Program of Shenzhen, China(No.JCYJ20210324103608023).

Abstract: Electrocatalytic nitrogen reduction reaction(NRR) is a promising way to produce ammonia(NH3) at ambient temperature and pressure. Herein, we have constructed single Fe dimer catalysts on a molybdenum disulfide monolayer for potential nitrogen activation. By employing ab initio molecular dynamics simulations, it is suggested that a dual iron-single atom site can be dynamically formed, which exhibits the similar Fe-S-Fe structure as the nitrogenase. We further identify an iron dimer with a sulfur vacancy as the active center for realistic nitrogen activation by the free energy calculations since the bridged sulfur is easy to be released in the form of H2S during the reduction process. It is shown that N2 mainly adsorbs on the Fe2 dimer at the sulfur vacancies in the pattern of side-on configuration, and the nitrogen reduction reaction is proceeded by an enzymatic mechanism. Charge analyses further show that the Fe2 dimer mainly works as an electron reservoir while MoS2 substrate with one sulfur vacancy acts as an inert carrier to stabilize the Fe2 dimer. Overall, our work provides important insights into how N2 molecules were adsorbed and activated on Fe2-doped MoS2, and provides new ideas for the transformation of actual reaction sites during electrochemical reactions.

Key words: Nitrogen reduction reaction, Ab initio molecular dynamics simulation, Single iron-dimer catalyst