Liu Pingping, Fu Cheng, Li Yafei, Wei Haiyan
Jiangsu Key Laboratory of Biofunctional Materials, School of Chemistry and Materials Science, Jiangsu Key Lab for NSLSCS, Nanjing Normal University, Nanjing 210097, China.
Phys Chem Chem Phys. 2020 May 7;22(17):9322-9329. doi: 10.1039/c9cp06112f. Epub 2020 Apr 20.
The reduction of molecular dinitrogen (N) to ammonia (NH) under mild conditions is attractive due to the wide application of ammonia. In this work, we systematically investigated a series of single metal atoms including Sc to Zn, Mo, Ru, Rh, Pd and Ag anchored on defective graphene sheets for the N reduction reaction (NRR) by density functional theory computations. Our calculations revealed that single Mo embedded on nitrogen doped divacancy 555-777 graphene exhibits excellent catalytic performance for the NRR, with low overpotentials of 0.32 V for MoCN@555-777 graphene and 0.41 V for MoN@555-777 graphene. In particular, the removal of produced ammonia from the catalyst surface is a rapid process with a free energy change of less than 0.50 eV. Our study provides a useful guideline for further developing highly effective SACs based on defective graphene for electrochemical reduction reactions.
由于氨的广泛应用，在温和条件下将分子态二氮（N₂）还原为氨（NH₃）具有吸引力。在这项工作中，我们通过密度泛函理论计算系统地研究了一系列锚定在缺陷石墨烯片上的单金属原子，包括从钪（Sc）到锌（Zn）、钼（Mo）、钌（Ru）、铑（Rh）、钯（Pd）和银（Ag）用于氮还原反应（NRR）的情况。我们的计算表明，嵌入氮掺杂双空位555-777石墨烯中的单原子钼对NRR表现出优异的催化性能，对于MoCN@555-777石墨烯，过电位低至0.32 V，对于MoN@555-777石墨烯为0.41 V。特别地，从催化剂表面去除生成的氨是一个快速过程，自由能变化小于0.50 eV。我们的研究为进一步开发基于缺陷石墨烯的高效单原子催化剂用于电化学还原反应提供了有用的指导。
