Single Manganese Atom Anchored on N-doped Graphene as a Promising Catalyst for Nitrogen Reduction Reaction:A First-Principles Study  

MnNx-graphene作为氮还原反应催化剂的第一性原理研究

作　　者：Li Xu Yong Tang Mengge Cao Kuan Zhou Hongbao Li 徐丽;唐勇;曹梦鸽;周宽;李宏保(安徽大学物质科学与信息技术研究院,杂化材料结构与功能调控教育部重点实验室(教育部),安徽省石墨烯工程实验室,合肥230601)

机构地区：[1]Institutes of Physical Science and Information Technology,Key Laboratory of Structure and Functional Regulation of Hybrid Materials(Ministry of Education)

出　　处：《Chinese Journal of Chemical Physics》2025年第2期189-198,I0013-I0019,I0040,共18页化学物理学报(英文)

基　　金：supported by the Excellent Research and Innovation Team Project of Anhui Province(2022AH010001)。

摘　　要：Electrochemical synthesis of ammonia represents a green and environmental-ly friendly method distinct from tradi-tional Harper-Bosch processes,which demand stringent conditions.However,identifying a catalyst with high selec-tivity and catalytic activity to cleave the robust triple bond of N_(2)remains a formidable challenge.Herein,we present a systematic study on the geo-metrical and electronic structure,intensity of N_(2)adsorption,reaction intermediates,change in Gibbs free energy,and desorption of by-product hydrazine for the nitrogen reduction reac-tion employing a MnNx-graphene(x=3,4)catalyst from a theoretical perspective.The com-putational results reveal that MnN3-graphene exhibits superior catalytic performance pre-dominantly via the distal mechanism,with a low potential of 0.49 V.Moreover,the detach-ment of the produced NH3 is facilitated with a free energy of only 0.27 eV,significantly lower than those of previous catalysts,ensuring the exceptional durability of MnN_(3)-graphene.This study offers theoretical insights guiding the exploration of single Mn atom catalysts in ammo-nia synthesis.不同于传统的需要严格条件的哈勃-博世工艺,氨的电化学合成是一种绿色环保的方法.然而,设计出一种具有高选择性和催化活性的催化剂来裂解N2中牢固的氮氮三键仍然面临艰巨的挑战.本文从理论计算角度对MnNx-graphene(x=3,4)催化剂催化氮还原反应的几何结构、电子结构、N2吸附强度、反应中间体、吉布斯自由能变化和副产N2H4解吸附等进行了系统研究.计算结果表明,MnN3-graphene主要通过远端机理表现出优异的催化性能,其电位低至0.49 V,明显低于文献中其他Mn单原子催化剂.此外,0.27 eV的自由能促进了NH3的脱附,确保了MnN3-graphene出色的催化活性.本文从理论计算角度为单Mn原子催化剂在氨合成领域的探索提供了理论启示.

关 键 词：MANGANESE N-doped graphene Nitrogen reduction reaction 

分 类 号：O643.36[理学—物理化学]