Ni-MoTiNO用于电化学N2还原反应的理论研究

doi:10.16553/j.cnki.issn1000-985x.2024.0242

摘要/Abstract

摘要： 电化学氮气还原反应(ENRR)是替代Haber-Bosch工艺合成氨的可持续发展技术之一,其核心问题是寻找高催化活性和高选择性的稳定电催化剂。过渡金属氮氧化物(TMNO)表面遵循Mars-van Krevelen(MvK)机理路径进行合成氨反应,表现出比传统缔合机理更有利的N₂吸附和活化,其设计双位点活性催化剂成为高效催化研究的热点。本文选用具有最佳ENRR表现的双位点MoTiNO作为基底,通过密度泛函理论(DFT)计算方法负载Ni构建了Ni-MoTiNO 结构作为电化学N₂还原催化剂,进行了结构稳定性、双位点吸附行为、基于原子氢(^*H)迁移辅助MvK机理的ENRR催化活性和电子性质分析四方面的研究。计算结果表明,Ni-MoTiNO表面的双位点(Ni和Nv)协同作用既促进了^*H迁移,又有效打破了ENRR中^*N相关中间体吸附能力和产物脱附能力的线性比例关系。实验证明,合成的Ni-MoTiNO能够有效实现NH₃合成并具有较高的选择性。

关键词: 合成氨, MvK机理, 电催化, 氮空位, MoTiNO, 负载

Abstract: The electrochemical nitrogen reduction reaction (ENRR) is one of the sustainable development technologies for the synthesis of NH₃ to replace the Haber-Bosch process. The core issue is to find stable electrocatalysts with high catalytic activity and selectivity. Since the transition metal oxynitrides (TMNO) surface follows the Mars-van Krevelen (MvK) mechanism pathway for ammonia synthesis reaction, it exhibits more favorable N₂ adsorption and activation than the conventional association mechanism. Based on this, Ni was selected to be loaded on dual-sites MoTiNO with the best ENRR performance, and the Ni-MoTiNO structure was constructed as an electrochemical N₂ reduction catalyst by the density function theory (DFT) calculation method, and four aspects, including the structural stability, two-site adsorption behaviors, ENRR catalytic activity based on the ^*H-migration-assisted MvK mechanism, and the analysis of the electronic properties, were investigated. Results show that the synergistic action of the dual sites (Ni and Nv) on the surface of Ni-MoTiNO both promotes ^*H migration and effectively breaks the linear proportionality between the strong adsorption of ^*N-related intermediates and the difficulty in resolving the products in ENRR. Experiments have proved that the synthesized Ni-MoTiNO can effectively achieve ammonia synthesis and has a relatively high selectivity.

Key words: ammonia synthesis, MvK mechanism, electrocatalysis, nitrogen vacancy, MoTiNO, loading

中图分类号:

O643.3

曹琦, 崔璐瑶. Ni-MoTiNO用于电化学N₂还原反应的理论研究[J]. 人工晶体学报, 2025, 54(4): 708-716.

CAO Qi, CUI Luyao. Theoretical Study of Ni-MoTiNO for Electrochemical N₂ Reduction Reaction[J]. Journal of Synthetic Crystals, 2025, 54(4): 708-716.

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Ni-MoTiNO用于电化学N₂还原反应的理论研究

Theoretical Study of Ni-MoTiNO for Electrochemical N₂ Reduction Reaction

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