钼掺杂电子修饰Fe3N表面氨分解机理的DFT研究,The Journal of Physical Chemistry C

当前位置： X-MOL 学术 › J. Phys. Chem. C › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

钼掺杂电子修饰Fe3N表面氨分解机理的DFT研究
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-08-09 , DOI: 10.1021/acs.jpcc.3c04207
Diksha Praveen Pathak ₁ , Anwesh Kumar ₁ , Balathanigaimani Marriyappan Sivagnanam ₁ , A. S. K. Sinha ₁ , J. Karthikeyan _{2,

3}

Affiliation

氨是现场输送氢气的潜在无碳载体，对于氢经济的发展至关重要。_{设计用于NH 3}低温分解的无贵金属催化剂是该路线中的一项具有挑战性的任务。我们进行了第一性原理研究，以全面了解钼掺杂氮化铁（Fe ₃ N）表面的氨分解机理。_{结果表明，当Mo掺杂在Fe 3} N(111)表面时，它会向表面提供电子并改变催化剂的整体电子结构。_{Mo掺杂Fe 3}上氨分解中间步骤的活化能显着降低与未掺杂的Fe ₃ N相比，N 表面。相比于Mo 掺杂的Fe ₃ N(111)， NH _{3优先吸附在Mo 位点上。}然而，随后的中间物质NH ₂和NH更喜欢Fe位点进行吸附。与Mo掺杂Fe _{3 N(111)上NH}₃分解中的其他基本步骤相比，氮吸附原子的重组和解吸的活化势垒最高，因此限制了氨分解反应的总速率。巴德电荷、态密度 (DOS) 和晶体轨道哈密顿布居 (COHP) 计算阐明了催化剂的电子特性。

"点击查看英文标题和摘要"

A DFT Study of the Ammonia Decomposition Mechanism on the Electronically Modified Fe3N Surface by Doping Molybdenum

Ammonia is a potential carbon-free carrier for the on-site delivery of hydrogen and is critical in the development of a hydrogen economy. Designing a noble metal-free catalyst for the low-temperature decomposition of NH₃ is a challenging task in this route. We conducted first-principles studies to have a comprehensive understanding of the ammonia decomposition mechanism on the molybdenum-doped iron nitride (Fe₃N) surface. The results indicate that when Mo is doped on the surface of Fe₃N(111) it donates electrons to the surface and alters the overall electronic structure of the catalyst. The activation energy for the intermediate steps of ammonia decomposition is substantially reduced on the Mo-doped Fe₃N surface compared to undoped Fe₃N. NH₃ adsorbs preferably on Mo sites over Mo-doped Fe₃N(111). However, subsequent intermediate species NH₂ and NH prefer Fe sites for adsorption. The activation barrier for the recombination and desorption of nitrogen adatoms is highest compared to the other elementary steps in the breakdown of NH₃ on Mo-doped Fe₃N(111) and therefore limits the overall rate of the decomposition reaction of ammonia. The Bader charge, density of state (DOS), and crystal orbital Hamiltonian population (COHP) calculations elucidate the electronic properties of the catalyst.

更新日期：2023-08-09

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南