MoP(001)表面苯胺C―N键断裂机理

引用本文: 李邵仁, 鲁效庆, 朱后禹, 郭文跃. MoP(001)表面苯胺C―N键断裂机理[J]. 物理化学学报, 2016, 32(2): 465-473. doi: 10.3866/PKU.WHXB201511242 shu

Citation: LI Shao-Ren, LU Xiao-Qing, ZHU Hou-Yu, GUO Wen-Yue. Mechanism of C―N Bond Cleavage in Aniline on MoP(001) Surface[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 465-473. doi: 10.3866/PKU.WHXB201511242 shu

MoP(001)表面苯胺C―N键断裂机理

1.
中国石油大学(华东)理学院, 山东青岛 266580

通讯作者: 鲁效庆

基金项目:
国家自然科学基金(21303266) (21303266)

中国石油科技创新基金(2013D-5006-0406)资助项目 (2013D-5006-0406)

摘要: 油品脱氮可以减少燃烧过程中氮氧化物的排放,并且减弱催化剂的中毒现象,过渡金属磷化物因具有高催化活性和优异的稳定性而成为最具应用前景的新型加氢脱氮(HDN)催化剂。本工作基于周期性平板模型,通过密度泛函理论(DFT)计算研究了苯胺在磷化钼(MoP)(001)表面的吸附以及C―N断键机理。结果表明在MoP(001)表面,苯胺吸附以平躺吸附构型为主,有较大的吸附能,C―C键和C―N键均被吸附活化;苯胺C―N键的直接断裂路径主要起始于与共吸附H₂发生反应,产物为苯和氨,吸附的环己胺的C―N键断裂主要路径是环己胺与共吸附的H发生反应脱去氨基,生成产物为环己烯和氨。

关键词:

English

Mechanism of C―N Bond Cleavage in Aniline on MoP(001) Surface

1.
College of Science, China University of Petroleum, Qingdao 266580, Shandong Province, P. R. China

Corresponding author: 鲁效庆

Received Date: 19 August 2015
Fund Project:
国家自然科学基金(21303266)

中国石油科技创新基金(2013D-5006-0406)资助项目

Abstract: Denitrogeneration of petroleum products can reduce NO_x emission during combustion, and relieve the poisoning of catalysts. Because of their high catalytic activities and excellent stabilities, transition metal phosphides exhibit great potential as novel, promising hydrodenitrogeneration (HDN) catalysts. Based on a periodic slab model, we investigated the adsorption and C―N bond cleavage mechanism of aniline on MoP(001) surface by density functional theory (DFT) calculations. The results show that aniline adsorption prefers a flat configuration, with larger adsorption energies, in which the C―C and C―N bonds are activated. The direct C―N bond cleavage mechanism of aniline proceeds mainly via deamination with co-adsorbed H₂, producing benzene and ammonia. The C―N bond cleavage mechanism for adsorbed cyclohexylamine proceeds via deamination, with co-adsorbed H, and the main products are cyclohexene and ammonia.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

MoP(001)表面苯胺C―N键断裂机理

通讯作者: 鲁效庆

English

Mechanism of C―N Bond Cleavage in Aniline on MoP(001) Surface

Corresponding author: 鲁效庆

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

MoP(001)表面苯胺C―N键断裂机理

通讯作者: 鲁效庆

English

Mechanism of C―N Bond Cleavage in Aniline on MoP(001) Surface

Corresponding author: 鲁效庆

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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