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

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: LU Xiao-Qing,
Received Date: 19 August 2015
Available Online: 16 November 2015
Fund Project: 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)

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.
- Molybdenum phosphide,
- Aniline,
- Hydrodenitrogeneration,
- C―N bond,
- Density functional theory
1. [1]
  (1) Zeuthen, P.; Knudsen, K. G.; Whitehurst, D. D. Catal. Today 2001, 65 (2-4), 307. doi: 10.1016/S0920-5861(00)00566-6
2. [2]
  (2) Phillips, D. C.; Sawhill, S. J.; Self, R.; Bussell, M. E. J. Catal. 2002, 207 (2), 266. doi: 10.1006/jcat.2002.3524
3. [3]
  (3) Clark, P.; Wang, X.; Oyama, S. T. J. Catal. 2002, 207 (2), 256. doi: 10.1006/jcat.2002.3520
4. [4]
  (4) Oyama, S. T.; Wang, X.; Lee, Y. K.; Chun, W. J. J. Catal. 2004, 221 (2), 263. doi: 10.1016/S0021-9517(03)00017-4
5. [5]
  (5) Oyama, S. T. J. Catal. 2003, 216 (1-2), 343. doi: 10.1016/S0021-9517(02)00069-6
6. [6]
  (6) Stinner, C.; Prins, R.; Weber, T. J. Catal. 2000, 191 (2), 438. doi: 10.1006/jcat.1999.2808
7. [7]
  (7) Li, W.; Dhandapani, B.; Oyama, S. T. Chem. Lett. 1998, 168(3), 207.
8. [8]
  (8) Oyama, S. T.; Clark, P.; Teixiera da Silva, V. L. S.; Lede, E. J.; Requejo, F. G. J. Phys. Chem. B 2001, 105 (21), 4961. doi: 10.1021/jp004500q
9. [9]
  (9) Lü , C. Q.; Ling, K. C.; Wang, G. C. Acta Phys. -Chim. Sin. 2009, 25 (11), 2336. [吕存琴, 凌开成, 王贵昌. 物理化学学报, 2009, 25 (11), 2336.] doi: 10.3866/PKU.WHXB20091038
10. [10]
  (10) Zuzaniuk, V.; Prins, R. J. Catal. 2003, 219 (1), 85. doi: 10.1016/S0021-9517(03)00149-0
11. [11]
  (11) Sun, F. X.; Wu, W. C.; Wu, Z. L.; Guo, J.; Wei, Z. B.; Yang, Y.X.; Jiang, Z. X.; Tian, F. P.; Li, C. J. Catal. 2004, 228 (2), 298. doi: 10.1016/j.jcat.2004.09.002
12. [12]
  (12) Clark, P.; Oyama, S. T. J. Catal. 2003, 218 (1), 78. doi: 10.1016/S0021-9517(03)00086-1
13. [13]
  (13) Rodriguez, J. A.; Kim, J. Y.; Hanson, J. C.; Sawhill, S. J.; Bussell, M. E. J. Phys. Chem. B 2003, 107 (26), 6276. doi: 10.1021/jp022639q
14. [14]
  (14) Geneste, P.; Moulinas, C.; Olivé , J. L. J. Catal. 1987, 105 (1), 254. doi: 10.1016/0021-9517(87)90025-X
15. [15]
  (15) Rota, F.; Prins, R. J. Mol. Catal. A: Chem. 2000, 162 (1-2), 367. doi: 10.1016/S1381-1169(00)00303-4
16. [16]
  (16) Mou, J.; Kapteijn, F.; Prins, R. J. Catal. 1997, 168 (2), 491. doi: 10.1006/jcat.1997.1650
17. [17]
  (17) Li, Y.; Guo, W. Y.; Zhu, H. Y.; Zhao, L. M.; Li, M.; Li, S. R.; Fu, D. L.; Lu, X. Q.; Shan, H. H. Langmuir 2012, 28 (6), 3129. doi: 10.1021/la2051004
18. [18]
  (18) Delley, B. J. Chem. Phys. 1990, 92 (1), 508. doi: 10.1063/1.458452
19. [19]
  (19) Delley, B. J. Chem. Phys. 1996, 100 (15), 6107 doi: 10.1021/jp952713n
20. [20]
  (20) Delley, B. J. Chem. Phys. 2000, 113 (18), 7756. doi: 10.1063/1.1316015
21. [21]
  (21) Perdew, J. P.; Wang, Y. Phys. Rev. B 1986, 33 (12), 8800. doi: 10.1103/PhysRevB.33.8800
22. [22]
  (22) Perdew, J. P.; Wang, Y. Phys. Rev. B 1992, 45 (23), 13244. doi: 10.1103/PhysRevB.45.13244
23. [23]
  (23) Ren, J.; Huo, C. F.; Wen, X. D.; Cao, Z.; Wang, J. G.; Li, Y.W.; Jiao, H. J. J. Phys. Chem. B 2006, 110 (45), 22563. doi: 10.1021/jp0640474
24. [24]
  (24) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13 (12), 5188. doi: 10.1103/PhysRevB.13.5188
25. [25]
  (25) Rundgvist, S.; Lundströ m, T. Acta Chem. Scand. 1962, 17 (1), 37.
26. [26]
  (26) Winkler, B.; Knorr, K.; Hytha, M.; Milman, V. J. Phys. Chem. Solids 2003, 64 (3), 405. doi: 10.1016/S0022-3697(02)00293-7
27. [27]
  (27) Halgren, T. A.; Lipscomb, W. N. Chem. Phys. Lett. 1977, 49(2), 225. doi: 10.1016/0009-2614(77)80574-5
28. [28]
  (28) Milman, V.; Winkler, B.; Gomperts, R. Chem. -Eur. J. 2004, 10(24), 6279.
29. [29]
  (29) Liu, P.; Rodriguez, J. A. Catal. Lett. 2003, 91 (3), 247.
30. [30]
  (30) Oyama, S. T.; Lee, Y. K. J. Phys. Chem. B 2005, 109 (6), 2109 doi: 10.1021/jp049194l
31. [31]
  (31) Rota, F.; Prins, R. Stud. Surf. Sci. Catal. 1999, 127, 319. doi: 10.1016/S0167-2991(99)80423-6
1. [1]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
2. [2]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
3. [3]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
4. [4]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
5. [5]
  Yinuo Wang , Siran Wang , Yilong Zhao , Dazhen Xu . Selective Synthesis of Diarylmethyl Anilines and Triarylmethanes via Multicomponent Reactions: Introduce a Comprehensive Experiment of Organic Chemistry. University Chemistry, 2024, 39(8): 324-330. doi: 10.3866/PKU.DXHX202401063
6. [6]
  Lanjun Cheng , Xinyuan Wang , Jie An , Xiang Wu , Chengfeng Zhu , Yanming Fu , Yougui Li . Improvement of the Resolution Experiment of Racemic Tartaric Acid. University Chemistry, 2025, 40(7): 277-285. doi: 10.12461/PKU.DXHX202408010
7. [7]
  Jiaxi Xu , Yuan Ma . Stable Conformation of Several Common Aromatic Compounds. University Chemistry, 2025, 40(12): 183-186. doi: 10.12461/PKU.DXHX202508007
8. [8]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
9. [9]
  Tongqi Ye , Yanqing Wang , Qi Wang , Huaiping Cong , Xianghua Kong , Yuewen Ye . Reform of Classical Thermodynamics Curriculum from the Perspective of Computational Chemistry. University Chemistry, 2025, 40(7): 387-392. doi: 10.12461/PKU.DXHX202409128
10. [10]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
11. [11]
  Xiaochen Zhang , Fei Yu , Jie Ma . Cutting-Edge Applications of Multi-Angle Numerical Simulations for Capacitive Deionization. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-0. doi: 10.3866/PKU.WHXB202311026
12. [12]
  Xinwan Zhao , Yue Cao , Minjun Lei , Zhiliang Jin , Tsubaki Noritatsu . Constructing S-scheme heterojunctions by integrating covalent organic frameworks with transition metal sulfides for efficient noble-metal-free photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(12): 100152-0. doi: 10.1016/j.actphy.2025.100152
13. [13]
  Yuai Duan , Xuanyu Gan , Yao Fu , Yingjie Cao , Hongliang Han , Zhanfang Ma . Application and Innovative Design of Digital Technology in the Preparation Experiment of Cis(Trans)-Diglycine Copper Complexes. University Chemistry, 2026, 41(1): 373-381. doi: 10.12461/PKU.DXHX202504048
14. [14]
  Chenxu Gong , Weizhen Wang , Ruiying Zhang , Wenfeng Wang , Yuanming Li , Yaofeng Yuan , Keyin Ye . Computational Chemistry-Assisted Organic Structure Analysis (CCAOSA): A Case Study of Propeller-Shaped Hexabenzotriphenylene. University Chemistry, 2026, 41(4): 438-446. doi: 10.12461/PKU.DXHX202503076
15. [15]
  Shuangshuang Mao , Juhua Luo , Bingjie Han , Jiahuan Shi , Yujia Gu . Covalent organic framework-derived Fe₃C/NC/TiO₂ heterostructures for high-performance electromagnetic wave absorption. Acta Physico-Chimica Sinica, 2026, 42(7): 100290-. doi: 10.1016/j.actphy.2026.100290
16. [16]
  Hao Wu , Fengqi Li , Xinwei Shi , Haifeng Bian , Qing Zhou , Shunshun Jia , Yujie Ma , Jian Gu , Jingzi Zhang , Shuijian He , Xiangkang Meng . Machine-learning guides discovery of multi-principal element alloys as electrocatalyst for hydrogen evolution reaction. Acta Physico-Chimica Sinica, 2026, 42(8): 100227-0. doi: 10.1016/j.actphy.2025.100227
17. [17]
  Weiheng Liu , Juhua Luo , Jiahuan Shi , Di Lan , Shuangshuang Mao , Yu Xie . Honeycomb-like BiCo@NC composites derived from bimetallic organic frameworks for high-efficiency electromagnetic wave absorption. Acta Physico-Chimica Sinica, 2026, 42(8): 100313-0. doi: 10.1016/j.actphy.2026.100313
18. [18]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
19. [19]
  Yupeng TANG , Haiying YANG , Fan JIN , Nan LI . Hydrogen storage properties of C₆S₆Li₆: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1827-1839. doi: 10.11862/CJIC.20240460
20. [20]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(886)
HTML views(51)

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