气相中Co+催化N2O与C2H6循环反应催化剂活性的理论研究

引用本文: 吴晶晶, 王永成, 蔡君, 金燕子, 王环江, 甘延珍. 气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究[J]. 催化学报, 2014, 35(4): 579-589. doi: 10.1016/S1872-2067(14)60037-1 shu

Citation: Jingjing Wu, Yongcheng Wang, Jun Cai, Yanzi Jin, Huanjiang Wang, Yanzhen Gan. Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase[J]. Chinese Journal of Catalysis, 2014, 35(4): 579-589. doi: 10.1016/S1872-2067(14)60037-1 shu

气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究

通讯作者: 王永成

基金项目:
国家自然科学基金(21263023). (21263023)

摘要: 采用密度泛函理论UB3LYP方法对Co⁺在三重态及五重态势能面上催化N₂O与C₂H₆进行循环反应的两态反应机理进行了研究. 运用Harvery方法优化了两自旋态势能面5个最低能量交叉点(MECP), 计算了MECP处自旋-轨道耦合作用. 采用Landau-Zener公式计算了自旋翻转处的系间窜越几率, 各MECP处均可发生有效系间窜越. 通过应用Kozuch提出的能量跨度模型, Co⁺催化N₂O与C₂H₆在298K下反应生成CH₃CHO时有最大的TOF值3.35×10^-21s^-1.

关键词:

English

Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase

1.
Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China

Corresponding author: 王永成

Received Date: 18 November 2013
Available Online: 20 April 2014
Fund Project:
国家自然科学基金(21263023).

Abstract: The spin-forbidden mechanism of the reaction between N₂O and C₂H₆ catalyzed by Co⁺ has been investigated using UB3LYP density functional theory. The Harvey method has been applied to optimize five minimum energy crossing points (MECP) on both triplet and quintet potential energy surfaces. Possible spin inversion processes are discussed by means of spin-orbit coupling calculations. According to the calculation of probability of electron hopping using the Landau-Zener formula, effective intersystem crossing may occur at each MECP. The energetic span model proposed by Kozuch has been applied to the catalytic cycles, and shows the turnover frequency reaches 3.35×10^-21 s^-1 when Co⁺ catalyzes the reaction to produce CH₃CHO at 298K.

Key words:

1. [1] Schröder D, Schwarz H. Angew Chem Int Ed, 1995, 34: 1973[1] Schröder D, Schwarz H. Angew Chem Int Ed, 1995, 34: 1973
2. [2] Yoshizawa K, Shiota Y, Yamabe T. J Am Chem Soc, 1998, 120: 564[2] Yoshizawa K, Shiota Y, Yamabe T. J Am Chem Soc, 1998, 120: 564
3. [3] Shiota Y, Yoshizawa K. J Am Chem Soc, 2000, 122: 12317[3] Shiota Y, Yoshizawa K. J Am Chem Soc, 2000, 122: 12317
4. [4] Blagojevic V, Orlova G, Bohme D K. J Am Chem Soc, 2005, 127: 3545[4] Blagojevic V, Orlova G, Bohme D K. J Am Chem Soc, 2005, 127: 3545
5. [5] Liu F S, Chu W, Sun W J, Xue Y, Jiang Q. J Nat Gas Chem, 2012, 21: 708[5] Liu F S, Chu W, Sun W J, Xue Y, Jiang Q. J Nat Gas Chem, 2012, 21: 708
6. [6] Wen Z G, Li H, Weng W Z, Xia W S, Huang C J, Wan H L. Chin J Catal (温在恭, 李虎, 翁维正, 夏文正, 黄传敬, 万惠霖. 催化学报), 2012, 33: 1183[6] Wen Z G, Li H, Weng W Z, Xia W S, Huang C J, Wan H L. Chin J Catal (温在恭, 李虎, 翁维正, 夏文正, 黄传敬, 万惠霖. 催化学报), 2012, 33: 1183
7. [7] Ryan M F, Fiedler A, Schroeder D, Schwarz H. Organometallics, 1994, 13: 4072[7] Ryan M F, Fiedler A, Schroeder D, Schwarz H. Organometallics, 1994, 13: 4072
8. [8] Zhao L M, Lu X Q, Li Y Y, Chen J, Guo W Y. J Phys Chem A, 2012, 116: 3282[8] Zhao L M, Lu X Q, Li Y Y, Chen J, Guo W Y. J Phys Chem A, 2012, 116: 3282
9. [9] Harvey J N, Poli R, Smith K M. Coord Chem Rev, 2003, 238-239: 347[9] Harvey J N, Poli R, Smith K M. Coord Chem Rev, 2003, 238-239: 347
10. [10] Danovich D, Shaik S. J Am Chem Soc, 1997, 119: 1773[10] Danovich D, Shaik S. J Am Chem Soc, 1997, 119: 1773
11. [11] Nian J Y, Wang J, Wang Y C. Comput Theoret Chem, 2011, 974: 143[11] Nian J Y, Wang J, Wang Y C. Comput Theoret Chem, 2011, 974: 143
12. [12] Ma W P, Wang Y C, Lü L L, Jin Y Z, Nian J Y, Ji D F, Wang C L, La M J, Wang X B, Wang Q. Comput Theoret Chem, 2011, 977: 69[12] Ma W P, Wang Y C, Lü L L, Jin Y Z, Nian J Y, Ji D F, Wang C L, La M J, Wang X B, Wang Q. Comput Theoret Chem, 2011, 977: 69
13. [13] Zeng X L, HuangShan Q S, Ju X H. Acta Phys-Chim Sin (曾秀琳, 黄山奇松, 居学海. 物理化学学报), 2013, 29: 2308[13] Zeng X L, HuangShan Q S, Ju X H. Acta Phys-Chim Sin (曾秀琳, 黄山奇松, 居学海. 物理化学学报), 2013, 29: 2308
14. [14] Schröder D, Shaik S, Schwarz H. Acc Chem Res, 2000, 33: 139[14] Schröder D, Shaik S, Schwarz H. Acc Chem Res, 2000, 33: 139
15. [15] Kozuch S, Shaik S. J Am Chem Soc, 2006, 128: 3355[15] Kozuch S, Shaik S. J Am Chem Soc, 2006, 128: 3355
16. [16] Kozuch S, Shaik S. J Phys Chem A, 2008, 112: 6032[16] Kozuch S, Shaik S. J Phys Chem A, 2008, 112: 6032
17. [17] Kozuch S, Shaik S. Acc Chem Res, 2011, 44: 101[17] Kozuch S, Shaik S. Acc Chem Res, 2011, 44: 101
18. [18] Nian J Y, Wang Y C, Ma W P, Ji D F, Wang C L, La M J. J Phys Chem A, 2011, 115: 11023[18] Nian J Y, Wang Y C, Ma W P, Ji D F, Wang C L, La M J. J Phys Chem A, 2011, 115: 11023
19. [19] Uhe A, Kozuch S, Shaik S. J Comput Chem, 2011, 32: 978[19] Uhe A, Kozuch S, Shaik S. J Comput Chem, 2011, 32: 978
20. [20] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A J, Vreven T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G l. Gaussian 03 (Revision-E. 01). Pittsburgh P A: Gaussian Inc, 2003[20] Frisch M J, Trucks G W, Schlegel H B, Scuseria G E, Robb M A, Cheeseman J R, Montgomery J A J, Vreven T, Kudin K N, Burant J C, Millam J M, Iyengar S S, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson G A, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox J E, Hratchian H P, Cross J B, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann R E, Yazyev O, Austin A J, Cammi R, Pomelli C, Ochterski J W, Ayala P Y, Morokuma K, Voth G A, Salvador P, Dannenberg J J, Zakrzewski V G, Dapprich S, Daniels A D, Strain M C, Farkas O, Malick D K, Rabuck A D, Raghavachari K, Foresman J B, Ortiz J V, Cui Q, Baboul A G, Clifford S, Cioslowski J, Stefanov B B, Liu G l. Gaussian 03 (Revision-E. 01). Pittsburgh P A: Gaussian Inc, 2003
21. [21] Su M D, Chu S Y. J Am Chem Soc, 1999, 121: 4229[21] Su M D, Chu S Y. J Am Chem Soc, 1999, 121: 4229
22. [22] Lee C, Yang W T, Parr R G. Phys Rev B, 1988, 37: 785[22] Lee C, Yang W T, Parr R G. Phys Rev B, 1988, 37: 785
23. [23] Chiodo S, Russo N, Sicilia E. J Comput Chem, 2004, 26: 175[23] Chiodo S, Russo N, Sicilia E. J Comput Chem, 2004, 26: 175
24. [24] Raghavachari K, Trucks G W. J Chem Phys, 1989, 91: 1062[24] Raghavachari K, Trucks G W. J Chem Phys, 1989, 91: 1062
25. [25] Yoshizawa K, Shiota Y, Yamabe T. J Chem Phys, 1999, 111: 538[25] Yoshizawa K, Shiota Y, Yamabe T. J Chem Phys, 1999, 111: 538
26. [26] Glendening E D, Badenhoop J K, Reed A E, Carpenter J E, Bohmann J A, Morales C M, Weinhold F. NBO 5.0. Madison: University of Wisconsin, 2001[26] Glendening E D, Badenhoop J K, Reed A E, Carpenter J E, Bohmann J A, Morales C M, Weinhold F. NBO 5.0. Madison: University of Wisconsin, 2001
27. [27] Harvey J N, Aschi M. Faraday Discuss, 2003, 124: 129[27] Harvey J N, Aschi M. Faraday Discuss, 2003, 124: 129
28. [28] Harvey J N. Phys Chem Chem Phys, 2007, 9: 331[28] Harvey J N. Phys Chem Chem Phys, 2007, 9: 331
29. [29] Chu T S, Zhang Y, Han K L. Int Rev Phys Chem, 2006, 25: 201[29] Chu T S, Zhang Y, Han K L. Int Rev Phys Chem, 2006, 25: 201
30. [30] Fedorov D G, Koseki S, Schmidt M W, Gordon M S. Int Rev Phys Chem, 2003, 22:551[30] Fedorov D G, Koseki S, Schmidt M W, Gordon M S. Int Rev Phys Chem, 2003, 22:551
31. [31] Christiansen J A. Adv Catal, 1953, 5: 311[31] Christiansen J A. Adv Catal, 1953, 5: 311
32. [32] Kozuch S, Shaik S. J Phys Chem A, 2008, 112: 6032[32] Kozuch S, Shaik S. J Phys Chem A, 2008, 112: 6032
33. [33] Kozuch S, Martin J M L. ACS Catal, 2011, 1: 246[33] Kozuch S, Martin J M L. ACS Catal, 2011, 1: 246
34. [34] Lavrov V V, Blagojevic V, Koyanagi G K, Orlova G, Bohme D K. J Phys Chem A, 2004, 108: 5610[34] Lavrov V V, Blagojevic V, Koyanagi G K, Orlova G, Bohme D K. J Phys Chem A, 2004, 108: 5610
35. [35] Reed A E, Curtiss L A, Weinhold F. Chem Rev, 1988, 88: 899[35] Reed A E, Curtiss L A, Weinhold F. Chem Rev, 1988, 88: 899
36. [36] Harvey J N, Aschi M, Schwarz H, Koch W. Theor Chem Accts, 1998, 99: 95[36] Harvey J N, Aschi M, Schwarz H, Koch W. Theor Chem Accts, 1998, 99: 95
37. [37] Kang H, Beauchamp J L. J Am Chem Soc, 1986, 108: 5663[37] Kang H, Beauchamp J L. J Am Chem Soc, 1986, 108: 5663
38. [38] Wan Y L, Zhang C H, Guo Y L, Guo Y, Lu G Z. Chin J Catal (万义玲, 张传辉, 郭杨龙, 郭耘, 卢冠忠. 催化学报), 2012, 33: 557[38] Wan Y L, Zhang C H, Guo Y L, Guo Y, Lu G Z. Chin J Catal (万义玲, 张传辉, 郭杨龙, 郭耘, 卢冠忠. 催化学报), 2012, 33: 557

扫一扫看文章

计量

PDF下载量: 531
文章访问数: 881
HTML全文浏览量: 43

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

气相中Co⁺催化N₂O与C₂H₆循环反应催化剂活性的理论研究

通讯作者: 王永成

English

Theoretical investigation into the Co⁺ catalytic activity in the cycle reaction of N₂O with C₂H₆ in the gas phase

Corresponding author: 王永成

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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处