Ni掺杂对Ni/MgO体系中电荷分配影响

引用本文: 郭云鹏, 冯杰, 李文英. Ni掺杂对Ni/MgO体系中电荷分配影响[J]. 物理化学学报, 2017, 33(9): 1796-1802. doi: 10.3866/PKU.WHXB201705081 shu

Citation: GUO Yun-Peng, FENG Jie, LI Wen-Ying. Effect of Ni Doping on Electron Transfer in Ni/MgO Catalysts[J]. Acta Physico-Chimica Sinica, 2017, 33(9): 1796-1802. doi: 10.3866/PKU.WHXB201705081 shu

Ni掺杂对Ni/MgO体系中电荷分配影响

太原理工大学;山西省煤科学与技术省部共建国家重点实验培育基地, 太原 030024
基金项目:
国家自然科学基金重点支持项目（U1361202）和国家重点研发计划重点专项（2016YFB0600305）资助

摘要: 采用密度泛函理论（DFT）计算方法，研究了载体Ni掺杂对Ni/MgO催化剂的电子结构及其对CH₄/CO₂重整反应的影响。结果显示，随着载体Ni ： Mg比的增加，CH₄解离吸附和CH_x氧化过程的反应能垒均会随之升高，CH也更容易产生热解C，从而导致催化剂的活性和稳定性的下降。通过分析重整过程的Hirshfeld电荷分配，发现金属载体之间电子转移的方向会随着载体中Ni含量的上升由载体向Ni金属转移变为由Ni金属向载体转移。当Ni金属富电子时，反应物活化时电子的转移主要发生在表层Ni原子与吸附物种之间，参与氧化的CH_x物种为CH₂；当Ni金属缺电子时，反应物活化时Ni簇的电子结构基本保持稳定，电子主要在载体表层的Ni原子与反应物之间转移，CH是主要参与氧化的CH_x物种。

关键词:

CH₄/CO₂重整
/ Ni/MgO
/ Ni掺杂
/ 电荷分配
/ DFT

English

Effect of Ni Doping on Electron Transfer in Ni/MgO Catalysts

Training Base of State Key Laboratory of Coal Science and Technology Jointly Constructed by Shanxi Province and Ministry of Science and Technology; Taiyuan University of Technology, Taiyuan 030024, P. R. China
Received Date: 03 April 2017
Revised Date: 20 April 2017
Available Online: 08 May 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (U1361202) and the National Key Research and DevelopmentProgram of China.

Abstract: First-principles calculations based on density functional theory (DFT) have been used to investigate how Ni doping in the supporter impacts CH₄/CO₂ reforming over Ni/MgO catalysts. Ni8 clusters supported on different Ni_xMg_yO₂₇(100) slabs (x+y= 27) have been selected to model Ni/MgO catalysts with different Ni : Mg ratio. The CH₄/CO₂ reforming mechanisms on different Ni8/Ni_xMg_yO₂₇(100) slabs indicate that the energy barriers of CH₄ dissociated adsorption and CH_x oxidation both increase with an increase in the Ni : Mg ratio of the supporter. CH would be easily generated from the pyrolytic carbon. The electron structure analysis shows that the direction of electron transfer changes to “between metal and supporter” with increasing Ni : Mg ratio of the supporter, but not to “from supporter to metal” on pure Ni/MgO. When the Ni cluster is negative, electron transfer occurs between adsorbed species and Ni atoms in the surface layer of the Ni cluster, and CH₂ is the main species for CH_x oxidation. When the Ni cluster is positive, its Hirshfeld is stable, electron transfer occurs between adsorbed species and Ni atoms in the surface layer of the NiO-MgO solid solution, and CH is the main oxidative species. The electron deficiency of the Ni cluster is the reason for the poor catalytic performance of Ni/MgO with a high Ni doping ratio.

Key words:

1. [1]
  (1) Ashcroft, A. T.; Cheetham, A. K.; Green, M. L. H.; Vernon, P. D. F.Nautre 1991, 352, 225. doi: 10.1038/352225a0
2. [2]
  (2) Chen, J. X.; Wang, R. J.; Zhang, J. Y.; He, F.; Han, S. J. Mol. Catal. A:Chem. 2005, 235, 302. doi: 10.1016/j.molcata.2005.04.023
3. [3]
  (3) Inui, T.; Spivey, J. J., Reforming of CH4 by CO₂, O₂, and/or H₂O. InCatalysis, Spivey, J. J. Ed.; The Royal Society of Chemistry:Cambridge, 2002; pp 133-154.
4. [4]
  (4) Kim, G. J.; Cho, D. S.; Kim, K. H.; Kim, J. H. Catal. Lett. 1994, 28,41. doi: 10.1007/BF00812468
5. [5]
  (5) Hu, Y. H.; Ruckenstein, E. Catal. Lett. 1997, 43, 71.doi: 10.1023/A:1018982304573
6. [6]
  (6) Song, C.; Pan, W. Catal. Today 2004, 98, 463.doi: 10.1016/j.cattod.2004.09.054
7. [7]
  (7) Tomishige, K.; Himeno, Y.; Matsuo, Y.; Yoshinaga, Y.; Fujimoto,K. Ind. Eng. Chem. Res. 2000, 39, 1891. doi: 10.1021/ie990884z
8. [8]
  (8) Özdemir, H.; Faruk Öksüzömer, M. A.; Ali Gürkaynak, M. Int. J. Hydrog. Energy 2010, 35, 12147.doi: 10.1016/j.ijhydene.2010.08.091
9. [9]
  (9) Ruckenstein, E.; Hu, Y. H. J. Catal. 1996, 162, 230.doi: 10.1006/jcat.1996.0280
10. [10]
  (10) Wang, S. B.; Lu, G. Q. M. J. Chem. Technol. Biotechnol. 2000, 75, 589. doi: 10.1002/1097-4660(200007)75:7<589::AID-JCTB241>3.0.CO;2-7
11. [11]
  (11) Guo, F.; Chu, W.; Huang, L. Q.; Xie, Z. K. Chin. J. Systhe. Chem. 2008, 16, 495. [郭芳, 储伟, 黄丽琼, 谢在库. 合成化学,2008, 16, 495.]doi: 10.3969/j.issn.1005-1511.2008.05.001
12. [12]
  (12) Hu, Y. H.; Ruckenstein, E. Catal. Lett. 1996, 36, 145.doi: 10.1007/bf00807611
13. [13]
  (13) Hu, Y. H.; Ruckenstein, E. J. Catal. 1999, 184, 298.doi: 10.1006/jcat.1999.2449
14. [14]
  (14) Hu, Y. H.; Ruckenstein, E. Catal. Rev. 2002, 44, 423.doi: 10.1081/CR-120005742
15. [15]
  (15) Guo, J. J.; Lou, H.; Zhao, H.; Chai, D. F.; Zheng, X. M. Appl. Catal. A 2004, 273, 75. doi: 10.1016/j.apcata.2004.06.014
16. [16]
  (16) García, V.; Fernández, J. J.; Ruíz, W.; Mondragón, F.; Moreno, A. Catal. Commun. 2009, 11, 240.doi: 10.1016/j.catcom.2009.10.003
17. [17]
  (17) Naeem, M. A.; Al-Fatesh, A. S.; Abasaeed, A. E.; Fakeeha,A. H. Fuel Process. Technol. 2014, 122, 141.doi: 10.1016/j.fuproc.2014.01.035
18. [18]
  (18) Wang, S. B.; Lu, G. Q. M. Appl. Catal. B 1998, 16, 269.doi: 10.1016/S0926-3373(97)00083-0
19. [19]
  (19) Wei, H. S.; Liu, X. Y.; Wang, A. Q.; Zhang, L. L.; Qiao, B.T.; Yang, X. F.; Huang, Y. Q.; Miao, S.; Liu, J. Y.; Zhang, T.Nat. Commun. 2014, 5, 1. doi: 10.1038/ncomms6634
20. [20]
  (20) Yang, X. F.; Wang, A. Q.; Qiao, B. T.; Li, J.; Liu, J. Y.; Zhang, T. Acc. Chem. Res. 2013, 46, 1740.doi: 10.1021/ar300361m
21. [21]
  (21) Valden, M.; Lai, X.; Goodman, D. W. Science 1998, 281,1647. doi: 10.1126/science.281.5383.1647
22. [22]
  (22) Cargnello, M.; Doan-Nguyen, V. V. T.; Gordon, T. R.; Diaz,R. E.; Stach, E. A.; Gorte, R. J.; Fornasiero, P.; Murray, C. B.Science 2013, 341, 771. doi: 10.1126/science.1240148
23. [23]
  (23) Shi, K. Y.; Xu, H. Y.; Zhang, G. L.; Wang, Y. Z.; Lin, X. G.; Wei, Y. D. Chin. J. Catal. 2002, 23, 15. [史克英, 徐恒泳, 张桂玲, 王玉忠, 徐国林, 韦永德. 催化学报,2002, 23, 15.]doi: 10.3321/j.issn:0253-9837.2002.01.004
24. [24]
  (24) Guo, Y. P.; Feng, J.; Li, W. Y. Chin. J. Chem. Eng. 2017,doi: 10.1016/j.cjche.2017.03.024
25. [25]
  (25) Milman, V.; Winkler, B.; White, J. A.; Pickard, C. J.; Payne,M. C.; Akhmatskaya, E. V.; Nobes, R. H. Int. J. Quantum Chem. 2000, 77, 895. doi: 10.1002/(SICI)1097-461X(2000)77:5<895::AID-QUA10>3.0.CO;2-C
26. [26]
  (26) Payne, M. C.; Teter, M. P.; Allan, D. C.; Arias, T. A.; Joannopoulos, J. D. Rev. Mod. Phys. 1992, 64, 1045.doi: 10.1103/RevModPhys.64.1045
27. [27]
  (27) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B 1992, 46, 6671. doi: 10.1103/PhysRevB.46.6671
28. [28]
  (28) Perdew, J. P.; Zunger, A. Phys. Rev. B 1981, 23, 5048.doi: 10.1103/PhysRevB.23.5048
29. [29]
  (29) Vanderbilt, D. Phys. Rev. B 1990, 41, 7892.doi: doi.org/10.1103/PhysRevB.41.7892
30. [30]
  (30) Kresse, G.; Furthmüller, J. Comput. Mater. Sci. 1996, 6, 15.doi: 10.1016/0927-0256(96)00008-0
31. [31]
  (31) Kresse, G.; Furthmüller, J. Phys. Rev. B 1996, 54, 11169.doi: 10.1103/PhysRevB.54.11169
32. [32]
  (32) Kresse, G.; Hafner, J. Phys. Rev. B 1993, 47, 558.doi: 10.1103/PhysRevB.47.558
33. [33]
  (33) Kresse, G.; Hafner, J. Phys. Rev. B 1994, 49, 14251.doi: 10.1103/PhysRevB.49.14251
34. [34]
  (34) Monkhorst, H. J.; Pack, J. D. Phys. Rev. B 1976, 13, 5188.doi: 10.1103/PhysRevB.13.5188
35. [35]
  (35) Speziale, S.; Zha, C. S.; Duffy, T. S.; Hemley, R. J.; Mao, H.K. J. Geophys. Res. 2001, 106, 515. doi: 10.1029/2000JB900318
36. [36]
  (36) Halgrena, T. A.; Lipscomb, W. N. Chem. Phys. Lett. 1977, 49,225. doi: 10.1016/0009-2614(77)80574-5
37. [37]
  (37) Guo, Y. P.; Li, W. Y.; Feng, Surf. Sci. 2017, 660, 22.doi: 10.1016/j.susc.2017.02.010
38. [38]
  (38) Sao-Joao, S.; Giorgio, S.; Mottet, C.; Goniakowski, J.; Henry,C. R. Surf. Sci. 2006, 600, L86.doi: 10.1016/j.susc.2006.01.045
39. [39]
  (39) Zhou, J. L.; Xin, M.; Chen, Y. J. Mol. Catal (Chin.) 1993, 7 (6), 411. [周建略, 辛梅, 陈豫. 分子催化,1993, 7(6), 411.]
40. [40]
  (40) Bradford, M. C. J.; Vannice, M. A. Appl. Catal. A 1996, 142,97. doi: 10.1016/0926-860X(96)00066-X
41. [41]
  (41) Wei, J. M.; Iglesia, E. J. Catal. 2004, 224, 370.doi: 10.1016/j.jcat.2004.02.032

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沈阳化工大学材料科学与工程学院沈阳 110142

Ni掺杂对Ni/MgO体系中电荷分配影响

English

Effect of Ni Doping on Electron Transfer in Ni/MgO Catalysts

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通讯作者: 陈斌, bchen63@163.com

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Ni掺杂对Ni/MgO体系中电荷分配影响

English

Effect of Ni Doping on Electron Transfer in Ni/MgO Catalysts

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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