N2O 在 Cu/t-ZrO2(101) 表面的吸附与解离

doi:10.3724/SP.J.1088.2012.20458

摘要/Abstract

摘要： 运用广义梯度密度泛函理论结合周期性平板模型方法研究了 N₂O 在完整及负载 Cu 的四方相 ZrO₂(101) 表面的吸附与解离. 结果表明, N₂O 在完整 ZrO₂(101) 表面的吸附均为物理吸附, Cu 在其完整表面的次表层第一氧位为最稳定吸附位, 且覆盖度为 0.25 ML 时的吸附最为稳定, 吸附能为 155.8 kJ/mol; N₂O 分子中 O 端弱物理吸附于 Cu/ZrO₂(101) 表面, 其 N 端及平行吸附方式得到的稳定吸附能分别为 121.6 和 66.8 kJ/mol. 频率及电荷布居计算表明, 吸附后对称和反对称伸缩振动频率均发生红移, 电子由 Cu 负载底物表面转移给 N₂O 分子. 对 N₂O 分子的解离考虑了 N 端垂直吸附和平行吸附两种解离反应过程, 发现平行吸附过程的解离更易发生.

关键词: 密度泛函理论, 一氧化二氮, 四方相二氧化锆, 铜, 吸附, 解离

Abstract: The density functional theory and slab models have been applied to investigate the adsorption and dissociation of N₂O on perfect t-ZrO₂(101) and Cu/t-ZrO₂(101) surfaces. The results indicated that N₂O adsorption on the ZrO₂(101) surface is physical adsorption. The first of sub-surface oxygen site is the most stable adsorption site for the Cu/ZrO₂(101) surface, and when the coverage is 0.25 ML, the most stable models were obtained with adsorption energy of 155.8 kJ/mol. The adsorption of N₂O on the Cu/t-ZrO₂(101) surface by O-end is weak physical adsorption, and the N-end and parallel adsorption energy is 121.6 and 66.8 kJ/mol, respectively. Vibrational frequency and the Mulliken population were calculated, and the results indicated that the symmetric and antisymmetric vibrational frequencies are red-shifted and the charge transfers from Cu/t-ZrO₂(101) to N₂O after adsorption. The N-end and parallel dissociation process were considered and the parallel dissociation process is more feasible.

Key words: density functional theory, nitrous oxide tetragonal, zirconia, copper, adsorption, dissociation

满梅玲, 辜家芳, 李璐, 林华香, 李奕, 陈文凯. N₂O 在 Cu/t-ZrO₂(101) 表面的吸附与解离[J]. 催化学报, 2012, 33(11): 1850-1856.

MAN Mei-Ling, GU Jia-Fang, LI Lu, LIN Hua-Xiang, LI Yi, CHEN Wen-Kai. Adsorption and Decomposition of N₂O on Cu/t-ZrO₂(101) Surfaces[J]. Chinese Journal of Catalysis, 2012, 33(11): 1850-1856.

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参考文献

1 Thiemens M H, Trogler W C. Science, 1991, 251: 932
2 Kapteijn F, Rodriguez-Mirasol J, Moulijn J A. Appl Catal B, 1996, 9: 25
3 Dickinson R E, Cicerone R J. Nature, 1986, 319: 109
4 Arai N. J Inst Energy, 1994, 67: 61
5 Satsuma A, Maeshima H, Watanabe K, Hattori T. Energy Convers Manage, 2001, 42: 1997
6 Perez-Ramirez J. Appl Catal B, 2007, 70: 31
7 Russo N, Mescia D, Fino D, Saracco G, Specchia V. Ind Eng Chem Res, 2007, 46: 4226
8 Martinez A, Goursot A, Coq B, Delahay G. J Phys Chem B, 2004, 108: 8823
9 Shimizu A, Tanaka K, Fujimori M. Chemosphere-Global Change Science, 2000, 2: 425
10 Centi G, Generali P, dall'Olio L, Perathoner S, Rak Z. Ind Eng Chem Res, 2000, 39: 131
11 Wójtowicz M A, Miknis F P, Grimes R W, Smith W W, Se-rio M A. J Hazard Mater, 2000, 74: 81
12 Shen Q, Li L D, Li J J, Tian H, Hao Z P. J Hazard Mater, 2009, 163: 1332
13 Asano K, Ohnishi C, Iwamoto S, Shioya Y, Inoue M. Appl Catal B, 2008, 78: 242
14 Ito T, Wang J X, Lin C H, Lunsford J H. J Am Chem Soc, 1985, 107: 5062
15 Russo N, Mescia D, Fino D, Saracco G, Specchia V. Ind Eng Chem Res, 2007, 46: 4226
16 Nakamura M, Mitsuhashi H, Takezawa N. J Catal, 1992, 138: 686
17 Nakamura M, Fujita S, Takezawa N. Catal Lett, 1992, 14: 315
18 Yamamoto H, Chu H Y, Xu M T, Shi C L, Lunsford J H. J Catal, 1993, 142: 325
19 Hutchings G J, Scurrell M S, Woodhouse J R. Chem Soc Rev, 1989, 18: 251
20 Heyden A, Peters B, Bell A T, Keil F J. J Phys Chem B, 2005, 109: 1857
21 Nakamura M, Yanagibashi H, Mitsuhashi H, Takezawa N. Bull Chem Soc Jpn, 1993, 66: 2467
22 Li Y J, Armor J N. Appl Catal B, 1992, 1: L21
23 Ma Z Y, Yang C, Wei W, Li W H, Sun Y H. J Mol Catal A, 2005, 227: 119
24 Centi G, Cerrato G, D'Angelo S, Finardi U, Giamello E, Morterra C, Perathoner S. Catal Today, 1996, 27: 265
25 Sun Y H, Sermon P A. J Chem Soc, Chem Commun, 1993: 1242
26 Bianchi D, Chafik T, Khalfallah M, Teichner S J. J Appl Catal A, 1994, 112: 219
27 Ma Z Y, Xu R, Yang C, Dong Q N, Wei W, Sun Y H. Stud Surf Sci Catal, 2004, 147: 625
28 Saito M, Murata K. Catal Surv Asia, 2004, 8: 285
29 Ko J B, Bae C M, Jung Y S, Kim D H. Catal Lett, 2005, 105: 157
30 Ma Z Y, Yang C, Wei W, Li W H, Sun Y H. J Mol Catal A, 2005, 231: 75
31 Fellah M F, Pidko E A, van Santen R A, Onal I. J Phys Chem C, 2011, 115: 9668
32 Orita H, Kubo T, Matsushima T, Kokalj A. J Phys Chem C, 2010, 114: 21444
33 Stelmachowski P, Zasada F, Piskorz W, Kotarba A, Paul J-F, Sojka Z. Catal Today, 2008, 137: 423
34 Zhang B, Lu Y A, He H, Wang J G, Zhang C B, Yu Y B, Xue L. J Environ Sci, 2011, 23: 681
35 Manzhos S, Yamashita K. Surf Sci, 2010, 604: 555
36 Lü Y A, Zhuang G L, Wang J G, Jia Y B, Xie Q. Phys Chem Chem Phys, 2011, 13: 12472
37 Hofmann A, Clark S J, Oppel M, Hahndorfk I. Phys Chem Chem Phys, 2002, 4: 3500
38 曾庆松, 陈文凯, 戴文新, 章永凡, 李奕, 郭欣. 催化学报 (Zeng Q S, Chen W K, Dai W X, Zhang Y F, Li Y, Guo X. Chin J Catal), 2010, 31: 423
39 杜玉栋, 郭欣, 陈文凯, 李奕, 章永凡. 催化学报 (Du Y D, Guo X, Chen W K, Li Y, Zhang Y F. Chin J Catal), 2011, 32: 1046
40 Du Y D, Chen W K, Zhang Y F, Guo X. J Nat Gas Chem, 2011, 20: 60
41 Delly B. J Chem Phys, 1990, 92: 508
42 Delly B. J Chem Phys, 2000, 113: 7756
43 Delly B. J Phys Chem, 1996, 100: 6107
44 Perdew J P, Wang Y. Phys Rev B, 1992, 45: 13244
45 Lide D R. CRC Handbook of Chemistry and Physics. 81st Ed. Boca Raton: CRC Press, 2003. 9
46 Fellah M F, van Santen R A, Onal I. J Phys Chem C, 2009, 113: 15307
47 Walter E J, Lewis S P, Rappe A M. Surf Sci, 2001, 495: 44
48 Tang Q L, Liu Z P. J Phys Chem C, 2010, 114: 8423
49 Yang Y L, Chen W K, Guo X, Li Y, Zhang Y F. Chin J Struct Chem, 2010, 29: 1021
50 Wu S Y, Su C H, Chang J G, Chen H T, Hou C H, Chen H L. Comput Mater Sci, 2011, 50: 3311
51 Sun B Z, Chen W K, Wang X, Lu C H. Appl Surf Sci, 2007, 253: 7501
52 Herzberg G. Infrared and Raman Spectra and Molecular Structure. Vol. 2. New York: D. Van Nostrand Company, Inc, 1945
53 Plíva J. J Mol Spectrosc, 1964, 12: 360
54 Ohno Y, Kimura K, Bi M, Matsushima T. J Chem Phys, 1999, 110: 8221

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N₂O 在 Cu/t-ZrO₂(101) 表面的吸附与解离

Adsorption and Decomposition of N₂O on Cu/t-ZrO₂(101) Surfaces

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