Theoretical Studies on Suppression of Carbon Deposition over Titania Supported Monometallic Nickel(Platinum) Catalysts in Methane Dissociation†

doi:10.7503/cjcu20140478

Abstract

Abstract:

The adsorption behavior of carbon atom adsorbed by one atom of Ni or Pt supported on the anatase TiO₂(101) surface was studied which could provide a thermodynamics clue for elucidating the carbon deposition. The calculated results by PBE based on generalized gradient approximation indicated that the adsorption energy of the most stable configuration for Ni and Pt adsorbed on the TiO₂ surface were 347.16 and 315.9 kJ/mol, respectively, corresponding to the bridge site between the two O_2c atoms. After adsorbing metal atom, the density of state for TiO₂ moved to the lower energy, leading to a more stable system. The density of state was confirmed that there was a significant overlap between p-orbital of carbon atom and d-levels of the metal atom, indicating the effective bonding of carbon and metal atoms, which could attenuate the interaction between these two atoms. When carbon was adsorbed on the Ni/TiO₂(101) or Pt/TiO₂(101) surface, the adsorption energies for the preferable structure were 474.19 or 570.08 kJ/mol. Our work demonstrates the Pt supported on TiO₂ support possessed the better ability for inhibiting the carbon deposition.

Key words: TiO2, Carbon deposition, Density of state, Nickel, Platinum, Methane dissociation

CLC Number:

O641

TrendMD:

WANG Xiujun, QI Qiuhong, CHEN Li. Theoretical Studies on Suppression of Carbon Deposition over Titania Supported Monometallic Nickel(Platinum) Catalysts in Methane Dissociation^†[J]. Chem. J. Chinese Universities, 2014, 35(10): 2138.

Figures/Tables 11

Fig.1 Density of states for the Pt(A) or Ni(B) atom adsorbed on TiO2(101) surfaceα-Spin: spin-up; β-spin: spin-down.

Fig.2 Side view(A) and top view(B) of the optimized structural models of the TiO2(101) clean surface

Fig.3 Side views(A1—F1) and top views(A2—F2) of the optimized configurations Ni and Pt adsorbed on the TiO2(101) surface

Table 1 Optimazated chemisorptions energies and structural parameters of Ni(Pt) atom adsorbed on anatase TiO2(101) surface

Adsorption system	E_ads/(kJ·mol^-1)	$R Ni (Pt) — O 2 c a$ /nm	$R Ni (Pt) — O 3 c$ /nm	$R Ni (Pt) — T i 5 c a$ /nm	$R Ni (Pt) — T i 6 c a$ /nm
Ni-B1	347.16	0.1904	0.2056	0.2774	0.2658
Pt-B1	315.90	0.2059(0.204)^b		0.2778(0.278)^b	0.2826(0.279)^b
Ni-B3	311.61	0.1844	0.1862		0.2315
Pt-B4	309.60	0.2015			0.2353
Ni-B2	244.22	0.1765		0.2419
Pt-B2	235.35	0.1972		0.2498

Table 1 Optimazated chemisorptions energies and structural parameters of Ni(Pt) atom adsorbed on anatase TiO2(101) surface

Adsorption system	E_ads/(kJ·mol^-1)	$R Ni (Pt) — O 2 c a$ /nm	$R Ni (Pt) — O 3 c$ /nm	$R Ni (Pt) — T i 5 c a$ /nm	$R Ni (Pt) — T i 6 c a$ /nm
Ni-B1	347.16	0.1904	0.2056	0.2774	0.2658
Pt-B1	315.90	0.2059(0.204)^b		0.2778(0.278)^b	0.2826(0.279)^b
Ni-B3	311.61	0.1844	0.1862		0.2315
Pt-B4	309.60	0.2015			0.2353
Ni-B2	244.22	0.1765		0.2419
Pt-B2	235.35	0.1972		0.2498

Table 2 Mulliken charge population of Ni(Pt) atom adsorbed on TiO2(101) surface

Adsorption site	q_Ni(Pt)/e	/e	/e	/e	/e
Ni-B1	0.49	-0.66	-0.70	1.30	1.25
Ni-B2	0.43	-0.65		1.06
Ni-B3	0.46	-0.66	-0.72		1.11
Pt-B1	0.18	-0.64		1.30	1.24
Pt-B2	0.18	-0.62		1.17
Pt-B4	0.21	-0.57			1.09

Fig.4 Density of states for the TiO2(101) surface and the most stable structural of Pt/TiO2(101) surface(A) and Ni/TiO2(101) surface(B) The vertical dot lines at the energy zero represent the Fermi level.

Fig.5 Partial density of states for the most stable structural of Pt/TiO2(101)(A) and Ni/TiO2(101)(B)

Fig.6 Charge difference density contour maps of the most stable structural of Ni(Pt) adsorbed on TiO2(101) surface (A) Ni-B1; (B) Pt-B1.

Fig.7 Side views(A1—C1) and top views(A2—C2)of the optimized configuration about the carbon atoms on Ni(Pt)/TiO2(101) surface Black balls indicate C atoms.

Table 3 Adsorption energies(Eads), geometric parameters of different configurations about carbon atom adsorbed on Ni(Pt)/TiO2(101) surface(R) and the mulliken population for C atom adsorbed on Ni(Pt)/TiO2(101) surface(q)

Adsorption site	E_ads/(kJ·mol^-1)	R_C—Ni(Pt)/nm	$R Ni (Pt) — O 2 c$ /nm	$R Ni (Pt) — O 3 c$ /nm	q_C/e	q_Ni(Pt)/e	$q O 2 c$ /e	$q O 3 c$ /e
C1—Ni	474.19	0.1623	0.1986^*	0.2236	-0.16	0.60	-0.69	-0.72
C2—Ni	462.63	0.1621	0.1939^*		-0.15	0.56	-0.71
C3—Pt	570.08	0.1754	0.2201		-0.10	0.10	-0.71

Adsorption site	E_ads/(kJ·mol^-1)	R_C—Ni(Pt)/nm	$R Ni (Pt) — O 2 c$ /nm	$R Ni (Pt) — O 3 c$ /nm	q_C/e	q_Ni(Pt)/e	$q O 2 c$ /e	$q O 3 c$ /e
C1—Ni	474.19	0.1623	0.1986^*	0.2236	-0.16	0.60	-0.69	-0.72
C2—Ni	462.63	0.1621	0.1939^*		-0.15	0.56	-0.71
C3—Pt	570.08	0.1754	0.2201		-0.10	0.10	-0.71

Fig.8 Partial density of the states for the most stable structural of C adsorbed on Ni(Pt)/TiO2(101) surface (A) Free C; (B) C on the Pt/TiO2(101) surface; (C) C adsorbed on the Ni/TiO2(101) surface.

References 50

[1]	Luntz A. C., Bethune D. S., J. Chem. Phys., 1989, 90(2), 1274—1280
[2]	San Jose-Alonso D., Illan-Gomez M. J., Roman-Martinez M. C., Int. J. Hydrog. Energy,2013, 38(5), 2230—2239
[3]	Lv X. Y., Chen J. F., Tan Y. S., Zhang Y., Catal. Commun., 2012, 20(5), 6—11
[4]	Solymosi F., Erdohelyi A., Cserenyi J., Felvegi A., J. Catal., 1994, 147(1), 272—278
[5]	Mateos-Pedrero C., Gonzalez-Carrazan S. R., Soria M. A., Ruiz P., Catal. Today,2013, 203(30), 158—162
[6]	Zhang Z. L., Verykios X. E., App. Catal. A,1996, 138(1), 109—133
[7]	Nagaoka K., Seshan K., Aika K., Lercher J. A., J. Catal., 2001, 197(1), 34—42
[8]	Bitter J., Seshan K., Lercher J., J. Catal., 1998, 176(1), 93—101
[9]	Li G. S., Li L. P., Boerio-Goates J., Woodfield B. F., J. Am. Chem. Soc., 2005, 127(24), 8659—8666
[10]	Lazzeri M., Vittadini A., Selloni A., Phys. Rev. B,2002, 65(11), 119901
[11]	Herman G. S., Dohnalek Z., Ruzycki N., Diebold U., J. Phys. Chem. B,2003, 107(12), 2788—2795
[12]	Hengerer R., Bolliger B., Erbudak M., Gratzel M., Surf. Sci., 2000, 460(1/3), 162—169
[13]	Lazzeri M., VittadiniA., Selloni A., Phys. Rev. B,2001, 63(15), 155409—155418
[14]	Wang F. C., Wan H. L., Tsai K. R., Wang S. J., Xu F. C., Catal. Lett., 1992, 12(1/3), 319—325
[15]	Stakheev A. Y., Gololobov A. M., Beck I. E., Bragina G. O., Zaikovsky V. I., Ayupov A. B., Telegina N. S., Bukhtiyarov V. I., Russ. Chem. Bull., 2010, 59(9), 1713—1719
[16]	Zou J. J., He H., Cui L., Du H. Y., Int. J. Hydrog. Energy,2007, 32(12), 1762—1770
[17]	Bitter J. H., Seshan K., Lercher J. A., J. Catal., 1999, 183(2), 336—343
[18]	Li C. L., Chen W., Yuan J., Shangguan W. F., Acta Phys. Chim. Sinica,2012, 28(2), 450—456
	(李曹龙, 陈威, 袁坚, 上官文峰. 物理化学学报, 2012, 28(2), 450—456)
[19]	Bradford M. C., Vannice M. A., Appl. Catal. A,1996, 142(1), 73—96
[20]	Bradford M. C., Vannice M. A., Appl. Catal. A,1996, 142(1), 97—122
[21]	Yan Q. G., Weng W.Z., Wan H. L., Toghiani H., Toghiani R. K., Pittman C. U., Appl. Catal. A,2003, 239(1/2), 43—58
[22]	Takanabe K., Nagaoka K., Nariai K., Aika K., J. Catal., 2005, 232(2), 268—275
[23]	Wanbayor R., Ruangpornvisuti V., Appl. Surf. Sci., 2012, 258(7), 3298—3301
[24]	Zhou Y., Muhich C. L., Neltner B. T., Weimer A. W., Musgrave C. B., J. Phys. Chem. C,2012, 116(22), 12114—12123
[25]	Celik V., Unal H., Mete E., Ellialtioglu S., Phys. Rev. B,2010, 82(20), 205113—205125
[26]	Zhang R. G., Song L. Z., Wang Y. H., Appl. Surf. Sci., 2012, 258(18), 7154—7160
[27]	He P. L., Mao Y. L., Sun L. Z., Zhong J. X., J. Comput. Theor. Nanosci., 2010, 7(10), 2063—2067
[28]	Escamilla-Roa E., Timon V., Hernandez-Laguna A., Comput. Theor. Chem., 2012, 981(1), 59—67
[29]	Yang Z. X., He B. L., Lu Z. S., Hermansson K. T., J. Phys. Chem. C,2010, 114(10), 4486—4494
[30]	Cheng D. J., Lan J. H., Cao D. P., Wang W. C., Appl. Catal. B,2010, 106(3/4), 510—519
[31]	Delley B., J. Phys. Chem., 1996, 100(15), 6107—6110
[32]	Delley B., J. Chem. Phys., 1990, 92(1), 508—517
[33]	Delley B., Phys. Rev. B, 2002, 66(15), 155125—155134
[34]	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(11), 6671—6687
[35]	Ernzerhof M., Scuseria G. E., J. Chem. Phys., 1999, 110(11), 5029—5036
[36]	Iwaszuk A., Mulheran P. A., Nolan M., J. Mater. Chem. A,2013, 1(7), 2515—2525
[37]	Burdett J. K., Hughbanks T., Miller G. J., Richardson J. W. Jr, Smith J. V., J. Am. Chem. Soc., 1987, 109(12), 3639—3646
[38]	Goldwasser M. R., Rivas M. E., Pietri E., Perez-Zurita M. J., Cubeiro M. L., Gingembre L., Leclercq L., Leclercq G., Appl. Catal. A,2003, 255(1), 45—57
[39]	Ding K. N., Zhang Y. F., Li Y., Li J. J., J. Fuzhou. Univ. Nat. Sci. Ed., 2005, 33(4), 528—532
	(丁开宁, 章永凡, 李奕, 李俊籛. 福州大学学报自然科学版, 2005, 33(4), 528—532)
[40]	Han Y., Liu C. J., Ge Q. F., J. Phys. Chem. B,2006, 110(14), 7463—7472
[41]	Li S. R., Lu X. Q., Guo W. Y., Zhu H. Y., Li M., Zhao L. M., Li Y., Shan H. H., J. Organomet. Chem., 2012, 704(1), 38—48
[42]	Chen Y. F., Zhang M. H., Jiang H. X., Mol. Catal.(China), 2007, 21(4), 351—355
	(陈毅飞, 张敏华, 姜浩锡. 分子催化, 2007, 21(4), 351—355)
[43]	Zhao Y., Teng B. T., Wen X. D., Zhao Y., Zhao L. H., Luo M. F., Catal. Commun., 2012, 27(5), 63—68
[44]	Zhao Y., Teng B. T., Yang Z. X., Zhao Y., Zhao L. H., Luo M., J. Phys. Chem. C,2011, 115(33), 16461—16466
[45]	Zhang W. D., Liu B. S., Zhu C., Tian Y. L., Appl. Catal. A,2005, 292(18), 138—143
[46]	Fan C., Zhu Y. A., Zhou X. G., Chem. Re. Eng. Technol., 2012, 28(2), 117—121
[47]	Xu Y., Ruban A. V., Mavrikakis M., J. Am. Chem. Soc., 2004, 126(14), 4717—4725
[48]	Greeley J., Norskov J. K., Surf. Sci., 2005, 592(1/3), 104—111
[49]	Tomishige K., Kanazawa S., Suzuki K., Asadullah M., Sato M., Ikushima K., Kunimori K., Appl. Catal. A,2002, 233(1/2), 35—44
[50]	Wang S. B., Lu G. Q., Millar G. J., Energ. Fuel,1996, 10(4), 896—904