Comparative Study on the Properties and Adsorption of Furfural of Pd(111) Surface Before and After Ru Modification†

doi:10.7503/cjcu20170189

Abstract

Abstract:

The properties of Pd(111), Ru-Pd(111) surfaces and their adsorption of furfural were investigated via periodic density functional theory(DFT) calculations. The results of atomic size factor, relative bond length, formation energy and d-band center showed that Ru-Pd(111) surface was more stable and active than Pd(111), Ru modification could improve the geometric configuration. For the adsorption of furfural on Pd(111) and Ru-Pd(111) surfaces, the results showed that when the initial adsorption at P(top-bridge) or P(Pd-fcc-Ru-fcc) site, the adsorption energy was the highest and the adsorption configuration was the most stable. After analyzing Mulliken atomic charge population and the deformation density, it was found that for the adsorption of furfural on Ru-Pd(111) surface, the number of charge transferred was more and the interaction was stronger, therefore it’s adsorption energy was higher. The result of state density indicated that the main reason for the adsorption was that the p and d orbitals hybridization existed at -7.34 eV relative to Fermi level. Meanwhile, the p-orbital of furfural shifted to the low-level was more obvious on Ru-Pd(111) surface, so Pd catalyst after Ru modification had better catalytic activity.

Key words: Density functional theory, Furfural, Pd(111) surface, Ru-Pd(111) surface, Adsorption

TrendMD:

QIAN Mengdan, LUO Wei, NI Zheming, XIA Shengjie, XUE Jilong, JIANG Junhui. Comparative Study on the Properties and Adsorption of Furfural of Pd(111) Surface Before and After Ru Modification^†[J]. Chem. J. Chinese Universities, 2017, 38(9): 1611.

Figures/Tables 10

Fig.1 Structure of Ru-Pd(111)[N=4(A), 3(B)] plane surfaces model

Fig.3 Structure of furfural

Fig.4 Structure of Pd(111)(A) and Ru-Pd(111)(B) plane surface model

Fig.5 Top(A) and side(B) views of furfural molecule after adsorption on Pd(111) surface

Fig.6 Top(A) and side(B) views of furfural molecule after adsorption on Ru-Pd(111) surface

Table 1 Adsorption energy(Eads) of furfural molecule on Pd(111) and Ru-Pd(111) surfaces

Adsorption site (Pd-O3-Pd-O7)	E_ads/(kJ·mol^-1)		Adsorption site (Pd-O3-Pd-O7)	E_ads/(kJ·mol^-1)
Adsorption site (Pd-O3-Pd-O7)	Pd(111)		Ru-Pd(111)	Pd(111)	Ru-Pd(111)
Top-top	-77.86	-88.23	Fcc-top	-77.48	-110.58
Top-hcp	-77.58	-88.07	Fcc-hcp	-76.30	-86.63
Top-fcc	-77.59	-85.25	Fcc-fcc	-72.50	-85.62
Top-bridge	-79.44	-89.02	Fcc-bridge	-75.70	-86.25
Hcp-top	-75.14	-140.01	Bridge-top	-71.20	-138.32
Hcp-hcp	-75.24	-118.98	Bridge-hcp	-75.39	-118.78
Hcp-fcc	-76.61	-87.35	Bridge-fcc	-77.34	-81.26
Hcp-bridge	-75.20	-138.32	Bridge-bridge	-75.84	-134.08

Table 2 Structure parameters of the most stable adsorption configuration of furfural on Pd(111) and Ru-Pd(111) surfaces*

Model	d₁/nm	d₂/nm	d₃/nm	d₄/nm	d₅/nm	d₆/nm	d₇/nm	d₈/nm
Free-furfural	0.1399	0.1382	0.1402	0.1414	0.1420	0.1423	0.1274	0.1112
P(top-bridge)/Pd(111)	0.1392	0.1378	0.1400	0.1409	0.1417	0.1427	0.1259	0.1110
P(Pd-fcc-Ru-fcc)/Ru-Pd(111)	0.1400	0.1378	0.1401	0.1413	0.1419	0.1426	0.1271	0.1110
Δd₁(%)	-0.50	-0.29	-0.14	-0.35	-0.21	0.28	-1.18	-0.18
Δd₂(%)	0.07	-0.29	-0.07	-0.07	-0.07	0.21	-0.24	-0.18

Table 3 Mulliken atomic charge populations of furfural molecule at advantage adsorption site on the Pd(111) and Ru-Pd(111) surfaces

Atom	Charge/e
Atom	Free furfural	Furfural/Pd(111)	Furfural/Ru-Pd(111)
C1	-0.059	-0.097	-0.102
C2	0.196	0.153	0.186
O3	-0.371	-0.327	-0.346
C4	0.328	0.272	0.263
C5	-0.103	-0.118	-0.092
C6	0.169	0.134	0.170
O7	-0.351	-0.318	-0.315
H8	0.050	0.099	0.091
H9	0.062	0.100	0.093
H10	0.048	0.096	0.086
H11	0.031	0.064	0.057
Tol	0	0.058	0.091

Fig.7 Deformation density of furfural adsorption on Pd(111)(A) and Ru-Pd(111)(B) surfaces

Fig.8 Densities of states of furfural adsorption on Pd(111) and Ru-Pd(111) surfaces(A) Total DOS of furfural and Pd(111) surface after adsorption; (B) total DOS of furfural and Ru-Pd(111) surface after adsorption; (C) s,p orbitals of furfual molecule on Pd(111) after adsorption; (D) s,p orbitals of furfual molecule on Ru-Pd(111) after adsorption; (E) s,p,d orbitals of Pd(111) surface after adsorption; (F) s,p,d orbitals of Ru-Pd(111) surface after adsorption.

References 37

[1]	Juben N. C., George W. H., James A. D., Angew. Chem., 2007, 119, 7298—7318
[2]	George W. H., Sara I., Avelino C., Chem. Rev., 2006, 106, 4044—4098
[3]	Joseph J. B., Gene R. P., Green Chem., 2010, 12, 539—554
[4]	Amanda-Lynn M., Peter J. A., Chem. Eur. J., 2010, 16, 4970—4980
[5]	Saqib S. T., Lasse R., Andress R., Energy,2011, 36, 2328—2342
[6]	Tao R. R., Song H. L., Chou L. J., J. Mol. Catal. A-Chem., 2012, 357, 11—18
[7]	Pierre G., Chem. Soc. Rev., 2012, 41, 1538—1558
[8]	Saikat D., Sudipta D., Basudeb S., Md I.A., Catal. Sci. Technol., 2012, 2, 2025—2036
[9]	Yu Y. X., Zhang X. H., Wang T. J., Xu Y., Ma L. L., Zhang Q., Zhang L. M., Chem. J. Chinese Universities, 2013, 34(9), 2178—2183
	(于玉肖, 张兴华, 王铁军, 徐莹, 马隆龙, 张琦, 张丽敏.高等学校化学学报,2013, 34(9), 2178—2183)
[10]	Wu J., Gao G., Li J. L., Sun P., Long X. D., Li F. W., Appl. Catal. B Environ., 2017, 203, 227—236
[11]	Milan H., Katarina F., Catal. Commun., 2012, 24, 100—104
[12]	Zhang C., Lai Q. H., Joseph H. H., Catal. Commun., 2017, 89, 77—80
[13]	Rajesh V. S., Umashankar D., Ramaswami S., Ajay K. D., Appl. Catal. A Gen., 2013, 454, 127—136
[14]	Bhogeswararao S., Srinivas D., J. Catal., 2011, 327, 65—77
[15]	Zhao Y. Y., Environ Chem. Lett., 2014, 12, 185—190
[16]	Surapas S. D. E. R., Catal Lett., 2011, 141, 784—791
[17]	Zheng R. Y., Zhu Y. X., Chen J. G., Chem. Cat. Chem., 2011, 3, 578—581
[18]	Zheng R. Y., Humbert M. P., Zhu Y. X., Chen J. G., Catal. Sci. Technol., 2011, 1, 638—643
[19]	Sitthisa S., Pham T., Prasomsri T., Sooknoi T., Mallinson R. G., Resasco D. E., J. Catal., 2011, 280, 17—27
[20]	Sitthisa S., An W., Resasco D. E., J. Catal., 2011, 284, 90—101
[21]	Qiu J. S., Zhang H. Z., Wang X. N., Han H. M., Liang C. H., Li C., React. Kinet. Catal. Lett., 2006, 88, 269—275
[22]	Obaid F. A., Sarwat L., Peter J. M., Germma L. B., Daniel R. J., Xi L., Jenniffr K. E., David J. M., David K. K., Graham J. H., Catal. Sci. Technol., 2016, 6, 234—242
[23]	Sun X. L., Huo R. P., Bu Y. X., Li J. L., Chem. J. Chinese Universities, 2015, 36(8), 1570—1575
	(孙小丽, 霍瑞萍, 步宇翔, 李吉来.高等学校化学学报,2015, 36(8), 1570—1575)
[24]	Liu J. H., Lu C. Q., Jin. C., Guo Y., Wang G. C., Chem. Res. Chinese Universities, 2016, 32(2), 234—241
[25]	Yu Y. X., Phys. Chem. Chem. Phys., 2013, 15, 16819—16827
[26]	Gholizadeh R., Yu Y. X., Appl. Surf. Sci., 2015, 357, 1187—1195
[27]	Chen R. F., Xia W. S., Wan H. L., Chem. J. Chinese Universities, 2015, 36(9), 1743—1751
	(陈蓉芳, 夏文生, 万惠霖.高等学校化学学报,2015, 36(9), 1743—1751)
[28]	Jiang J. H., Xia S. J., Ni Z. M., Zhang L. Y., Chem. J. Chinese Universities, 2016, 37(4), 693—700
	(蒋军辉, 夏盛杰, 倪哲明, 张连阳.高等学校化学学报,2016, 37(5), 693—700)
[29]	Cao Y. Y., Jiang J. H., Ni Z. M., Xia S. J., Qian M. D., Xue J. L., Chem. J. Chinese Universities, 2016, 37(7), 1342—1350
	(曹勇勇, 蒋军辉, 倪哲明, 夏盛杰, 钱梦丹, 薛继龙.高等学校化学学报,2016, 37(7), 1342—1350)
[30]	Ge Q., Jenkins S. J., King D. A., Chem. Phys. Lett., 2000, 327, 125—130
[31]	Perdew J. P., Chewary J. A., Vosko S. H., Jackson K. A., Pedersone M. R., Singh D. J., Fiolhais C., Phys. Rev. B, 1992, 46, 6671—6687
[32]	Tao J., Yao Z.J., Xue F., Fundamentals of Material Science, Chemical Industry Press, Beijing, 2006, 50—51
	(陶杰, 姚正军, 薛烽. 材料科学基础, 北京: 化学工业出版社, 2006, 50—51)
[33]	Palotas K., Bako I., Bugyi L., Appl. Surf. Sci., 2016, 389, 1094—1103
[34]	Vorotnikov V., Mpourmpakis G., Vlachos D. G., ACS. Catal., 2012, 2, 2496—2504
[35]	Liu R. Q., Comput. Theor. Chem., 2013, 1019, 141—145
[36]	Teng B. T., Zhao Y., Wu F. M., Wen X. D., Chen Q. P., Huang W. X., Surf. Sci., 2012, 606, 1227—1232
[37]	Guo F. Y., Long G. G., Zhang J., Zhang Z., Liu C. H., Yu K., Appl. Surf. Sci., 2015, 324, 584—589