Cluster Properties of Au19Pt and Selective Hydrogenation Mechanism of Cinnamaldehyde on Au19Pt Cluster Surface†

doi:10.7503/cjcu20160314

Abstract

Abstract:

Structural stability, thermodynamic stability and chemical reactivity of the bimetallic Au₁₉Pt clusters were investigated based on the framework of the relativistic density functional theory. It was calculated that Au₁₉Pt-V cluster was chemically more active than Au₁₉Pt-S and Au₁₉Pt-E clusters but thermodynamically less stable. To explore the most stable adsorption configuration, the adsorption behavior of a cinnamaldehyde on three types of bimetallic Au₁₉Pt cluster was studied via analyzing the adsorption energy and Mulliken charge. The calculation results indicate that a cinnamaldehyde molecule is preferably adsorbed on Pt site in Au₁₉Pt-V cluster with C=C, in which the adsorption configuration is the most stable. In that condition, the adsorption energy and the amount of charge transfer are maximum. Moreover, 6 possible mechanisms were investigated of three kinds of selective hydrogenation reaction(1,2-additive reaction, 3,4-additive reaction and 1,4-conjugate additive reaction) of cinnamaldehyde on Au₁₉Pt-V cluster, on the basis of the most stable adsorption configuration. Compared with the reaction energy, activation energy and configuration change of each elementary steps, it suggests that the most favorable way of the cinnamaldehyde on the Au₁₉Pt-V cluster would be through 3,4-additive reaction(mechanism C). The specific reaction pathway involved a C3 atom preferentially hydrogenating to generate MS3 intermediate, another H atom added to intermediate to take shape C4—H bond. Then the final product phenylpropyl aldehyde is forming through the transition state TS34.

Key words: Density functional theory, Cinnamaldehyde, Au19Pt cluster, Selective hydrogenation, Phenyl-propyl aldehyde

CLC Number:

O643

TrendMD:

CAO Yongyong, JIANG Junhui, NI Zheming, XIA Shengjie, QIAN Mengdan, XUE Jilong. Cluster Properties of Au₁₉Pt and Selective Hydrogenation Mechanism of Cinnamaldehyde on Au₁₉Pt Cluster Surface^†[J]. Chem. J. Chinese Universities, 2016, 37(7): 1342.

Figures/Tables 12

Fig.1 Structure of cinnamaldehyde(CAL)

Fig.2 Optimized structures of Au20 and Au19Pt clusters (A) Au20; (B) Au19Pt-V; (C) Au19Pt-E; (D) Au19Pt-S.

Table 1 Relative bond length between the Pt atom and its nearest neighbor Au atom*

Pair	r_Au-Au/(r_Au+r_Pt)	r_Au-Pt/(r_Au+r_Pt)
Pt_E-Au_surface	1.018	0.977
Pt_E-A	1.070	1.021
Pt_E-A	0.968	0.958
Pt_V-Au_edge	0.985	0.946
Pt_S-Au_edge	1.018	1.008
Pt_S-Au_vertex	1.702	1.697

Table 2 Binding energy and d-band center of the pure Au20 and bimetallic tetrahedral Au19Pt clusters

System	ΔE_b/eV	E_{d-band center}/eV
Au₂₀	42.34	-3.24
Au₁₉Pt-S	43.42	-2.45
Au₁₉Pt-V	43.12	-2.39
Au₁₉Pt-E	43.40	-2.62

Fig.4 Optimized structure for the CAL molecule on the Au19Pt-E(A1—C1), Au19Pt-S(A2—C2) and Au19Pt-V(A3—C3) clusters(A1) PtE-σ(O); (A2) PtS-σ(O); (A3) PtV-σ(O); (B1) PtE-π(CO); (B2) PtS-π(CO); (B3) PtV-π(CO); (C1) PtE-π(CC); (C2) PtS-π(CC); (C3) PtV-π(CC).

Table 3 Adsorption energies(Eads) and Mulliken atomic charges(Q) of CAL on Au19Pt clusters

System	Final adsorption mode	E_ads/eV	Q_CAL/e
CAL/Au₁₉Pt-E	Pt_E-σ(O)	1.01	+0.185
	Pt_E-π(CO)	0.89	+0.138
	Pt_E-π(CC)	1.61	+0.220
CAL/Au₁₉Pt-S	Pt_S-σ(O)	0.66	+0.005
	Pt_S-π(CO)	0.82	+0.019
	Pt_S-π(CC)	0.74	+0.221
CAL/Au₁₉Pt-V	Pt_V-σ(O)	1.28	+0.113
	Pt_V-π(CO)	1.31	+0.270
	Pt_V-π(CC)	1.87	+0.272

Fig.5 Reaction mechanisms of CAL partial selective hydrogenation on Au19Pt-V cluster

Table 4 Activation energy(Ea) and reaction energy(ΔE) of possible six main reactions of CAL on Au19Pt cluster

Mechanism	Step	Reaction	E_a/eV	ΔE/eV
H₂ dissociation		H₂→H^+H^	0.99	-0.55
A	A(1)	CAL^+H^→MS1^*	0.51	0.17
	A(2)	MS1^+H^→COL^+	1.75	0.15
B	B(1)	CAL^+H^→MS2^*	3.97	1.12
	B(2)	MS2^+H^→COL^+	0.48	0.05
C	C(1)	CAL^+H^→MS3^*	1.08	0.33
	C(2)	MS3^+H^→HCAL^+	0.65	0.71
D	D(1)	CAL^+H^→MS4^*	1.38	1.03
	D(2)	MS4^+H^→HCAL^+	0.36	0.73
E	E(1)	CAL^+H^→MS1^*	0.51	0.17
	E(2)	MS1^+H^→ENOL^+	2.09	1.28
F	F(1)	CAL^+H^→MS4^*	1.38	1.03
	F(2)	MS4^+H^→ENOL^+	4.20	1.41

Fig.6 Simulation reaction process of mechanisms A and B(A) and energy diagrams of COL formation(B) a. Mechanism A; b. mechanism B.

Fig.7 Simulation reaction process of mechanisms C and D(A) and energy diagrams of HCAL formation(B) a. Mechanism C; b. mechanism D.

Fig.8 Simulation reaction process of mechanisms E and F(A) and energy diagrams of ENOL formation(B) a. Mechanism E; b. mechanism F.

Fig.9 Energy change of mechanisms A(a), C(b) and E(c) on Au19Pt-V cluster

References 33

[1]	Lee J. D., Christopher M. A., Parlett1 N. S., Scientific Reports,2015, 5(9426), 1—7
[2]	Kolodziej M., Drelinkiewicz A., Lalik E., Gurgul J., Duraczynska D., Kosydar R., Applied Catalysis A: General,2016, 515, 60—71
[3]	Karl R., Kahsar D. K., Schwartz J., Will M., J. Am. Chem. Soc., 2014, 136, 520—526
[4]	Fang C., Chen Y. J., Mao B., Zhao J., Jiang Y. F., Zhao S. L., Ma J., Chem. J. Chinese Universities,2015, 36(1), 124—130(方超, 陈亚君, 毛卉, 赵俊, 蒋云福, 赵仕林, 马骏. 高等学校化学学报, 2015, 36(1), 124—130)
[5]	Li H., Ma C.J., Li H. X., Acta Chimica Sinica, 2006, 24, 1947—1953(李辉, 马春景, 李和兴. 化学学报, 2006, 24, 1947—1953)
[6]	Xue Q. Q., Karine P., Pierre L., Philippe S., Dalton Trans., 2014, 43, 9283—9295
[7]	Haeck J.D., Veldeman N., J. Phys.Chem. A, 2011, 115, 2103—2109
[8]	Qian H., Jiang D., Gayathri C., J. Am. Chem. Soc., 2012, 134, 16159—16162
[9]	Cheng L., Xiao Y. K., Zhi W. L., J. Phys. Chem. A,2011, 115, 9273—9281
[10]	Zhang X. D., Gao M. L., Wu D., Int. J. Mol. Sci., 2011, 12, 2972—2981
[11]	Yuan D. W., Wang Y., Zenga Z., J. Chem. Phys., 2005, 122, 114310
[12]	Mondal K., Ghanty T. K., Banerjee A., Mol. Phys., 2013, 111, 725—734
[13]	Sinfelt J. H., Accounts Chem. Res., 1987, 20, 134—136
[14]	Gholizadeh R., Yu Y. X., Appl. Surf. Sci., 2015, 357, 1187—1195
[15]	Liu T. T., Lu X., Zhang M. T., Chem. Res. Chinese Universities,2014, 30(4), 656—660
[16]	Pan W., Ma G. W., Yang X. D., Chem. J. Chinese Universities,2015, 36(2), 325—329(潘威, 马广文, 杨小东. 高等学校化学学报, 2015, 36(2), 325—329)
[17]	Tapan K. G., J. Phys. Chem. C, 2014, 118, 11935—11945
[18]	Anna V., Beletskaya D. P., Alexander F. S., J. Phys. Chem. A,2013, 117, 6817—6826
[19]	Ke Q. S., Yong C. H., Gui R. Z., ACS Catal., 2011, 1, 1336—1346
[20]	Yong C. H., Ke Q. S., Gui R. Z., Chem. Commun., 2011, 47, 1300—1302
[21]	Delley B., J. Phys. Chem. A, 2006, 110, 13632—13639
[22]	Chen W. K., Cao M. J., Liu S. H., Acta Phys-Chim Sinica,2005, 21, 903—908(陈文凯, 曹梅娟, 刘书红. 物理化学学报, 2005,21, 903—908)
[23]	Xiao X. C., Shi W., Ni Z. M., Zhang L. Y., Acta Phys-Chim Sinica,2015, 31, 885—892(肖雪春, 施炜, 倪哲明, 张连阳. 物理化学学报, 2015,31, 885—892)
[24]	Tao J., Yao Z.J., Xue F., Fundamentals of Material Science, Chemical Industry Press, 2006, 50—51
	(陶杰, 姚正军, 薛烽. 化学工业出版社, 2006, 50—51)
[25]	Ham H. C., Hwang G. S., Han J., Nam S. W., Lim T. H., J. Phys. Chem. C,2010, 114, 14922—14928
[26]	Morrow B. H., Resasco D. E., Striolo A., Nardelli M. B., J. Phys. Chem. C,2011, 115, 5637—5647
[27]	Diego C. A., Maria P. O., Luis S., J. Phys. Chem. A,2015, 119, 6909—6918
[28]	Delbecq D., Sautet P., J. Catal., 1995, 152, 217—236
[29]	Mulliken R. S., J. Chem. Phys., 1955, 23, 1833—1840
[30]	Loffreda D., Delbecq F., Vigne F., Sautet P., J. Am. Chem. Soc., 2006, 128, 1316—1323
[31]	Shi W., Zhang L. Y., Ni Z. M., Xiao X. C., Xia S. J., RSC Advances,2014, 4, 27003—27012
[32]	Zhang L.Y., Jiang J. H., Shi W., Xia S. J., Ni Z. M., RSC Advances,2015, 5, 34319—34326
[33]	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(4), 693—700)

Cluster Properties of Au₁₉Pt and Selective Hydrogenation Mechanism of Cinnamaldehyde on Au₁₉Pt Cluster Surface^†

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 33

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	HE Hongrui, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane [J]. Chem. J. Chinese Universities, 2022, 43(8): 20220196.
[2]	SONG Youwei, AN Jiangwei, WANG Zheng, WANG Xuhui, QUAN Yanhong, REN Jun, ZHAO Jinxian. Effects of Ag，Zn，Pd-doping on Catalytic Performance of Copper Catalyst for Selective Hydrogenation of Dimethyl Oxalate [J]. Chem. J. Chinese Universities, 2022, 43(6): 20210842.
[3]	WONG Honho, LU Qiuyang, SUN Mingzi, HUANG Bolong. Rational Design of Graphdiyne-based Atomic Electrocatalysts： DFT and Self-validated Machine Learning [J]. Chem. J. Chinese Universities, 2022, 43(5): 20220042.
[4]	LIU Yang, LI Wangchang, ZHANG Zhuxia, WANG Fang, YANG Wenjing, GUO Zhen, CUI Peng. Theoretical Exploration of Noncovalent Interactions Between Sc₃C₂@C₈₀ and ［12］Cycloparaphenylene Nanoring [J]. Chem. J. Chinese Universities, 2022, 43(11): 20220457.
[5]	WANG Yuanyue, AN Suosuo, ZHENG Xuming, ZHAO Yanying. Spectroscopic and Theoretical Studies on 5-Mercapto-1，3，4-thiadiazole-2-thione Microsolvation Clusters [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220354.
[6]	CHENG Yuanyuan, XI Biying. Theoretical Study on the Fragmentation Mechanism of CH₃SSCH₃ Radical Cation Initiated by OH Radical [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220271.
[7]	LI Xueyu, WANG Zhao, CHEN Ya, LI Keke, LI Jianquan, JIN Shunjing, CHEN Lihua, SU Baolian. Enhanced Catalytic Performance of Supported Nano-gold by the Localized Surface Plasmon Resonance for Selective Hydrogenation of Butadiene [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220174.
[8]	ZHOU Chengsi, ZHAO Yuanjin, HAN Meichen, YANG Xia, LIU Chenguang, HE Aihua. Regulation of Silanes as External Electron Donors on Propylene/butene Sequential Polymerization [J]. Chem. J. Chinese Universities, 2022, 43(10): 20220290.
[9]	MA Lijuan, GAO Shengqi, RONG Yifei, JIA Jianfeng, WU Haishun. Theoretical Investigation of Hydrogen Storage Properties of Sc， Ti， V-decorated and B/N-doped Monovacancy Graphene [J]. Chem. J. Chinese Universities, 2021, 42(9): 2842.
[10]	HUANG Luoyi, WENG Yueyue, HUANG Xuhui, WANG Chaojie. Theoretical Study on the Structures and Properties of Flavonoids in Plantain [J]. Chem. J. Chinese Universities, 2021, 42(9): 2752.
[11]	ZHONG Shengguang, XIA Wensheng, ZHANG Qinghong, WAN Huilin. Theoretical Study on Direct Conversion of CH₄ and CO₂ into Acetic Acid over MCu₂O_x（M = Cu²⁺， Ce⁴⁺， Zr⁴⁺） Clusters [J]. Chem. J. Chinese Universities, 2021, 42(9): 2878.
[12]	ZHENG Ruoxin, ZHANG Igor Ying, XU Xin. Development and Benchmark of Lower Scaling Doubly Hybrid Density Functional XYG3 [J]. Chem. J. Chinese Universities, 2021, 42(7): 2210.
[13]	LIU Changhui, LIANG Guojun, LI Yanlu, CHENG Xiufeng, ZHAO Xian. Density Functional Theory Study of NH₃ Adsorption on Boron Nanotubes [J]. Chem. J. Chinese Universities, 2021, 42(7): 2263.
[14]	WANG Jian, ZHANG Hongxing. Theoretical Study on the Structural-photophysical Relationships of Tetra-Pt Phosphorescent Emitters [J]. Chem. J. Chinese Universities, 2021, 42(7): 2245.
[15]	HU Wei, LIU Xiaofeng, LI Zhenyu, YANG Jinlong. Surface and Size Effects of Nitrogen-vacancy Centers in Diamond Nanowires [J]. Chem. J. Chinese Universities, 2021, 42(7): 2178.