Adsorption and Selective Hydrogenation Mechanism of Crotonaldehyde on AuSurface

doi:10.7503/cjcu20150844

Abstract

Abstract:

The stabilities of four possible configurations for crotonaldehyde were investigated with density functional theory(DFT) model. The most favorable configuration of crotonaldehyde was selected to explore the adsorption and its selective hydrogenation mechanism on the Au(111) surface was also investigated. The calculated results showed that the E-(s)-trans-crotonaldehyde was the most stable configuration. The adsorption at the top site was most stable when the crotonaldehyde on the Au(111) surface with CO. And its adsorption energy was maximum. The d orbitals of the metal surface interact strongly with the p orbitals of the crotonaldehyde. And the crotonaldehyde losed 0.045 electrons after adsorption on the Au(111) surface. In addition, comparing the reaction energy, activation energy and structure change of each elementary steps, we obtained that the crotonaldehyde was more likely to follow the 2,1-addition mechanism(partial hydrogenation mechanism) to produce crotyl alcohol, and the lower temperature was helpful for the reaction to improve the conversion rate.

Key words: Density functional theory, Crotonaldehyde, Au(111) surface, Adsorption, Selective hydrogenation mechanism

CLC Number:

O643

TrendMD:

JIANG Junhui, XIA Shengjie, NI Zheming, Zhang Lianyang. Adsorption and Selective Hydrogenation Mechanism of Crotonaldehyde on AuSurface[J]. Chem. J. Chinese Universities, 2016, 37(4): 693.

Figures/Tables 12

References 32

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Initial adsorption site	Final adsorption site	E_ads/(kJ·mol^-1)	Initial adsorption site	Final adsorption site	E_ads/(kJ·mol^-1)
	O			C O, C C
Top	Top	-85.1	Top-Top	Bri-Top	-84.5
Bri	Bri	-86.8	Top-Bri	Bri-Bri	-84.5
Hcp	Hcp	-84.1	Top-Hcp	Top-Hcp	-84.2
Fcc	Fcc	-84.9	Top-Fcc	Top-Fcc	-84.3
	C O		Bri-Top	Bri-Top	-84.5
Top	Top	-93.7	Bri-Bri	Bri-Bri	-84.6
Bri	Bri	-90.5	Bri-Hcp	Bri-Top	-84.0
Hcp	Hcp	-85.0	Bri-Fcc	Bri-Fcc	-83.8
Fcc	Fcc	-86.7	Hcp-Top	Hcp-Top	-84.7
	C C		Hcp-Bri	Hcp-Bri	-84.5
Top	Top	-79.7	Hcp-Hcp	Bri-Fcc	-83.5
Bri	Bri	-80.4	Hcp-Fcc	Hcp-Fcc	-84.0
Hcp	Hcp	-81.8	Fcc-Top	Fcc-Top	-84.4
Fcc	Fcc	-82.6	Fcc-Bri	Fcc-Bri	-83.5
			Fcc-Hcp	Bri-Bri	-84.6
			Fcc-Fcc	Fcc-Fcc	-83.7

Initial adsorption site	Final adsorption site	E_ads/(kJ·mol^-1)	Initial adsorption site	Final adsorption site	E_ads/(kJ·mol^-1)
	O			C O, C C
Top	Top	-85.1	Top-Top	Bri-Top	-84.5
Bri	Bri	-86.8	Top-Bri	Bri-Bri	-84.5
Hcp	Hcp	-84.1	Top-Hcp	Top-Hcp	-84.2
Fcc	Fcc	-84.9	Top-Fcc	Top-Fcc	-84.3
	C O		Bri-Top	Bri-Top	-84.5
Top	Top	-93.7	Bri-Bri	Bri-Bri	-84.6
Bri	Bri	-90.5	Bri-Hcp	Bri-Top	-84.0
Hcp	Hcp	-85.0	Bri-Fcc	Bri-Fcc	-83.8
Fcc	Fcc	-86.7	Hcp-Top	Hcp-Top	-84.7
	C C		Hcp-Bri	Hcp-Bri	-84.5
Top	Top	-79.7	Hcp-Hcp	Bri-Fcc	-83.5
Bri	Bri	-80.4	Hcp-Fcc	Hcp-Fcc	-84.0
Hcp	Hcp	-81.8	Fcc-Top	Fcc-Top	-84.4
Fcc	Fcc	-82.6	Fcc-Bri	Fcc-Bri	-83.5
			Fcc-Hcp	Bri-Bri	-84.6
			Fcc-Fcc	Fcc-Fcc	-83.7

Species	Charge/e
Species	O1	C2	C3	C4	C5	H6	H7	H8	H9	H10	H11	Tol
CAL	-0.378	0.282	-0.050	0.010	-0.135	-0.009	0.042	0.044	0.055	0.069	0.070	0.000
CAL/Au(111)	-0.355	0.232	-0.086	-0.033	-0.281	0.032	0.099	0.100	0.099	0.118	0.120	0.045

Species	Charge/e
Species	O1	C2	C3	C4	C5	H6	H7	H8	H9	H10	H11	Tol
CAL	-0.378	0.282	-0.050	0.010	-0.135	-0.009	0.042	0.044	0.055	0.069	0.070	0.000
CAL/Au(111)	-0.355	0.232	-0.086	-0.033	-0.281	0.032	0.099	0.100	0.099	0.118	0.120	0.045

Mechanism	Reaction	E_a/ (kJ·mol^-1)	ΔE/ (kJ·mol^-1)	Mechanism	Reaction	E_a/ (kJ·mol^-1)	ΔE/ (kJ·mol^-1)
A1	CAL^+H^→MS2^+	35.1	-43.8	C1	CAL^+H^→MS2^+	35.1	-43.8
	MS2^+H^→COL^+	150.7	-47.5		MS2^+H^→ENOL^+	312.2	-89.6
A2	CAL^+H^→MS1^+	70.3	-10.2	C2	CAL^+H^→MS3^+	288.1	-0.4
	MS1^+H^→COL^+	28.4	-81.0		MS3^+H^→ENOL^+	42.6	-133.0
B1	CAL^+H^→MS4^+	240.2	-32.5		CAL+→CAL^		-93.7
	MS4^+H^→BAL^+	301.7	-124.7		COL^→COL +		51.6
B2	CAL^+H^→MS3^+	288.1	-0.4		ENOL^→ENOL +		56.2
	MS3^+H^→BAL^+	220.3	-156.9		BAL^→BAL +		60.9