Theoretical Studies on the Interaction of CO and CH3O on CuCl(111) Surface for Methanol Oxidative Carbonylation†

doi:10.7503/cjcu20140426

Abstract

Abstract:

Based on density functional theory method in the generalized gradient approximation, together with the periodic slab model, the single adsorption of CO and CH₃O, as well as the co-adsorption of CO and CH₃O on CuCl(111) surface involving in methanol oxidative carbonylation to dimethyl carbonate(DMC) were systematically investigated. The reaction mechanisms of CO interaction with CH₃O leading to CH₃OCO and CH₃OCO interaction with CH₃O to DMC on CuCl(111) surface were discussed. The calculated results indicate that the interaction between CO and CH₃O in the co-adsorption system is stronger than that between free CO and CH₃O in gas phase, CO insertion into adsorbed CH₃O on CuCl(111) surface to CH₃OCO species are the rate-limiting step for the oxidative carbonylation of methanol to DMC, and the corresponding activation barrier is 113.19 kJ/mol, the calculated results are in accordance with the reported experimental facts.

Key words: CuCl(111) surface, Carbon monoxide, Methoxide, Coadsorption, Density functional theory, Methanol oxidative carbonylation

CLC Number:

O643

TrendMD:

ZHENG Huayan, ZHANG Riguang, LI Zhong. Theoretical Studies on the Interaction of CO and CH₃O on CuCl(111) Surface for Methanol Oxidative Carbonylation^†[J]. Chem. J. Chinese Universities, 2014, 35(9): 1926.

Figures/Tables 10

Fig.1 CuCl(111)-[2×2] supercell (A) Side view; (B) top view. Green balls represent Cl atoms, orange balls represent Cu atoms.

Table 1 Bond length(R), stretching frequency(ν) and bond dissociation energy(BDE) for free CO molecule

Method	R(C—O)/nm	BDE/(kJ·mol^-1)	v(C—O)/cm^-1
GGA-BLYP	0.1143	1091.24	2128
Expt.	0.1128^[32]	1076.38±0.67^[33]	2138^[34]

Table 2 Predicted geometrical parameter, adsorption energies and Mulliken charge at four selected sites

Mode	Site	R(C—O)/ nm	R(Cu—C)/ nm	R(Cu—O)/ nm	∠C—O—Cl(Cu)/ (°)	∠O—C—Cu(Cl)/ (°)	q(CO)	E_ads/ (kJ·mol^-1)
CO(O-down)	Top	0.1145		0.3905	179.72		-0.005	11.23
	Cl-site	0.1145		0.4383	179.52		-0.005	10.90
	Hollow	0.1146		0.4135	179.82		-0.005	11.14
	Bridge	0.1145		0.4152	174.94		-0.004	11.12
CO(C-down)	Top	0.1153	0.1905			172.50	0.079	84.47
	Hollow	0.1158	0.2816			179.95	-0.093	18.97

Fig.2 Optimized structure of CO, CH3O and CH3OCO at the top site of CuCl(111) surface (A) CO; (B) CH3O; (C) CH3OCO. Green balls represent Cl atoms, orange balls represent Cu atoms, grey balls represent C atoms, white balls represent H atom, red balls represent O atoms.

Table 3 Predicted geometrical parameter, adsorption energies and Mulliken charge of CH3O

Site	R(C—O)/nm	R(Cu—O)/nm	∠C—O—Cu/(°)	∠O—C—Cl/(°)	$q (C H 3 O)$	E_ads/(kJ·mol^-1)
Hollow	0.1431	0.2508		179.723	-0.423	218.02
Top	0.1390	0.1930	175.751		-0.380	184.12

Table 3 Predicted geometrical parameter, adsorption energies and Mulliken charge of CH3O

Site	R(C—O)/nm	R(Cu—O)/nm	∠C—O—Cu/(°)	∠O—C—Cl/(°)	$q (C H 3 O)$	E_ads/(kJ·mol^-1)
Hollow	0.1431	0.2508		179.723	-0.423	218.02
Top	0.1390	0.1930	175.751		-0.380	184.12

Table 4 Predicted geometrical parameter, Mulliken charge and adsorption energy of CH3OCO at different adsorption sites

Site	R(C O)/ nm	R(C—O)/ nm	R( C—O)/ nm	R[Cu—C (nearest)]/nm	∠O—C—O/ (°)	∠C—O—C/ (°)	q(CH₃OCO)	E_ads/ (kJ·mol^-1)
Top	0.1258	0.1481	0.1367	0.2046	118.350	117.837	0.171	219.59
Bridge	0.1259	0.1480	0.1368	0.2045	118.164	117.846	0.170	219.54
Cl-site	0.1257	0.1480	0.1368	0.2052	118.517	117.887	0.171	219.27
Hollow	0.1260	0.1482	0.1369	0.2055	117.773	117.611	0.171	218.72

Fig.3 Optimized co-adsorbed structure of CO+CH3O and the corresponding transition state for CO interaction with CH3O to CH3OCO over CuCl(111) surface (A) CO+CH3O; (B) TS1. Bond lengths are in nm.

Table 5 Comparisons of theoretical calculation results between(CO+CH3O)/CuCl(111) co-adsorption and CO/CuCl(111) as well as CH3O/CuCl(111) single adsorption

Absorption	Molecule	R(C—O)/ nm	R(Cu—C)/ nm	R(Cu—O)/ nm	∠C—O—Cl/ (°)	∠O—C—Cu/ (°)	q(X)	E_ads/ (kJ·mol^-1)	E_cads/ (kJ·mol^-1)	E_int/ (kJ·mol^-1)
Co-adsorption	CO	0.1152	0.1918			174.247	0.212	89.74	294.92	2.89
	CH₃O	0.1425		0.2443	164.351		-0.410	208.07
Single adsorption	CO	0.1153	0.1905			175.502	0.186	84.47
	CH₃O	0.1431		0.2508	179.723		-0.423	218.02

Fig.4 Optimized co-adsorbed structure of CH3OCO and CH3O and the corresponding transition state for CH3OCO interaction with CH3O to DMC over CuCl(111) surface (A) CH3OCO+CH3O; (B) TS2; (C) DMC. Bond lengths are in nm.

Fig.5 Sketch for potential relative energy(Erel) for the reaction mechanism of DMC formation

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Theoretical Studies on the Interaction of CO and CH₃O on CuCl(111) Surface for Methanol Oxidative Carbonylation^†

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