Theoretical Studies on the Reaction Mechanisms of Methoxy Group and Carbon Monoxide over the Surfaces of Pd(111)†

doi:10.7503/cjcu20140260

Abstract

Abstract:

The possible reaction mechanisms of CH₃O and CO on Pd(111) surface were studied with GGA-PW91 in the DMol³ software package based on density functional theory(DFT). The relative calculated results indicate that the equilibrium state of CH₃O adsorbed at fcc position is the most stable configuration with more negative charges on O atom, be apt to be attacked by electrophilic reagents. While, CO adsorbed on top site perpendicularly by the interaction between C atom and Pd surface has lower adsorption energy, and its carbon atoms will possess more positive charges, which avail the migration for electrophilic insert reaction. Compared with CO on the bridge and hollow sites, CO adsorbed on the top sites is the optimistical configuration for the coupled reaction yielding CH₃OOC, which may be attributed to the mobility and electrophilcity of CO.

Key words: Density functional theory, Carbon monoxide, Surface of Pd(111), Surface adsorption, Reaction pathway

CLC Number:

O641

TrendMD:

DING Kaining, LI Yulu, CHENG Peisi, ZHANG Yongfan. Theoretical Studies on the Reaction Mechanisms of Methoxy Group and Carbon Monoxide over the Surfaces of Pd(111)^†[J]. Chem. J. Chinese Universities, 2014, 35(8): 1739.

Figures/Tables 11

References 28

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	(Ed.: Y, Z)

Layer	Δd_1-2(%)	Δd_2-3(%)	Δd_3-4(%)	E_surf /(J·m^-2)
3	0.33(0.44^[11])	-0.39(-0.32^[11])		1.26(1.40^[11])
4	0.34	-0.27		1.28
5	0.31	-0.31		1.30
6	0.33	-0.29		1.34
7	0.41	0.30	-0.33	1.32

Layer	Δd_1-2(%)	Δd_2-3(%)	Δd_3-4(%)	E_surf /(J·m^-2)
3	0.33(0.44^[11])	-0.39(-0.32^[11])		1.26(1.40^[11])
4	0.34	-0.27		1.28
5	0.31	-0.31		1.30
6	0.33	-0.29		1.34
7	0.41	0.30	-0.33	1.32

Layer	E_ads(CO)/(kJ·mol^-1)				E_ads(H₃CO)/( kJ·mol^-1)
Layer	Top	Bridge	fcc	hcp	Top	Bridge	fcc	hcp
3	-159.41	-144.87	-204.18	-201.67	-180.33	-211.71	-218.82	-197.48
4	-151.46	-186.61	-199.99	-196.23	-189.95	-200.41	-212.97	-196.72
5	-161.08	-173.22	-187.02	-144.78	-196.14	-210.04	-215.06	-196.42
6	-158.16	-176.98	-186.61	-187.86	-192.05	-203.76	-214.22	-212.55
7	-155.64	-187.02	-196.23	-192.88	-195.68	-205.43	-216.31	-210.87

Layer	E_ads(CO)/(kJ·mol^-1)				E_ads(H₃CO)/( kJ·mol^-1)
Layer	Top	Bridge	fcc	hcp	Top	Bridge	fcc	hcp
3	-159.41	-144.87	-204.18	-201.67	-180.33	-211.71	-218.82	-197.48
4	-151.46	-186.61	-199.99	-196.23	-189.95	-200.41	-212.97	-196.72
5	-161.08	-173.22	-187.02	-144.78	-196.14	-210.04	-215.06	-196.42
6	-158.16	-176.98	-186.61	-187.86	-192.05	-203.76	-214.22	-212.55
7	-155.64	-187.02	-196.23	-192.88	-195.68	-205.43	-216.31	-210.87

Species	E_ads/(kJ·mol^-1)				Species	E_ads/(kJ·mol^-1)
Species	N_t		N_b	N_f	N_h	N_t	N_b	N_f	N_h
1×1	-181.17	-171.96	-74.89	-84.94	Calcd.^[14]	-112.13	-141.84		-167.36
2×2	-178.66	-177.82	-79.08	-86.19	Calcd.^[12]	-131.38	-174.47	-194.14	-191.21
3×3	-159.41	-144.87	-204.18	-201.67	4×4	-181.60	-158.16	-184.51	-182.00
Calcd.^[13]	-161.92	-181.59	-185.35	-186.19