α,β-不饱和醛在Ni-Pt(111)面上吸附的理论研究

doi:10.7503/cjcu20180551

摘要/Abstract

摘要：

利用密度泛函理论研究了巴豆醛和肉桂醛分子在Pt-Ni-Pt(111)面的吸附构型以及相关电子性质. 吸附构型与吸附能结果表明, 巴豆醛和肉桂醛在覆盖度为1/25 ML的条件下, 以C=C和C=O双键协同吸附在Pt-Ni-Pt(111)面较为稳定, 且肉桂醛与Pt-Ni-Pt(111)面的吸附能远大于巴豆醛. 由Mulliken电荷布局和差分电荷密度可知, 在吸附过程中肉桂醛分子向Pt-Ni-Pt(111)面上转移的电荷数较巴豆醛更多, 相互作用更大. 由电子态密度分析结果可知, 不饱和醛与Pt-Ni-Pt(111)面的吸附作用主要是由于分子的p轨道电子与催化剂d轨道电子之间的相互作用. 由于苯基的存在使肉桂醛分子在Pt-Ni-Pt(111)面上的吸附更强, 且平行于催化剂表面.

关键词: 密度泛函理论, 巴豆醛, 肉桂醛, Ni-Pt(111)面, 吸附

Abstract:

The adsorption configurations of crotonaldehyde and cinnamaldehyde molecules on Pt-Ni-Pt(111) surface and their electronic properties were studied with density functional theory(DFT). The adsorption configurations and adsorption energy values illustrate that synergistic adsorption of crotonaldehyde and cinnamaldehyde molecules on Pt-Ni-Pt(111) surface with C=O and C=C bonds are most stable under the coverage of 1/25 ML. Moreover, the adsorption energy values of cinnamaldehyde on Pt-Ni-Pt(111) surface are much larger than that of crotonaldehyde. By analyzing Mulliken atomic charge population and the deformation density, it is found that the cinnamaldehyde molecule transfers more electrons to the Pt-Ni-Pt(111) surface and interact more strongly. The result of partial density of states(PDOS) indicates that the main reason for the adsorption is due to the interaction of the p orbital electrons of the unsaturated aldehyde molecules with the d orbital electrons of metal surface. And, due to the presence of the phenyl group, the cinnamaldehyde molecule is parallel to the surface of the Pt-Ni-Pt(111) and adsorbed more strongly.

Key words: Density functional theory, Crotonaldehyde, Cinnamaldehyde, Ni-Pt(111) surface, Adsorption

中图分类号:

O641

TrendMD:

罗伟, 方镭, 孟跃, 薛继龙, 陈涛, 夏盛杰, 倪哲明. α,β-不饱和醛在Ni-Pt(111)面上吸附的理论研究. 高等学校化学学报, 2019, 40(1): 115.

LUO Wei,FANG Lei,MENG Yue,XUE Jilong,CHEN Tao,XIA Shengjie,NI Zheming. Theoretical Study on Adsorption of α,β-Unsaturated Aldehydes on Ni-Pt(111) Surface^†. Chem. J. Chinese Universities, 2019, 40(1): 115.

图/表 10

Fig.1 Molecular models of the isomers of unsaturated aldehyde (A) Crotonaldehyde; (B) cinnamaldehyde.

Table 1 Relative energy of unsaturated aldehyde models

Molecule	ΔE/(kJ·mol^-1)
Molecule	E-(s)-trans	E-(s)-cis	Z-(s)-trans	Z-(s)-cis
Crotonaldehyde	0	8.46	10.73	14.92
Cinnamaldehyde	0	7.82	18.64	23.07

Fig.2 Structures of crotonaldehyde(A), cinnamaldehyde(B) and Pt-Ni-Pt(111) surface(C)

Table 2 Adsorption energy(Eads) of unsaturated aldehyde molecules on Ni-Pt(111) surface

Species	Adsorption site	E_ads/(kJ·mol^-1)		Species	Adsorption site	E_ads/(kJ·mol^-1)
Species	Adsorption site	Crotonaldehyde	Cinnamaldehyde	Species	Adsorption site	Crotonaldehyde	Cinnamaldehyde
O	top	47.15	69.70	C=O, C=C	top-hcp	61.58	98.80
	bri	44.81	75.99		top-fcc	61.37	98.52
	hcp	44.52	85.77		bri-top	61.92	99.21
	fcc	45.20	76.33		bri-bri	61.50	98.82
C=C	top	60.59	96.81		bri-hcp	58.57	98.72
	bri	61.86	98.42		bri-fcc	61.92	98.61
	hcp	61.43	97.76		hcp-top	61.94	99.10
	fcc	60.70	97.93		hcp-bri	61.86	98.93
C=O	top	60.96	97.81		hcp-hcp	61.66	98.79
	bri	61.78	96.16		hcp-fcc	61.68	98.60
	hcp	61.60	98.54		fcc-top	61.60	98.70
	fcc	60.19	97.93		fcc-bri	61.71	98.80
C=O, C=C	top-top	60.98	98.24		fcc-hcp	62.32	98.38
	top-bri	61.84	98.56		fcc-fcc	59.49	99.85

Fig.3 Top(A1, B1) and side(A2, B2) views of the most stable adsorption configuration for crotonaldehyde(A1, A2) and cinnamaldehyde(B1, B2) on Ni-Pt(111) surface

Table 3 Structure parameters of crotonaldehyde for the most stable adsorption configuration*

Crotonaldehyde	d₁/nm	d₂/nm	d₃/nm	d₄/nm
Free	0.1271	0.1429	0.1393	0.1481
fcc-hcp	0.1269	0.1435	0.1396	0.1480
Δd/nm	0.0002	0.0006	0.0003	0.0001

Table 4 Structure parameters of cinnamaldehyde for the most stable adsorption configuration*

Cinnamaldehyde	d₁/nm	d₂/nm	d₃/nm	d₄/nm	d₅/nm	d₆/nm	d₇/nm	d₈/nm	d₉/nm	d₁₀/nm
Free	0.1272	0.1425	0.1404	0.1430	0.1433	0.1407	0.1414	0.1414	0.1408	0.1432
fcc-fcc	0.1270	0.1431	0.1406	0.1434	0.1436	0.1411	0.1416	0.1416	0.1412	0.1434
Δd/nm	0.0002	0.0006	0.0002	0.0004	0.0003	0.0004	0.0002	0.0002	0.0004	0.0002

Fig.4 Mulliken charge populations of crotonaldehyde(A) and cinnamaldehyde(B)The values outside the parentheses are the amount of charge of each atom for free molecules. The values in parentheses are the amount of charge of the atom after the adsorption, and the adsorption configuration modes are shown in Fig.3.

Fig.5 Deformation density of crotonaldehyde(A) and cinnamaldehyde(B) for the most stable adsorption on Pt-Ni-Pt(111) surface

Fig.6 Densities of states of crotonaldehyde(A, C, E) and cinnamaldehyde(B, D, F) for the most stable adsorption configuration(A), (B) Represent the electron density of molecule after adsorption; (C), (D) represent electron density of of Pt-Ni-Pt(111) surface after adsorption; (E), (F) represent total DOS most stable adsorption configuration.

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