Ag表面乙醇选择性催化氧化的密度泛函理论研究

doi:10.11949/0438-1157.20190480

摘要/Abstract

摘要：

采用密度泛函理论计算对Ag(111)和Ag(211)表面乙醇催化氧化过程进行了系统性研究。研究发现原子氧物种是常温下乙醇氧化的关键中间体。在表面原子氧物种辅助下，乙醇O—H键和α-C—H键依次断裂，生成乙氧基中间体和乙醛产物（活化能（E _a）<38.0 kJ/mol）。乙醛随后与表面原子氧和羟基氧物种作用，导致CCOO（在Ag(111)表面发生CCOO $→$ C+ CO₂）和CH₂COO（在Ag(211)表面发生CH₂COO $→$ CH₂+ CO₂）中间体C—C键断裂生成CO₂，该过程是速率控制步骤（E _a>95.5 kJ/mol）。计算结果表明乙醇在Ag表面催化氧化过程为结构敏感反应，降低表面缺陷位数量可提高产物中乙醛选择性。

关键词: 分子模拟, 银, 催化, 部分氧化

Abstract:

A systematic study on the catalytic oxidation of Ag(111) and Ag(211) on the surface of Ag(111) was carried out by density functional theory. It was found that atomic O* is necessary to initiate the reaction at the ambient conditions. The O—H bond in the ethanol is activated with the help of adsorbed atomic O* to form ethoxy, which then further transfers hydrogen in α-C—H to adsorbed O* forming the acetaldehyde (E _a<38 kJ/mol), which, in turn, reacts with atomic O*/OH* to form final product CO₂. To generate CO₂, C—C bond breaking (CCOO $→$ C+ CO₂ on Ag(111) and CH₂COO $→$ CH₂+ CO₂ on Ag(211)) exhibits the highest barriers (E _a>95.5 kJ/mol), which indicated it is the rate-determining step. The results indicate that the catalytic oxidation of ethanol on silver surfaces is structural sensitive. Selectivity towards value-added products like acetaldehyde would be improved by reducing the density of defected sites.

Key words: molecular simulation, silver, catalysis, partial oxidation

中图分类号:

TQ 032.4

徐新潮, 田鹏飞, 徐晶, 韩一帆. Ag表面乙醇选择性催化氧化的密度泛函理论研究[J]. 化工学报, 2019, 70(10): 3967-3975.

Xinchao XU, Pengfei TIAN, Jing XU, Yifan HAN. Density functional study of selective oxidation of ethanol over silver catalysts[J]. CIESC Journal, 2019, 70(10): 3967-3975.

图/表 9

图1 Ag(111)表面俯视图和侧视图

Fig.1 Top and side view of Ag(111) surface

图2 Ag(211)表面俯视图和侧视图（台阶边缘Ag原子以浅色标示）

Fig.2 Top and side view of Ag(211) surface(Ag atoms on step edge were labeled by light color)

表1 反应物和可能中间物种在Ag表面的最优吸附位和对应的结合能

Table 1 Preferred adsorption configurations and corresponding binding energies of reactants and surface intermediate species on Ag(111) and Ag(211)

吸附物种	Ag(111)		Ag(211)
吸附物种	吸附位	结合能/（kJ/mol）	吸附位	结合能/（kJ/mol）
CH₃CH₂OH	O-top	-14.4	O-top	-18.3
O₂	O-brg	1.9	O-4f	-49.0
O	fcc	-339.4	O-4f	-379.8
H	fcc	-197.1	fcc	-219.2
OH	O-fcc	-240.4	fcc	-271.2
H₂O	O-top	-8.7	O-top	-17.3
CH₃CH₂O	O-top	-101.9	O-top	-150.0
CH₃CHOH	C_α-top	-41.4	C_α-top	-76.9
CH₂CH₂OH	C_β-top, O-top	-90.4	C_β-top, O-top	-140.4
CH₃CHO	O-top	-8.7	O-top	-18.3
CH₃CO	C_α-top	-81.7	C_α-top	-116.4
CH₂CHO	O-top	-106.7	O-top	-120.2
CH₃COO	C_β-fcc, O-top	-195.2	C_β-fcc, O-top	-238.5
CH₃COOH	O_OH-top	-7.7	O-top	-23.1
CH₂CO	C_α-top	-5.8	C_α-top	-8.7
CH₂COO	C_β-top, O-brg	-209.6	C_β-top, O-top	-242.3
CHCO	C_β-brg	-180.8	C_β-brg	-235.6
CHCOO	C_β-fcc, O-top	-245.2	C_β-brg, O-top	-310.6
CCO	C_β-fcc	-318.3	C_β-4f	-364.4
CCOO	C_β-fcc, O-brg	-247.1	C_β-brg, O-top	-292.3
OCCO	C_α-top, C_β-top	-225.4	—	—
CO₂	C-top	-1.9	C-top	-2.9

图3 关键反应物种在Ag(111)和Ag(211)表面吸附构型示意图

Fig.3 Preferred adsorption configurations of key reactants on Ag(111) and Ag(211) surfaces

表2 Ag(111)和Ag(211)表面不同脱氢路径下乙醇活化的反应热和活化能

Table 2 Reaction energies (E r) and activation barriers (E a) of the first dehydrogenation reaction in different dehydrogenation paths on Ag(111) and Ag(211) surfaces

反应路径	O—H断裂		α-C—H断裂		β-C—H断裂
反应路径	E _r/ (kJ/mol)	E _a/ (kJ/mol)	E _r/ (kJ/mol)	E _a/ (kJ/mol)	E _r/ (kJ/mol)	E _a/ (kJ/mol)
Ag(111)
直接脱氢	160.2	226.7	192.0	>192.0	193.9	>193.9
O辅助脱氢	-13.5	*7.7*	-1.9	74.3	16.4	33.8
OH辅助脱氢	34.7	64.6	100.3	>100.3	83.0	>83.0
Ag(211)
直接脱氢	84.9	>84.9	138.0	>138.0	151.5	>151.5
O辅助脱氢	-32.8	2.9	2.9	51.5	3.8	86.8
OH辅助脱氢	22.2	31.8	46.3	166.9	54.0	98.4

表3 Ag(111)表面乙醇氧化反应基元步骤反应热和活化能

Table 3 Activation barriers and reaction energies for elementary reaction steps on Ag(111)

编号	基元反应	E _a/ (kJ/mol)	E _r/ (kJ/mol)
1	O₂* $→$ O+O	108.1	-35.7
2	CH₃CH₂OH+O $→$ CH₃CH₂O+OH	7.7	-13.5
	CH₃CH₂OH+OH $→$ CH₃CH₂O+H₂O	64.6	34.7
	CH₃CH₂OH+ $→$ CH₃CH₂O+H	—	154.3
3	CH₃CH₂OH+O $→$ CH₂CH₂OH+OH	33.8	16.4
	CH₃CH₂OH+OH $→$ CH₂CH₂OH+H₂O	—	83.0
	CH₃CH₂OH+ $→$ CH₂CH₂OH+H	—	193.9
4	CH₃CH₂OH+O $→$ CH₃CHOH+OH	74.3	-1.9
	CH₃CH₂OH+OH $→$ CH₃CHOH+H₂O	—	100.3
	CH₃CH₂OH+ $→$ CH₃CHOH+H	—	192.0
5	CH₃CH₂O+O $→$ CH₃CHO+OH	38.6	-212.3
	CH₃CH₂O+OH $→$ CH₃CHO+ H₂O	62.7	-73.3
	CH₃CH₂O+ $→$ CH₃CHO+ H	46.3	2.9
6	CH₃CH₂O+O $→$ CH₂CH₂O+OH	95.5	-5.8
	CH₃CH₂O+OH $→$ CH₂CH₂O+H₂O	—	62.7
	CH₃CH₂O+ $→$ CH₂CH₂O+ H	—	139.9
7	CH₃CHO+O $→$ CH₃CO+OH	67.5	-41.5
	CH₃CHO+ $→$ CH₃CO+H	—	120.6
	CH₃CHO+OH $→$ CH₃CO+H₂O	102.3	29.9
8	CH₃CHO+O $→$ CH₂CHO+OH	49.2	-21.2
	CH₃CHO+OH $→$ CH₂CHO+H₂O	31.8	11.6
	CH₃CHO+ $→$ CH₂CHO+H	—	128.3
9	CH₂CHO+O $→$ CH₂CO+OH	29.9	-33.8
	CH₂CHO+OH $→$ CH₂CO+H₂O	59.8	-26.1
	CH₂CHO+ $→$ CH₂CO+H	—	63.7
10	CH₂CHO+O $→$ CHCHO+OH	61.8	19.3
	CH₂CHO+OH $→$ CHCHO+H₂O	54.0	47.3
	CH₂CHO+ $→$ CHCHO+H	—	165.0
11	CH₂CO+O $→$ CHCO+OH	33.8	-26.1
	CH₂CO+OH $→$ CHCO+H₂O	101.3	-17.4
	CH₂CO+O $→$ CH₂COO*	6.8	-115.8
12	CHCO+O $→$ CCO+OH	21.2	-30.9
	CHCO+OH $→$ CCO+H₂O	16.4	-28.0
	CHCO+O $→$ CHCOO+	15.4	-93.6
13	CCO+O $→$ CCOO+	21.2	-100.3
14	CH₃CO+ $→$ CH₃+CO	173.7	106.1
	CH₂CO+ $→$ CH₂+CO	—	228.7
	CHCO+ $→$ CH+CO	—	225.8
15	CH₂COO+ $→$ CH₂+CO₂	155.3	38.6
	CHCOO+ $→$ CH+CO₂	137.0	9.7
	CCOO+ $→$ C+CO₂	126.4	-13.5
16	CCO+O $→$ OCCO+	53.1	-83.5

表3 Ag(111)表面乙醇氧化反应基元步骤反应热和活化能

Table 3 Activation barriers and reaction energies for elementary reaction steps on Ag(111)

编号	基元反应	E _a/ (kJ/mol)	E _r/ (kJ/mol)
1	O₂* $→$ O+O	108.1	-35.7
2	CH₃CH₂OH+O $→$ CH₃CH₂O+OH	7.7	-13.5
	CH₃CH₂OH+OH $→$ CH₃CH₂O+H₂O	64.6	34.7
	CH₃CH₂OH+ $→$ CH₃CH₂O+H	—	154.3
3	CH₃CH₂OH+O $→$ CH₂CH₂OH+OH	33.8	16.4
	CH₃CH₂OH+OH $→$ CH₂CH₂OH+H₂O	—	83.0
	CH₃CH₂OH+ $→$ CH₂CH₂OH+H	—	193.9
4	CH₃CH₂OH+O $→$ CH₃CHOH+OH	74.3	-1.9
	CH₃CH₂OH+OH $→$ CH₃CHOH+H₂O	—	100.3
	CH₃CH₂OH+ $→$ CH₃CHOH+H	—	192.0
5	CH₃CH₂O+O $→$ CH₃CHO+OH	38.6	-212.3
	CH₃CH₂O+OH $→$ CH₃CHO+ H₂O	62.7	-73.3
	CH₃CH₂O+ $→$ CH₃CHO+ H	46.3	2.9
6	CH₃CH₂O+O $→$ CH₂CH₂O+OH	95.5	-5.8
	CH₃CH₂O+OH $→$ CH₂CH₂O+H₂O	—	62.7
	CH₃CH₂O+ $→$ CH₂CH₂O+ H	—	139.9
7	CH₃CHO+O $→$ CH₃CO+OH	67.5	-41.5
	CH₃CHO+ $→$ CH₃CO+H	—	120.6
	CH₃CHO+OH $→$ CH₃CO+H₂O	102.3	29.9
8	CH₃CHO+O $→$ CH₂CHO+OH	49.2	-21.2
	CH₃CHO+OH $→$ CH₂CHO+H₂O	31.8	11.6
	CH₃CHO+ $→$ CH₂CHO+H	—	128.3
9	CH₂CHO+O $→$ CH₂CO+OH	29.9	-33.8
	CH₂CHO+OH $→$ CH₂CO+H₂O	59.8	-26.1
	CH₂CHO+ $→$ CH₂CO+H	—	63.7
10	CH₂CHO+O $→$ CHCHO+OH	61.8	19.3
	CH₂CHO+OH $→$ CHCHO+H₂O	54.0	47.3
	CH₂CHO+ $→$ CHCHO+H	—	165.0
11	CH₂CO+O $→$ CHCO+OH	33.8	-26.1
	CH₂CO+OH $→$ CHCO+H₂O	101.3	-17.4
	CH₂CO+O $→$ CH₂COO*	6.8	-115.8
12	CHCO+O $→$ CCO+OH	21.2	-30.9
	CHCO+OH $→$ CCO+H₂O	16.4	-28.0
	CHCO+O $→$ CHCOO+	15.4	-93.6
13	CCO+O $→$ CCOO+	21.2	-100.3
14	CH₃CO+ $→$ CH₃+CO	173.7	106.1
	CH₂CO+ $→$ CH₂+CO	—	228.7
	CHCO+ $→$ CH+CO	—	225.8
15	CH₂COO+ $→$ CH₂+CO₂	155.3	38.6
	CHCOO+ $→$ CH+CO₂	137.0	9.7
	CCOO+ $→$ C+CO₂	126.4	-13.5
16	CCO+O $→$ OCCO+	53.1	-83.5

表4 Ag(211)表面乙醇氧化反应基元步骤反应热和活化能

Table 4 Activation barriers and reaction energies for elementary reaction steps on Ag(211)

编号	基元反应	E _a/ (kJ/mol)	E _r/ (kJ/mol)
1	O₂* $→$ O+O	60.8	-65.2
2	CH₃CH₂OH+O $→$ CH₃CH₂O+OH	2.9	-32.8
	CH₃CH₂OH+OH $→$ CH₃CH₂O+H₂O	31.8	22.2
	CH₃CH₂OH+ $→$ CH₃CH₂O+H	—	84.9
3	CH₃CH₂OH+O $→$ CH₂CH₂OH+OH	86.8	3.8
	CH₃CH₂OH+OH $→$ CH₂CH₂OH+H₂O	98.4	54.0
	CH₃CH₂OH+ $→$ CH₂CH₂OH+H	—	151.5
4	CH₃CH₂OH+O $→$ CH₃CHOH+OH	51.1	2.9
	CH₃CH₂OH+OH $→$ CH₃CHOH+H₂O	166.9	46.3
	CH₃CH₂OH+ $→$ CH₃CHOH+H	—	138.0
5	CH₃CH₂O+O $→$ CH₃CHO+OH	19.3	-175.6
	CH₃CH₂O+OH $→$ CH₃CHO+ H₂O	42.4	-64.6
	CH₃CH₂O+ $→$ CH₃CHO+ H	40.5	-2.9
6	CH₃CH₂O+O $→$ CH₂CH₂O+OH	98.4	-24.1
	CH₃CH₂O+OH $→$ CH₂CH₂O+H₂O	58.8	-67.5
	CH₃CH₂O+ $→$ CH₂CH₂O+ H	—	165.9
7	CH₃CHO+O $→$ CH₃CO+OH	56.0	-43.4
	CH₃CHO+ $→$ CH₃CO+H	115.8	100.3
	CH₃CHO+OH $→$ CH₃CO+H₂O	68.5	22.2
8	CH₃CHO+O $→$ CH₂CHO+OH	6.7	-56.0
	CH₃CHO+OH $→$ CH₂CHO+H₂O	7.7	7.7
	CH₃CHO+ $→$ CH₂CHO+H	—	93.6
9	CH₂CHO+O $→$ CH₂CO+OH	42.4	-76.2
	CH₂CHO+OH $→$ CH₂CO+H₂O	66.6	-43.4
	CH₂CHO+ $→$ CH₂CO+H	112.9	69.5
10	CH₂CHO+O $→$ CHCHO+OH	113.8	-25.1
	CH₂CHO+OH $→$ CHCHO+H₂O	81.0	30.9
	CH₂CHO+ $→$ CHCHO+H	—	150.5
11	CH₂CO+O $→$ CHCO+OH	0	-97.4
	CH₂CO+OH $→$ CHCO+H₂O	15.4	-17.4
	CH₂CO+O $→$ CH₂COO*	0	-163.0
12	CHCO+O $→$ CCO+OH	36.7	-50.2
	CHCO+OH $→$ CCO+H₂O	47.3	11.6
	CHCO+O $→$ CHCOO+	0	-123.5
13	CCO+O $→$ CCOO+	110.0	-16.4
14	CH₃CO+ $→$ CH₃+CO	136.0	60.8
	CH₂CO+ $→$ CH₂+CO	169.8	133.1
	CHCO+ $→$ CH+CO	—	208.4
15	CH₂COO+ $→$ CH₂+CO₂	95.5	34.3
	CHCOO+ $→$ CH+CO₂	103.2	37.6
	CCOO+ $→$ C+CO₂	85.9	17.5

表4 Ag(211)表面乙醇氧化反应基元步骤反应热和活化能

Table 4 Activation barriers and reaction energies for elementary reaction steps on Ag(211)

编号	基元反应	E _a/ (kJ/mol)	E _r/ (kJ/mol)
1	O₂* $→$ O+O	60.8	-65.2
2	CH₃CH₂OH+O $→$ CH₃CH₂O+OH	2.9	-32.8
	CH₃CH₂OH+OH $→$ CH₃CH₂O+H₂O	31.8	22.2
	CH₃CH₂OH+ $→$ CH₃CH₂O+H	—	84.9
3	CH₃CH₂OH+O $→$ CH₂CH₂OH+OH	86.8	3.8
	CH₃CH₂OH+OH $→$ CH₂CH₂OH+H₂O	98.4	54.0
	CH₃CH₂OH+ $→$ CH₂CH₂OH+H	—	151.5
4	CH₃CH₂OH+O $→$ CH₃CHOH+OH	51.1	2.9
	CH₃CH₂OH+OH $→$ CH₃CHOH+H₂O	166.9	46.3
	CH₃CH₂OH+ $→$ CH₃CHOH+H	—	138.0
5	CH₃CH₂O+O $→$ CH₃CHO+OH	19.3	-175.6
	CH₃CH₂O+OH $→$ CH₃CHO+ H₂O	42.4	-64.6
	CH₃CH₂O+ $→$ CH₃CHO+ H	40.5	-2.9
6	CH₃CH₂O+O $→$ CH₂CH₂O+OH	98.4	-24.1
	CH₃CH₂O+OH $→$ CH₂CH₂O+H₂O	58.8	-67.5
	CH₃CH₂O+ $→$ CH₂CH₂O+ H	—	165.9
7	CH₃CHO+O $→$ CH₃CO+OH	56.0	-43.4
	CH₃CHO+ $→$ CH₃CO+H	115.8	100.3
	CH₃CHO+OH $→$ CH₃CO+H₂O	68.5	22.2
8	CH₃CHO+O $→$ CH₂CHO+OH	6.7	-56.0
	CH₃CHO+OH $→$ CH₂CHO+H₂O	7.7	7.7
	CH₃CHO+ $→$ CH₂CHO+H	—	93.6
9	CH₂CHO+O $→$ CH₂CO+OH	42.4	-76.2
	CH₂CHO+OH $→$ CH₂CO+H₂O	66.6	-43.4
	CH₂CHO+ $→$ CH₂CO+H	112.9	69.5
10	CH₂CHO+O $→$ CHCHO+OH	113.8	-25.1
	CH₂CHO+OH $→$ CHCHO+H₂O	81.0	30.9
	CH₂CHO+ $→$ CHCHO+H	—	150.5
11	CH₂CO+O $→$ CHCO+OH	0	-97.4
	CH₂CO+OH $→$ CHCO+H₂O	15.4	-17.4
	CH₂CO+O $→$ CH₂COO*	0	-163.0
12	CHCO+O $→$ CCO+OH	36.7	-50.2
	CHCO+OH $→$ CCO+H₂O	47.3	11.6
	CHCO+O $→$ CHCOO+	0	-123.5
13	CCO+O $→$ CCOO+	110.0	-16.4
14	CH₃CO+ $→$ CH₃+CO	136.0	60.8
	CH₂CO+ $→$ CH₂+CO	169.8	133.1
	CHCO+ $→$ CH+CO	—	208.4
15	CH₂COO+ $→$ CH₂+CO₂	95.5	34.3
	CHCOO+ $→$ CH+CO₂	103.2	37.6
	CCOO+ $→$ C+CO₂	85.9	17.5

图4 Ag(111)表面乙醇氧化反应路线

Fig.4 Preferred reaction pathway of ethanol oxidation on Ag(111)

图5 Ag(211)表面乙醇氧化反应路线

Fig.5 Preferred reaction pathway of ethanol oxidation on Ag(211)

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