Density functional study of selective oxidation of ethanol over silver catalysts

doi:10.11949/0438-1157.20190480

Abstract

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

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

CLC Number:

TQ 032.4

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.

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.

Figures/Tables 9

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

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

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

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

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

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

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

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

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

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

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

References 29

1	Nair H , Liszka M J , Gatt J E , et al . Effects of metal oxide domain size, dispersion, and interaction in mixed WO _x /MoO _x catalysts supported on Al₂O₃ for the partial oxidation of ethanol to acetaldehyde[J]. J. Phy. Chem. C, 2008, 112(5): 1612-1620.
2	Chimentão R J , Herrera E , Kwak J H , et al . Oxidation of ethanol to acetaldehyde over Na-promoted vanadium oxide catalyst[J]. Appl. Catal. A, 2007, 332(2): 263-272.
3	Sheldon R A , Arends I , ten Brink G , et al . Green, catalytic oxidations of alcohols[J]. Acc. Chem. Res., 2002, 35(9): 774-781.
4	李振宇, 李顶杰, 黄格省, 等 . 燃料乙醇发展现状及思考[J]. 化工进展, 2013, 32(7): 1457-1467.
	Li Z Y , Li D J , Huang G S , et al . Insights on current development of fuel ethanol[J]. Chem. Ind. & Eng. Pro., 2013, 32(7): 1457-1467.
5	Shi Z Z , Zhang C , Tang C H , et al . Recent advances in transition-metal catalyzed reactions using molecular oxygen as the oxidant[J]. Chem. Soc. Rev., 2012, 41(8): 3381-3430.
6	王洁莹, 陈声培, 孙世刚, 等 . 纳米FePt/GC催化剂的制备及其对乙醇的电氧化性能[J]. 化工学报, 2010, 61(S1): 101-105.
	Wang J Y , Chen S P , Sun S G , et al . Preparation of FePt/GC nanocatalysts and their electrocatalytic activities for ethanol oxidation[J]. CIESC Journal, 2010, 61(S1): 101-105.
7	王亮, 孟祥举, 肖丰收 . 水滑石负载Au纳米粒子的制备及其催化醇氧化反应[J]. 催化学报, 2010, 31(8): 943-947.
	Wang L , Meng X J , Xiao F S . Au nanoparticles supported on a layered double hydroxide with excellent catalytic properties for the aerobic oxidation of alcohols[J]. Chinese J. Catal., 2010, 31(8): 943-947.
8	Jørgensen B , Christiansen S E , Thomsen M L D , et al . Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: efficient routes to acetic acid and ethyl acetate[J]. J. Catal., 2007, 251(2): 332-337.
9	Takei T , Iguchi N , Haruta M . Synthesis of acetoaldehyde, acetic acid, and others by the dehydrogenation and oxidation of ethanol[J]. Catal. Surv. Asia, 2011, 15(2): 80-88.
10	Christensen C H , Jørgensen B , Andersen H , et al . Formation of acetic acid by aqueous-phase oxidation of ethanol with air in the presence of a heterogeneous gold catalyst[J]. Angew. Chem. Int. Ed., 2006, 45(28): 4648-4651.
11	Gong J L , Mullins C B . Selective oxidation of ethanol to acetaldehyde on gold[J]. J. Am. Chem. Soc., 2008, 130(49): 16458-16459.
12	de Lima S , Davis B H , Noronha F B . Steam reforming, partial oxidation, and oxidative steam reforming of ethanol over Pt/CeZrO₂ catalyst[J]. J. Catal., 2008, 257(2): 356-368.
13	Ali A H , Zaera F . Kinetic study on the selective catalytic oxidation of 2-propanol to acetone over nickel foils[J]. J. Mol. Catal. A, 2002, 177(2): 215-235.
14	Faith W L , Keyes D B , Clark R L . Industrial Chemicals[M]. 2nd ed.New York: John Wiley & Sons, Inc., 1957: 325.
15	Xu J , Xu X C , Yang X J , et al . Silver/hydroxyapatite foam as a highly selective catalyst for acetaldehyde production via ethanol oxidation[J]. Catal. Today, 2016, 276(1): 19-27.
16	Yang Z , Li J , Yang X , et al . Gas-phase oxidation of alcohols over silver: the extension of catalytic cycles of oxidation of alcohols in liquid-phase[J]. J. Mol. Catal. A, 2005, 241(1/2): 15-22.
17	Chen J , Tang X , Liu J , et al . Synthesis and characterization of Ag-hollandite nanofibers and its catalytic application in ethanol oxidation[J]. Chem. Mater., 2007, 19(17): 4292-4299.
18	Wachs I E , Madix R J . The oxidation of methanol on a silver (110) catalyst[J]. Surf. Sci., 1978, 76(2): 531-558.
19	Wachs I E , Madix R J . The oxidation of ethanol on Cu(110) and Ag(110) catalysts[J]. Appl. Surf. Sci., 1978, 1(3): 303-328.
20	Sim W S , Gardner P , King D A . Structure and reactivity of the surface methoxy species on Ag(111)[J]. J. Phys. Chem., 1995, 99(43): 16002-16010.
21	Perdew J P , Pederson M R , Singh D J , et al . Atoms, molecules, solids, and surfaces: applications of the generalized gradient approximation for exchange and correlation[J]. Phys. Rev. B, 1992, 46(11): 6671-6683.
22	Blöchl B E . Projector augmented-wave method[J]. Phys. Rev. B, 1994, 50(24): 17953-17979.
23	Kresse G , Joubert D . From ultrasoft pseudopotentials to the projector augmented-wave method[J]. Phys. Rev. B, 1999, 59(3): 1758-1775.
24	Li J , Zhuang Y , Lin W . Measurement of Ag lattice parameters by magnetic and electronic techniques[J]. J. Alloy. Compd., 1993, 191(3): 187-193.
25	Sheppard D , Xiao P , Chemelewski W , et al . A generalized solid-state nudged elastic band method[J]. J. Chem. Phys., 2012, 136(7): 103-115.
26	Henkelman G , Uberuaga B P , Jónsson H . A climbing image nudged elastic band method for finding saddle points and minimum energy paths[J]. J. Chem. Phys., 2000, 113(22): 9901-9923.
27	Alcalá R , Mavrikakis M , Dumesic J A . DFT studies for cleavage of C-C and C-O bonds in surface species derived from ethanol on Pt(111)[J]. J. Catal., 2003, 218(1): 178-190.
28	Wang H F , Liu Z P . Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network[J]. J. Am. Chem. Soc., 2008, 139(33): 10996-11004.
29	Ferrin P , Simonetti D , Nørskov J K , et al . Modeling ethanol decomposition on transition metals: a combined application of scaling and Brønsted-Evans-Polanyi relations[J]. J.Am. Chem. Soc., 2009, 131(16): 5809-5815.

[1]	Minghao SONG, Fei ZHAO, Shuqing LIU, Guoxuan LI, Sheng YANG, Zhigang LEI. Multi-scale simulation and study of volatile phenols removal from simulated oil by ionic liquids [J]. CIESC Journal, 2023, 74(9): 3654-3664.
[2]	Jianbo HU, Hongchao LIU, Qi HU, Meiying HUANG, Xianyu SONG, Shuangliang ZHAO. Molecular dynamics simulation insight into translocation behavior of organic cage across the cellular membrane [J]. CIESC Journal, 2023, 74(9): 3756-3765.
[3]	Jiajia ZHAO, Shixiang TIAN, Peng LI, Honggao XIE. Microscopic mechanism of SiO₂-H₂O nanofluids to enhance the wettability of coal dust [J]. CIESC Journal, 2023, 74(9): 3931-3945.
[4]	Yepin CHENG, Daqing HU, Yisha XU, Huayan LIU, Hanfeng LU, Guokai CUI. Application of ionic liquid-based deep eutectic solvents for CO₂ conversion [J]. CIESC Journal, 2023, 74(9): 3640-3653.
[5]	Linzheng WANG, Yubing LU, Ruizhi ZHANG, Yonghao LUO. Analysis on thermal oxidation characteristics of VOCs based on molecular dynamics simulation [J]. CIESC Journal, 2023, 74(8): 3242-3255.
[6]	Ji CHEN, Ze HONG, Zhao LEI, Qiang LING, Zhigang ZHAO, Chenhui PENG, Ping CUI. Study on coke dissolution loss reaction and its mechanism based on molecular dynamics simulations [J]. CIESC Journal, 2023, 74(7): 2935-2946.
[7]	Yaxin CHEN, Hang YUAN, Guanzhang LIU, Lei MAO, Chun YANG, Ruifang ZHANG, Guangya ZHANG. Advances in enzyme self-immobilization mediated by protein nanocages [J]. CIESC Journal, 2023, 74(7): 2773-2782.
[8]	Xiaoling TANG, Jiarui WANG, Xuanye ZHU, Renchao ZHENG. Biosynthesis of chiral epichlorohydrin by halohydrin dehalogenase based on Pickering emulsion system [J]. CIESC Journal, 2023, 74(7): 2926-2934.
[9]	Ming DONG, Jinliang XU, Guanglin LIU. Molecular dynamics study on heterogeneous characteristics of supercritical water [J]. CIESC Journal, 2023, 74(7): 2836-2847.
[10]	Tan ZHANG, Guang LIU, Jinping LI, Yuhan SUN. Performance regulation strategies of Ru-based nitrogen reduction electrocatalysts [J]. CIESC Journal, 2023, 74(6): 2264-2280.
[11]	Lei MAO, Guanzhang LIU, Hang YUAN, Guangya ZHANG. Efficient preparation of carbon anhydrase nanoparticles capable of capturing CO₂ and their characteristics [J]. CIESC Journal, 2023, 74(6): 2589-2598.
[12]	Yuanchao LIU, Xuhao JIANG, Ke SHAO, Yifan XU, Jianbin ZHONG, Zhuan LI. Influence of geometrical dimensions and defects on the thermal transport properties of graphyne nanoribbons [J]. CIESC Journal, 2023, 74(6): 2708-2716.
[13]	Hao GU, Fujian ZHANG, Zhen LIU, Wenxuan ZHOU, Peng ZHANG, Zhongqiang ZHANG. Desalination performance and mechanism of porous graphene membrane in temporal dimension under mechanical-electrical coupling [J]. CIESC Journal, 2023, 74(5): 2067-2074.
[14]	Chenxin LI, Yanqiu PAN, Liu HE, Yabin NIU, Lu YU. Carbon membrane model based on carbon microcrystal structure and its gas separation simulation [J]. CIESC Journal, 2023, 74(5): 2057-2066.
[15]	Tianhao BAI, Xiaowen WANG, Mengzi YANG, Xinwei DUAN, Jie MI, Mengmeng WU. Study on release and inhibition behavior of COS during high-temperature gas desulfurization process using Zn-based oxide derived from hydrotalcite [J]. CIESC Journal, 2023, 74(4): 1772-1780.