n(H2O)(n=1,2)在HO2+NOHNO3反应中的催化机制研究

doi:10.7503/cjcu20160775

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (3): 429.doi: 10.7503/cjcu20160775

n(H₂O)(n=1,2)在HO₂+NOHNO₃反应中的催化机制研究

王睿¹, 李一粒¹, 凤旭凯¹, 宋亮¹, 张田雷¹(), 王竹青², 靳玲侠¹, 张强¹, 许琼¹, 王志银¹

1. 陕西理工大学化学与环境科学学院, 陕西省催化基础与应用重点实验室, 汉中 723001;
2. 四川理工学院分析测试中心, 自贡 643000

收稿日期:2016-11-08 出版日期:2017-03-10 发布日期:2017-02-23
作者简介:联系人简介: 张田雷, 男, 博士, 副教授, 主要从事理论与计算化学研究. E-mail: ztianlei88@163.com
基金资助:
国家自然科学基金(批准号: 21603132, 21502109)、陕西省教育厅项目(批准号: 15JK1138)和陕西理工学院科研计划项目[批准号: SLGQD13(2)-3, SLGQD13(2)-4]资助.

Catalytic Effect of n(H₂O)(n=1,2) on the Reaction of HO₂+NOHNO₃ ^†

WANG Rui¹, LI Yili¹, FENG Xukai¹, SONG Liang¹, ZHANG Tianlei^1,^*(), WANG Zhuqing², JIN Lingxia¹, ZHANG Qiang¹, XU Qiong¹, WANG Zhiyin¹

1. Shaanxi Key Laboratory of Catalysis, School of Chemical and Environment Science, Shaanxi University of Technology, Hanzhong 723001, China;
2. Analytical and Testing Center, Sichuan University of Science & Engineering, Zigong 643000, China;

Received:2016-11-08 Online:2017-03-10 Published:2017-02-23
Contact: ZHANG Tianlei E-mail:ztianlei88@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21603132, 21502109), the Project of Education Department of Shaanxi Province, China(No.15JK1138) and the Funds of Research Programs of Shaanxi Sci-Tech University, China[Nos.SLGQD13(2)-3, SLGQD13(2)-4].

摘要/Abstract

摘要：

采用CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p)方法对n(H₂O)(n=0,1,2)参与HO₂+NOHNO₃反应的微观机理和速率常数进行了研究. 结果表明, 由于水分子与HO₂形成的复合物(H₂O…HO₂, HO₂…H₂O)结合NO与水分子形成的复合物(NO…H₂O, ON…H₂O)的反应方式具有较高能垒和较低有效速率, 其对HO₂+NOHNO₃反应的影响远小于双体水(H₂O)₂与HO₂(或NO)形成复合物然后再与另一分子反应物NO(或HO₂)的反应方式, 因此n(H₂O)(n=1,2)催化HO₂+NOHNO₃反应主要经历了HO₂…(H₂O)_n(n=1,2)+NO和NO…(H₂O)_n(n=1,2)+HO₂ 2种反应类型. 由于HO₂…(H₂O)_n(n=1, 2)+NO反应的低能垒和高速率, HO₂…(H₂O)_n(n=1,2)+NO反应优于NO…(H₂O)_n(n=1,2)+HO₂反应. 与此同时, 由于计算温度范围内HO₂…H₂O+NO反应的有效速率常数比HO₂…(H₂O)₂+NO反应对应的有效速率常数大了10~12数量级, 可推测(H₂O)_n(n=1,2)催化HO₂+NOHNO₃反应主要来自于单个水分子. 此外, 在216.7~298.6 K范围内水分子对HO₂+NOHNO₃反应起显著的正催化作用, 且随温度的升高有明显增大的趋势, 在298.2 K时增强因子k'_RW1/k_total达到67.93%, 表明在实际大气环境中水蒸气对HO₂+NOHNO₃反应具有显著影响.

关键词: HO2, NO, 水簇催化, 反应机理, 速率常数

Abstract:

The mechanism and rate constant for the HO₂+NOHNO₃ reaction, without and with n(H₂O)(n=1,2) was investigated at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-311+G(2df,2p) level. The results show that, incorporation of the catalyst[n(H₂O)(n=1,2)] into the reaction of HO₂+NOHNO₃, the reactions between NO radical and HO₂…(H₂O)_n(n=1,2) complexes are more favorable than the corresponding reactions of HO₂ radical with NO…(H₂O)_n(n=1,2) complexes, as well as the reactions of HO₂…H₂O+NO…H₂O, H₂O…HO₂+NO…H₂O and H₂O…HO₂+ON…H₂O due to the lower barrier of the former reactions and the larger rate constant of the reaction between HO₂…(H₂O)_n(n=1,2) complexes and NO. Meanwhile, the catalytic effect of n(H₂O)(n=1,2) is mainly taken from the contribution of a single water vapor, due to the effective rate constant of H₂O…HO₂+NO reaction was larger by 10—12 orders of magnitude than that of NO+HO₂…(H₂O)₂ reaction. Compared with the reaction of HO₂+NOHNO₃ without water molecule, the single water molecule in H₂O…HO₂+NO reaction has a positive influence on enhancing the rate of HNO₃ formation, and the catalytic effect increase with the temperature increase. At 298.2 K, water vapor shows the most significant catalytic effect with the value of k'_RW1/k_total up to 67.93%, indicating that the single water molecule in H₂O…HO₂+NO channel shows a positive catalytic effect on enhancing the rate of HNO₃ formation under atmospheric conditions.

Key words: HO2, NO, Water-catalyzed, Reaction mechanism, Rate constant

中图分类号:

O643.1

TrendMD:

王睿, 李一粒, 凤旭凯, 宋亮, 张田雷, 王竹青, 靳玲侠, 张强, 许琼, 王志银. n(H₂O)(n=1,2)在HO₂+NOHNO₃反应中的催化机制研究. 高等学校化学学报, 2017, 38(3): 429.

WANG Rui, LI Yili, FENG Xukai, SONG Liang, ZHANG Tianlei, WANG Zhuqing, JIN Lingxia, ZHANG Qiang, XU Qiong, WANG Zhiyin. Catalytic Effect of n(H₂O)(n=1,2) on the Reaction of HO₂+NOHNO₃ ^†. Chem. J. Chinese Universities, 2017, 38(3): 429.

图/表 9

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System	ZPE/ (kJ·mol^-1)	S/ (J·mol^-1·K^-1)	ΔE/ (kJ·mol^-1)	ΔH/ (kJ·mol^-1)	ΔG/ (kJ·mol^-1)	(ΔE+ZPE)/ (kJ·mol^-1)
H₂O+NO+H₂O	0	148.76	0	0	0	0
H₂O…HOO+NO	10.65	121.69	-39.61	-32.02	1.75	-28.96
IMW1	19.36	88.12	-139.85	-125.57	-49.93	-120.49
TSW1	10.94	94.59	-22.68	-6.89	60.68	-3.62
IMWF1	28.94	79.91	-286.55	-266.43	-180.55	-257.62
HOO…H₂O+NO	6.60	129.24	-14.62	-8.34	16.01	-8.02
IMW2	16.05	94.65	-118.16	-105.26	-37.75	-102.11
TSW2	12.34	87.11	-0.17	5.22	82.12	12.16
IMWF2	24.87	91.60	-254.28	-235.17	-163.86	-229.42
NO…H₂O+HOO	2.49	137.10	-4.69	-0.85	13.69	-2.21
IMW3	15.74	95.45	-114.71	-101.86	-35.35	-98.97
TSW3	13.73	85.27	-4.35	1.72	80.92	9.38
IMWF3	25.16	79.93	-254.90	-235.69	-164.31	-229.74
H₂O…NO+HOO	2.92	129.99	-6.35	-4.87	18.54	-3.43
IMW4	16.04	90.76	-123.22	-111.02	-38.67	-107.18
TSW4	11.90	87.65	-2.10	3.82	80.05	9.79
HNO₃+H₂O	20.20	108.67	-242.49	-229.21	-179.20	-222.29

System	ZPE/ (kJ·mol^-1)	S/ (J·mol^-1·K^-1)	ΔE/ (kJ·mol^-1)	ΔH/ (kJ·mol^-1)	ΔG/ (kJ·mol^-1)	(ΔE+ZPE)/ (kJ·mol^-1)
H₂O+NO+H₂O	0	148.76	0	0	0	0
H₂O…HOO+NO	10.65	121.69	-39.61	-32.02	1.75	-28.96
IMW1	19.36	88.12	-139.85	-125.57	-49.93	-120.49
TSW1	10.94	94.59	-22.68	-6.89	60.68	-3.62
IMWF1	28.94	79.91	-286.55	-266.43	-180.55	-257.62
HOO…H₂O+NO	6.60	129.24	-14.62	-8.34	16.01	-8.02
IMW2	16.05	94.65	-118.16	-105.26	-37.75	-102.11
TSW2	12.34	87.11	-0.17	5.22	82.12	12.16
IMWF2	24.87	91.60	-254.28	-235.17	-163.86	-229.42
NO…H₂O+HOO	2.49	137.10	-4.69	-0.85	13.69	-2.21
IMW3	15.74	95.45	-114.71	-101.86	-35.35	-98.97
TSW3	13.73	85.27	-4.35	1.72	80.92	9.38
IMWF3	25.16	79.93	-254.90	-235.69	-164.31	-229.74
H₂O…NO+HOO	2.92	129.99	-6.35	-4.87	18.54	-3.43
IMW4	16.04	90.76	-123.22	-111.02	-38.67	-107.18
TSW4	11.90	87.65	-2.10	3.82	80.05	9.79
HNO₃+H₂O	20.20	108.67	-242.49	-229.21	-179.20	-222.29

System	ZPE/ (kJ·mol^-1)	S/ (J·mol^-1·K^-1)	ΔE/ (kJ·mol^-1)	ΔH/ (kJ·mol^-1)	ΔG/ (kJ·mol^-1)	(ΔE+ZPE)/ (kJ·mol^-1)
HO₂+NO+(H₂O)₂	0	173.153	0	0	0	0
[HO₂…(H₂O)₂]a+NO	14.53	132.57	-66.62	-57.71	-7.08	-52.09
IMWW1	22.08	99.25	-160.58	-145.38	-53.19	-138.51
TSWW1	14.81	88.92	22.32	23.75	128.82	37.12
IMWWF1	30.29	94.70	-308.12	-287.57	-189.70	-277.83
[HO₂…(H₂O)₂]b+NO	11.96	132.40	-28.38	-22.37	28.47	-12.74
IMWW2	21.88	100.62	-164.80	-149.80	-59.31	-142.91
TSWW2	14.86	105.12	-38.97	-30.15	54.71	-24.11
IMWWF2	28.15	101.28	-296.89	-276.46	-186.79	-268.74
NO…(H₂O)₂+HO₂	3.58	152.58	-9.35	-4.72	20.95	-5.77
IMWW3	20.87	90.25	-67.97	-58.68	44.75	-41.70
TSWW3	12.39	101.892	-29.09	-22.47	66.42	-16.70
HNO₃+(H₂O)₂	20.20	133.06	-242.49	-229.21	-179.20	-222.29

System	ZPE/ (kJ·mol^-1)	S/ (J·mol^-1·K^-1)	ΔE/ (kJ·mol^-1)	ΔH/ (kJ·mol^-1)	ΔG/ (kJ·mol^-1)	(ΔE+ZPE)/ (kJ·mol^-1)
HO₂+NO+(H₂O)₂	0	173.153	0	0	0	0
[HO₂…(H₂O)₂]a+NO	14.53	132.57	-66.62	-57.71	-7.08	-52.09
IMWW1	22.08	99.25	-160.58	-145.38	-53.19	-138.51
TSWW1	14.81	88.92	22.32	23.75	128.82	37.12
IMWWF1	30.29	94.70	-308.12	-287.57	-189.70	-277.83
[HO₂…(H₂O)₂]b+NO	11.96	132.40	-28.38	-22.37	28.47	-12.74
IMWW2	21.88	100.62	-164.80	-149.80	-59.31	-142.91
TSWW2	14.86	105.12	-38.97	-30.15	54.71	-24.11
IMWWF2	28.15	101.28	-296.89	-276.46	-186.79	-268.74
NO…(H₂O)₂+HO₂	3.58	152.58	-9.35	-4.72	20.95	-5.77
IMWW3	20.87	90.25	-67.97	-58.68	44.75	-41.70
TSWW3	12.39	101.892	-29.09	-22.47	66.42	-16.70
HNO₃+(H₂O)₂	20.20	133.06	-242.49	-229.21	-179.20	-222.29

h/km	T/K	10¹⁴k_R1	10¹³k_RW1	10¹⁵k'_RW1	10¹¹k_RWW2	10²⁵k'_RWW2	10¹⁵k_RWW3	10²⁸k'_RWW3	10¹³k_total	k'_RW1/k_total(%)
0	298.2	5.69	1.80	381	1.23	566	50.5	0.178	4.38	67.93
0	288.2	5.76	1.68	240	1.33	975	38.6	1.74	2.98	58.83
2	275.2	5.91	1.53	243	1.50	390	23.8	6.47	3.02	61.32
4	262.2	6.14	1.40	200	1.74	220	15.6	35.3	2.61	58.73
6	249.3	6.48	1.29	78.1	2.06	27.0	10.8	410	1.43	37.70
8	236.3	6.97	1.19	46.7	2.55	7.49	7.71	1010	1.16	28.15
10	223.3	7.72	1.12	27.2	3.29	1.85	5.72	2890	1.04	19.57
12	216.7	8.24	1.09	9.92	3.84	0.205	4.64	947	0.923	8.36

n(H₂O)(n=1,2)在HO₂+NOHNO₃反应中的催化机制研究

Catalytic Effect of n(H₂O)(n=1,2) on the Reaction of HO₂+NOHNO₃ ^†

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