高等学校化学学报2017，Vol.38Issue(3)：429-441,13.DOI:10.7503/cjcu20160775
n(H2O)(n=1,2)在HO2+NO→HNO3反应中的催化机制研究
Catalytic Effect of n (H2O) (n =1,2) on the Reaction of HO2+NO →HNO3
摘要
Abstract
The mechanism and rate constant for the HO2+NO →HNO3 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+NO →HNO3,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… (H2 O)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+NO→HNO3 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/ktotal 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.关键词
HO2/NO/水簇催化/反应机理/速率常数Key words
HO2/NO/Water-catalyzed/Reaction mechanism/Rate constant分类
化学化工引用本文复制引用
王睿,王志银,李一粒,凤旭凯,宋亮,张田雷,王竹青,靳玲侠,张强,许琼..n(H2O)(n=1,2)在HO2+NO→HNO3反应中的催化机制研究[J].高等学校化学学报,2017,38(3):429-441,13.基金项目
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.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]. （批准号:21603132,21502109）
