NH3与Cl2在γ-Al2O3颗粒物表面的非均相反应

doi:10.6023/A18090401

化学学报 ›› 2019, Vol. 77 ›› Issue (2): 160-165.DOI: 10.6023/A18090401 上一篇下一篇

研究论文

NH₃与Cl₂在γ-Al₂O₃颗粒物表面的非均相反应

唐思群^a,b, 马玲玲^a, 罗敏^a, 张朝晖^c, 邱烨^c, 冯烁^c, 夏传琴^b, 金永东^b, 徐殿斗^a

a 中国科学院高能物理研究所核技术应用研究中心北京 100049;
b 四川大学化学学院成都 610064;
c 北京出入境检验检疫局检验检疫技术中心北京 100026

投稿日期:2018-09-25 发布日期:2018-12-05
通讯作者: 马玲玲,E-mail:malingling@ihep.ac.cn;徐殿斗,E-mail:xudd@ihep.ac.cn E-mail:malingling@ihep.ac.cn;xudd@ihep.ac.cn
基金资助:
项目受国家自然科学基金（Nos.U1832212，11405184，11575210，91643206）和中科院重点部署项目（No.ZDRW-CN-2018-1）资助.

Heterogeneous Reaction of NH₃ and Cl₂ on the Surface of γ-Al₂O₃ Particles

Tang Siqun^a,b, Ma Lingling^a, Luo Min^a, Zhang Zhaohui^c, Qiu Ye^c, Feng Shuo^c, Xia Chuanqin^b, Jin Yongdong^b, Xu Diandou^a

a Division of Nuclear Technology and Applications, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049;
b College of Chemistry, Sichuan University, Chengdu 610064;
c Beijing Entry-Exit Inspection and Quarantine Bureau Technology Centre, Beijing 100026

Received:2018-09-25 Published:2018-12-05
Contact: 10.6023/A18090401 E-mail:malingling@ihep.ac.cn;xudd@ihep.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. U1832212, 11405184, 11575210, 91643206) and the Key Deployment Projects of Chinese Academy of Sciences (No. ZDRW-CN-2018-1).

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摘要/Abstract

使用离子色谱分析了常温、常压、湿润和氧气存在条件下，NH₃和Cl₂在γ-Al₂O₃颗粒物表面非均相反应的产物及其受NH₃浓度、反应时间等的影响；并定量分析了NH₃、Cl₂、SO₂和NO₂单独及共存条件下，γ-Al₂O₃表面Cl^-、NO₃^-和SO₄^2-等二次无机颗粒物的生成总量.结果表明：NH₃和Cl₂在γ-Al₂O₃表面具有协同作用，2 h后Cl^-的生成总量可达589.65 μg，其生成量随时间延长而不断增加.表面氯化物的生成量在NH₃浓度为400 ppm时达到峰值，且随NH₃浓度的增加呈先增加而后减少的趋势.活性氯存在下，NH₃对颗粒物表面Cl^-、NO₃^-和SO₄^2-的生成有促进作用，且四种气体共存时复合正反馈效应最明显.同时，本研究对NH₃和Cl₂在颗粒物表面的非均相反应机理及活性氯和氨的排放对大气中二次无机颗粒物的贡献进行了探讨.

关键词: 非均相反应, 二次无机颗粒物, NH₃, Cl₂

The effect of NH₃ concentration, reaction time and other conditions on the heterogeneous reaction of NH₃ and Cl₂ on the surface of γ-Al₂O₃ particles was investigated at the room temperature, pressure and in the presence of oxygen by ion chromatography (IC). The formation of the surface species (Cl^-, NO₃^-, and SO₄^2-) via both individual reaction and co-existing reaction of NH₃, Cl₂, SO₂ and NO₂ on the surface of γ-Al₂O₃ was investigated as well. The results revealed that NH₃ (400 ppm) and Cl₂ (400 ppm) had synergistic effect on the surface γ-Al₂O₃, and the total yield of Cl^- was 589.65 μg after reaction of 2 h. The formation of the surface chlorides increased firstly and then decreased with the increase of ammonia concentration, and the maximum yield of Cl^- was reached at 400 ppm of NH₃. In the presence of active chlorine, NH₃ significantly promoted the generation of the adsorptive species on the surface, such as Cl^-, NO₃^- and SO₄^2-, and the most obvious synergistic effect was induced to form on the conditions of four gases co-existence. The heterogeneous reaction mechanism of NH₃ with Cl₂ and the influence on the atmospheric environment were also discussed as well. Additionally, the mixing ratios used in the study are extremely high compared with ambient levels, which could be as a simulation to explore whether the synergistic effect obtained in this paper are also present in the real ambient conditions. We have studied a relatively low mixing ratios for heterogeneous reaction experiments, but the content of nitrate and chloride on the surface of γ-Al₂O₃ were lower than the limit of detection of ion chromatography. Therefore, other researches such as Knudsen cell and smog chamber study, field monitoring, and mode study are also worth for exploring in future study. The results of this study could provide reference data for the study of the contribution of active chlorine and ammonia to the formation of secondary inorganic particles.

Key words: heterogeneous reaction, secondary inorganic particles, NH₃, Cl₂

引用此文

唐思群, 马玲玲, 罗敏, 张朝晖, 邱烨, 冯烁, 夏传琴, 金永东, 徐殿斗. NH₃与Cl₂在γ-Al₂O₃颗粒物表面的非均相反应[J]. 化学学报, 2019, 77(2): 160-165.

Tang Siqun, Ma Lingling, Luo Min, Zhang Zhaohui, Qiu Ye, Feng Shuo, Xia Chuanqin, Jin Yongdong, Xu Diandou. Heterogeneous Reaction of NH₃ and Cl₂ on the Surface of γ-Al₂O₃ Particles[J]. Acta Chim. Sinica, 2019, 77(2): 160-165.

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[1] Kang, W.-B.; Xia, Y.; Wang, J.; Wang, W. Acta Chim. Sinica 2016, 74, 694. (康文斌, 夏耘, 王骏, 王炜, 化学学报, 2016, 74, 694.)
[2] Zhu, T.; Sang, J.; Zhao, D.-F. Sci. Sinica Chim. 2010, 40, 1731. (朱彤, 尚静, 赵德峰, 中国科学:化学, 2010, 40, 1731.)
[3] Hu, M.; Shang, D.-J.; Guo, S.; Wu, Z.-J. Acta Chim. Sinica 2016, 74, 385. (胡敏, 尚冬杰, 郭松, 吴志军, 化学学报, 2016, 74, 385.)
[4] Zhang, R.; Wang, G.; Guo, S.; Zamora, M.-L.; Ying, Q.; Lin, Y.; Wang, W.; Hu, M.; Wang, Y. Chem. Rev. 2015, 115, 3803.
[5] Behera, S. N.; Sharma, M. Atmos. Environ. 2011, 45, 4015.
[6] Yu, X.-C.; He, K.-B.; Ma, Y.-L.; Duan, F.-K.; Yang, F.-R. China Environ. Sci. 2004, 24, 53. (余学春, 贺克斌, 马永亮, 段风魁, 杨复沫, 中国环境科学, 2004, 24, 53.)
[7] Xu, W.-B.; Xu, Y.-L.; Tang, X.-L.; Lei, Y.; Wang, J.-N. China Environ. Sci. 2016, 36, 3531. (薛文博, 许艳玲, 唐晓龙, 雷宇, 王金南, 中国环境科学, 2016, 36, 3531.)
[8] Zhao, D.-F.; Song, X.-J.; Zhu, T.; Zhang, Z.-F.; Liu, Y.-J.; Shang, J. Atmos. Chem. Phys. 2018, 18, 2481.
[9] Wu, L.-Y.; Tong, S.-R.; Wang, W.-G.; Ge, M.-F. Atmos. Chem. Phys. 2011, 11, 6593.
[10] Clegg, S. M.; Abbatt, J. P. D. Atmos. Chem. Phys. 2001, 1, 73.
[11] Huang, L. B.; Zhao, Y.; Li, H.; Chen, Z. M. Environ. Sci. Technol. 2015, 49, 10797.
[12] Xie, S. D.; Yu, T.; Zhang, Y. H.; Zeng, L. M.; Qi, L.; Tang, X. Y. Sci. Total Environ. 2005, 345, 153.
[13] Bedjanian, Y.; Poulet, G. Chem. Rev. 2003, 103, 4639.
[14] Ge, M.-F.; Ma, C.-P. Prog. Chem. 2009, 21, 307. (葛茂发, 马春平, 化学进展, 2009, 21, 307.)
[15] Agarwal, H.; Stenger, H. G.; Wu, S.; Fan, Z. Energ. Fuel 2006, 20, 1068.
[16] Ariya, P. A.; Khalizov, A.; Gidas, A. J. Phy. Chem. A 2002, 106, 7310.
[17] Faxon, C.; Bean, J.; Ruiz, L. Atmosphere 2015, 6, 1487.
[18] Liao, J.; Huey, L. G.; Liu, Z.; Tanner, D. J.; Cantrell, C. A.; Orlando, J. J.; Flocke, F. M.; Shepson, P. B.; Weinheimer, A. J.; Hall, S. R.; Ullmann, K.; Beine, H. J.; Wang, Y. H.; Ingall, E. D.; Stephens, C. R.; Hornbrook, R. S.; Apel, E. C.; Riemer, D.; Fried, A.; Mauldin, R. L.; Smith, J. N.; Staebler, R. M.; Neuman, J. A.; Nowak, J. B. Nat. Geosci. 2014, 7, 91.
[19] Liu, X. X; Qu, H.; Huey, G.; Wang, Y. H.; Sjostedt, S.; Zeng, L.; Lu, K. D.; Wu, Y. S.; Hu, M.; Zhu, T.; Zhang, Y. H. Environ. Sci. Technol. 2017, 51, 9588.
[20] Tang, S. Q.; Ma, L. L.; Luo, M.; Zhang, Z. H.; Cao, X. Z.; Huang, Z. L.; Xia, R.; Qiu, Y.; Feng, S.; Zhang, P.; Xia, C. Q.; Jin, Y. D.; Xu, D. D. Atmos. Environ. 2018, 188, 25.
[21] Gard, E. E.; Kleeman, M. J.; Gross, D. S.; Hughes, L. S.; Allen, J. O.; Morrical, B. D.; Fergenson, D. P.; Dienes, T.; Galli, M. E.; Johnson, R. J.; Cass, G. R.; Prather, K. A. Science 1998, 279, 1184.
[22] Chen, H. H.; Navea, J. G.; Young, M. A.; Grassian, V. H. J. Phys. Chem. A 2011, 115, 490.
[23] He, H.; Wang, Y. S.; Ma, Q. X.; Ma, J. Z.; Chu, B. W.; Ji, D. S.; Tang, G. Q.; Liu, C.; Zhang, H. X.; Hao, J. M. Sci. Rep. 2014, 4, 4172.
[24] Xue, W.-B.; Fu, F.; Wang, J.-N.; Tang, G.-Q.; Lei, Y.; Yang, J.-T.; Wang, Y.-S. China Environ. Sci. 2014, 34, 1361. (薛文博, 付飞, 王金南, 唐贵谦, 雷宇, 杨金田, 王跃思, 中国环境科学, 2014, 34, 1361.)
[25] Wang, L.-H.; Zeng, F.-G.; Xiang, W.-L.; Wang, Z.-F.; Yang, W.-Y. China Environ. Sci. 2015, 35, 2546. (王凌慧, 曾凡刚, 向伟玲, 王自发, 杨文夷, 中国环境科学, 2015, 35, 2546.)
[26] Liu, J.; An, X. Q.; Zhu, T.; Zhai, S.-X.; Li, N. China Environ. Sci. 2014, 34, 2726. (刘俊, 安兴琴, 朱彤, 翟世贤, 李楠. 中国环境科学, 2014, 34, 2726.)
[27] Zhang, L.; Chen, Y. F.; Zhao, Y. H.; Henze, D. K.; Zhu, L. Y.; Song, Y.; Paulot, F.; Liu, X. J.; Pan, Y. P.; Lin, Y.; Huang, B. X. Atmos. Chem. Phys. 2018, 18, 339.
[28] Liu, L.; Zhang, X. Y.; Xu, W.; Liu, X. J.; Li, Y.; Lu, X. H.; Zhang, Y. H.; Zhang, W. T. Atmos. Chem. Phys. 2017, 17, 9365.
[29] Pepi, F.; Ricci, A.; Rosi, M. J. Phys. Chem. 2003, 107, 2085.
[30] Veirs, D. K.; Berg, J. M.; Worl, L. A.; Narlesky, J. E; Dunn, K. A.; Louthan, J. M. R. J. Nucl. Mat. Manag. 2010, 38, 25.
[31] Réti, F.; Josepovits, V.; Perczel, I. Appl. Surf. Sci. 1993, 65, 271.
[32] Sisler, H. H.; Neth, F. T.; Drago, R. S.; Yaney, D. J. Am. Chem. Soc. 1954, 76, 3906.
[33] Oldfield, J. W.; Todd, B. Brit. Corros. J. 1991, 26, 173.
[34] Goodman, A. L.; Miller, T. M.; Grassian, V. H. J. V. Sci. Technol. A 1998, 16, 2585.
[35] Miller, T. M.; Grassian, V. H. Geophy. Res. Lett. 1998, 25, 3835.
[36] Mitchell, M. B.; Sheinker, V. N. J. Phys. Chem. 1996, 100, 7550.
[37] Waqif, M.; Saad, A. M.; Bensitel, M.; Bachelier, J.; Saur, O.; Lavalley, J. C. J. Chem. Soc. Faraday. Trans. 1992, 88, 2931.
[38] Ma, Q.; Liu, Y.; He, H. J. Phy. Chem. A 2008, 112, 6630.
[39] Rossi, M. J. Chem. Rev. 2003, 103, 4823.
[40] Schweitzer, F.; Mirabel, P.; George, C. J. Phys. Chem. A 1998, 102, 3942.
[41] Keene, W. C.; Sander, R.; Pszenny, A. A. P.; Vogt, R.; Crutzen, P. J.; Galloway, J. N. J. Aerosol Sci. 1998, 29, 339.
[42] Huang, Z. L.; Zhang, Z. H.; Kong, W. H.; Feng, S.; Qiu, Y.; Tang, S. Q.; Xia, C. Q.; Ma, L. L.; Luo, M.; Xu, D. D. Atmos. Environ. 2017, 166, 403.

NH₃与Cl₂在γ-Al₂O₃颗粒物表面的非均相反应

Heterogeneous Reaction of NH₃ and Cl₂ on the Surface of γ-Al₂O₃ Particles

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