物理化学学报 >> 2013, Vol. 29 >> Issue (09): 2027-2034.doi: 10.3866/PKU.WHXB201306171

催化和表面科学 上一篇    下一篇

氨和有机胺对羰基硫与α-Fe2O3非均相反应的影响

张拴勤, 孔令东, 赵希, 罗兰·詹森, 陈建民   

  1. 复旦大学环境科学与工程系, 上海市大气颗粒物污染防治重点实验室, 上海 200433
  • 收稿日期:2013-03-22 修回日期:2013-06-17 发布日期:2013-08-28
  • 通讯作者: 孔令东, 陈建民 E-mail:ldkong@fudan.edu.cn;jmchen@fudan.edu.cn
  • 基金资助:

    国家自然科学基金(21077025, 21277028, 21190053);上海市科学技术委员会项目(10231203801, 10JC1401600)资助

Effects of Ammonia and Amines on Heterogeneous Oxidation of Carbonyl Sulfide on Hematite

ZHANG Shuan-Qin, KONG Ling-Dong, ZHAO Xi, Roel JANSEN, CHEN Jian-Min   

  1. Shanghai Key Laboratory of Atmospheric Particle Pollution and Prevention, Department of Environmental Science & Engineering, Fudan University, Shanghai 200433, P. R. China
  • Received:2013-03-22 Revised:2013-06-17 Published:2013-08-28
  • Contact: KONG Ling-Dong, CHEN Jian-Min E-mail:ldkong@fudan.edu.cn;jmchen@fudan.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21077025, 21277028, 21190053) and Science&Technology Commission of Shanghai Municipality, China (10231203801, 10JC1401600).

摘要:

利用原位漫反射傅里叶红外光谱(DRIFTS), 考察了室温下羰基硫(COS)在经氨气和有机胺预吸附的α-Fe2O3上的非均相反应, 并同时比较了氨气和不同有机胺(甲胺、三甲胺、三乙胺、苯胺、吡啶和吡咯)对反应活性的影响及其反应动力学. 结果表明, 经碱性物质预吸附后, COS可在α-Fe2O3表面发生氧化反应, 主要产物为气态CO2、表面HCO3-、表面CO32-和表面SO42-, 且α-Fe2O3表面预吸附的碱性物质大大提高了COS在α-Fe2O3上的反应能力, 在碱性物质的影响中, 甲胺对反应的促进能力最大, 相比纯α-Fe2O3反应的反应活性提高了约4.5倍, 然而苯胺和吡咯对COS的反应影响不是很明显.观察到的不同碱性物质对COS的转化能力依次为: 甲胺>三甲胺>氨气>三乙胺>吡啶>吡咯>苯胺≈纯样品, 受碱性物质的影响, COS的反应级数由一级转变为二级. 此外, 研究也发现碱性物质的覆盖度和表面吸附水对COS转化能力存在一定的影响. 这些实验结果表明在碱性物质存在下,表面M―O-是COS在α-Fe2O3发生氧化反应的关键活性位点, 对反应活性的贡献较大, 并在此基础上探讨碱性条件下COS的反应转化机制.

关键词: 羰基硫, 氨气, 有机胺, α-Fe2O3, 非均相反应

Abstract:

The heterogeneous oxidation of carbonyl sulfide (COS) on hematite pre-adsorbed with ammonia and methylamine, trimethylamine, triethylamine, phenylamine, pyridine, and pyrrole was investigated using in situ diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS) at room temperature. The products and kinetics of the heterogeneous reaction were investigated. The results showed that adsorbed COS could be oxidized on the surface of hematite pre-adsorbed with these basic substances, forming gaseous carbon dioxide (CO2), surface bicarbonate (HCO3-), surface carbonate (CO32-), and surface SO42-. Ammonia and amines pre-adsorbed on hematite significantly enhanced the reactivity of COS. Hematite with pre-adsorbed methylamine exhibited the highest reactivity, about 4.5 times higher than that of pure hematite, whereas the effects of phenylamine and pyrrole were not obvious. The reaction rates with the basic substances were in the order of methylamine>trimethylamine>ammonia>triethylamine>pyridine> pyrrole> phenylamine≈pure hematite. The basic substances changed the reaction order from first to second. Coverage by the basic substances and surface water also played important roles in the heterogeneous reaction of COS. These experimental results indicated that surface oxygen species (M―O-) were the key factor contributing to oxidizing activities in the presence of basic substances. The heterogeneous oxidation mechanism of COS on hematite with pre-adsorbed basic substances is discussed on the basis of the experimental results.

Key words: Carbonyl sulfide, Ammonia, Amine, Hematite, Heterogeneous reaction

MSC2000: 

  • O647