MnO<sub>2</sub>的晶相结构和表面性质对低温NH<sub>3</sub>-SCR反应的影响

引用本文: 戴韵, 李俊华, 彭悦, 唐幸福. MnO₂的晶相结构和表面性质对低温NH₃-SCR反应的影响[J]. 物理化学学报, 2012, 28(07): 1771-1776. doi: 10.3866/PKU.WHXB201204175 shu

Citation: DAI Yun, LI Jun-Hua, PENG Yue, TANG Xing-Fu. Effects of MnO₂ Crystal Structure and Surface Property on the NH₃-SCR Reaction at Low Temperature[J]. Acta Physico-Chimica Sinica, 2012, 28(07): 1771-1776. doi: 10.3866/PKU.WHXB201204175 shu

MnO₂的晶相结构和表面性质对低温NH₃-SCR反应的影响

戴韵 ^1, ,
李俊华 ^1, ,
彭悦 ^1, ,
唐幸福 ^2,

基金项目:
国家自然科学基金(51078203) (51078203)

国家高技术研究发展计划项目(863) (2010AA065002, 2009AA06Z301)资助 (863) (2010AA065002, 2009AA06Z301)

摘要:

采用水热法合成了两种具有相同形貌但是不同物相结构的MnO₂纳米棒, 分别为隧道状和层状结构, 考察其低温NH₃选择性催化还原NO_x (NH₃-SCR)的性能. 结果表明MnO₂纳米棒的比表面积不是影响活性的主要因素, 催化剂的晶相结构和表面性质对催化活性有很大影响, 隧道状α-MnO₂纳米棒的低温NH₃-SCR活性明显高于层状δ-MnO₂纳米棒. 结构分析和NH₃程序升温脱附(NH₃-TPD)实验表明, α-MnO₂纳米棒的暴露晶面(110)面存在大量的配位不饱和Mn离子, 形成较多的Lewis 酸性位点, 而且α-MnO₂较弱的Mn―O键和隧道结构都有利于NH₃的吸附; 而δ-MnO₂纳米棒的暴露晶面(001)面上的Mn离子已达到配位饱和, 所以其表面Lewis 酸性位点较少. X射线光电子能谱(XPS)和热重(TG)分析表明α-MnO₂纳米棒的表面更有利于NH₃和NO_x的活化. 具有有利于吸附NH₃和活化NH₃和NO_x的表面性质和晶型结构, 是α-MnO₂纳米棒活性高的主要原因.

关键词:

English

Effects of MnO₂ Crystal Structure and Surface Property on the NH₃-SCR Reaction at Low Temperature

1.
1. State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, P. R. China;
2. Department of Environmental Science and Engineering, Fudan University, Shanghai 200433, P. R. China
Received Date: 06 March 2012
Available Online: 07 June 2012
Fund Project:
国家自然科学基金(51078203)

国家高技术研究发展计划项目(863) (2010AA065002, 2009AA06Z301)资助

Abstract:

Two manganese oxides with the same nanorod-shaped morphology but different crystal structures, tunnel and layer structures, were synthesized and investigated for selective catalytic reduction of NO_x with NH₃ (NH₃-SCR) at low temperature. Tunneled α-MnO₂ had much higher catalytic activity than layered δ-MnO₂ under the same reaction conditions. Experiment results revealed that the surface area was not the main factor to affect the NH₃-SCR activities over the MnO₂ nanorods and that the activities were structure sensitive. Structure analysis and temperature-programmed desorption experiments of NH₃ (NH₃-TPD) suggested that the exposed (110) plane of α-MnO₂ had many Mn cations in coordinatively unsaturated environment, while all of the Mn cations on the exposed (001) plane of δ-MnO₂ were in coordinatively saturated environment. Thus, α-MnO₂ possessed many more Lewis acid sites. Furthermore, α-MnO₂ has weaker Mn―O bonds and an efficient tunnel structure, which are favorable characteristics for NH₃ adsorption. Moreover, X-ray photoelectron spectroscopy (XPS) and thermal gravimetric (TG) analysis indicated that α-MnO₂ obtained a higher capability for NH₃ and NO_x activation than δ-MnO₂. The crystal structure and surface properties of α-MnO₂ are more suitable to the adsorption of NH₃ and activation of NH₃ and NO_x, which accounts for the higher catalytic activity of the α-MnO₂ nanorods.

Key words:

α-MnO₂
/ δ-MnO₂
/ Low-temperature
/ Selective catalytic reduction of NO_x with NH₃
/ Crystal structure
/ Surface property

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沈阳化工大学材料科学与工程学院沈阳 110142

MnO₂的晶相结构和表面性质对低温NH₃-SCR反应的影响

English

Effects of MnO₂ Crystal Structure and Surface Property on the NH₃-SCR Reaction at Low Temperature

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