低温NH3-SCR新型MnOx@TiO2纳米棒核壳结构催化剂的合成及抗SO2性能研究

doi:10.1016/S1872-2067(18)63059-1

催化学报 ›› 2018, Vol. 39 ›› Issue (4): 821-830.DOI: 10.1016/S1872-2067(18)63059-1

低温NH₃-SCR新型MnO_x@TiO₂纳米棒核壳结构催化剂的合成及抗SO₂性能研究

盛重义^a,c, 麻丁仁^a, 俞丹青^b, 肖香^c, 黄冰洁^a, 杨柳^a, 王圣^d

a 南京师范大学环境学院, 江苏南京 210023;
b 武汉科技大学化学工程与技术学院, 湖北武汉 430081;
c 浙江大学苏州工业技术研究院, 江苏苏州 215163;
d 国电环境保护研究院, 江苏南京 210031

收稿日期:2018-02-19 修回日期:2018-03-12 出版日期:2018-04-18 发布日期:2018-04-08
通讯作者: 杨柳
基金资助:
国家自然科学基金（51508281，41771498）；江苏省高校自然科学研究面上项目（16KJD610001）.

Synthesis of novel MnO_x@TiO₂ core-shell nanorod catalyst for low-temperature NH₃-selective catalytic reduction of NO_x with enhanced SO₂ tolerance

Zhongyi Sheng^a,c, Dingren Ma^a, Danqing Yu^b, Xiang Xiao^c, Bingjie Huang^a, Liu Yang^a, Sheng Wang^d

a School of Environment, Nanjing Normal University, Nanjing 210023, Jiangsu, China;
b School of Chemical Engineering and Technology, Wuhan University of Science and Technology, Wuhan 430081, Hubei, China;
c Suzhou Industrial Technology Research Institute of Zhejiang University, Suzhou 215163, Jiangsu, China;
d State Power Environmental Protection Research Institute, Nanjing 210031, Jiangsu, China

Received:2018-02-19 Revised:2018-03-12 Online:2018-04-18 Published:2018-04-08
Contact: 10.1016/S1872-2067(18)63059-1
Supported by:
The work was supported by the National Natural Foundation of China (51508281, 41771498) and the Program of Natural Science Research of Jiangsu Higher Education Institutions of China (16KJD610001).

摘要/Abstract

摘要：

氮氧化物（NO_x）是造成大气污染的主要来源之一，严重威胁人类的身体健康.选择性催化还原（SCR）技术由于其独特的优势而受到青睐.但SCR催化剂容易受到SO₂的侵蚀而失活，使用寿命降低.开发具有抗硫能力强的高活性催化剂已成为脱硝技术研究的热点.核壳结构催化剂由于其独特的外壳结构能有效地减少活性物质与SO₂的接触，减少催化剂中毒，延长催化剂的使用寿命.而水热合成法能有效控制催化剂的外形结构，动力学外裹法能将物质均匀分布在被包裹物质的表面，两者结合有利于核壳结构催化剂的合成.
本文采用两步法（水热法+动力学外包裹法）制备的MnO_x@TiO₂纳米棒核壳结构低温脱硝催化剂具有高活性、高稳定性和优异的N₂选择性.此外，与MnO_x，TiO₂和MnO_x/TiO₂等纳米材料相比，MnO_x@TiO₂具有更好的SO₂和H₂O抗性，表明MnO_x@TiO₂具备良好的运用前景.采用TEM，HR-TEM，XRD，Raman，BET，XPS，NH₃-TPD和H₂-TPR等方法对催化剂进行了系统的表征.TEM和HR-TEM结果表明，MnO_x@TiO₂表现出明显的核壳结构，且TiO₂颗粒均匀分布在MnO_x纳米棒上.XRD和Raman结果发现MnO_x@TiO₂中含有MnO₂，从而保证了MnO_x@TiO₂具有良好的脱硝活性.同时，BET，NH₃-TPD和H₂-TPR等结果表明，MnO_x@TiO₂具有丰富的中孔结构和路易斯酸位点，以及强氧化还原能力，因而其催化性能提高.根据SO₂侵蚀后的XPS结果，MnO_x@TiO₂与MnO_x/TiO₂相比，两者中的S元素含量差异小，但前者中的Mn⁴⁺降低量远少于后者.表明MnO_x@TiO₂的核壳结构可以在SO₂存在条件下有效地保护活性位点，因而具有更强的SO₂抗性.

关键词: 低温选择性催化还原, 核壳结构, 纳米棒, 二氧化硫抗性, 锰氧化物

Abstract:

In this study, a MnO_x@TiO₂ core-shell catalyst prepared by a two-step method was used for the low-temperature selective catalytic reduction of NO_x with NH₃. The catalyst exhibits high activity, high stability, and excellent N₂ selectivity. Furthermore, it displays better SO₂ and H₂O tolerance than its MnO_x, TiO₂, and MnO_x/TiO₂ counterparts. The prepared catalyst was characterized systematically by transmission electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Raman, BET, X-ray photoelectron spectroscopy, NH₃ temperature-programmed desorption and H₂ temperature-programmed reduction analyses. The optimized MnO_x@TiO₂ catalyst exhibits an obvious core-shell structure, where the TiO₂ shell is evenly distributed over the MnO_x nanorod core. The catalyst also presents abundant mesopores, Lewis-acid sites, and high redox capability, all of which enhance its catalytic performance. According to the XPS results, the decrease in the number of Mn⁴⁺ active centers after SO₂ poisoning is significantly lower in MnO_x@TiO₂ than in MnO_x/TiO₂. The core-shell structure is hence able to protect the catalytic active sites from H₂O and SO₂ poisoning.

Key words: Low-temperature selective catalytic reduction, Core-shell, Nanorod, SO₂ resistance, MnO_x

盛重义, 麻丁仁, 俞丹青, 肖香, 黄冰洁, 杨柳, 王圣. 低温NH₃-SCR新型MnO_x@TiO₂纳米棒核壳结构催化剂的合成及抗SO₂性能研究[J]. 催化学报, 2018, 39(4): 821-830.

Zhongyi Sheng, Dingren Ma, Danqing Yu, Xiang Xiao, Bingjie Huang, Liu Yang, Sheng Wang. Synthesis of novel MnO_x@TiO₂ core-shell nanorod catalyst for low-temperature NH₃-selective catalytic reduction of NO_x with enhanced SO₂ tolerance[J]. Chinese Journal of Catalysis, 2018, 39(4): 821-830.

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低温NH₃-SCR新型MnO_x@TiO₂纳米棒核壳结构催化剂的合成及抗SO₂性能研究

Synthesis of novel MnO_x@TiO₂ core-shell nanorod catalyst for low-temperature NH₃-selective catalytic reduction of NO_x with enhanced SO₂ tolerance

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