一步水热法合成具有(001)高能晶面的SO42--TiO2及其NH3-SCR脱硝性能

引用本文: 文叶轩, 曹爽, 费晓琦, 王海强, 吴忠标. 一步水热法合成具有(001)高能晶面的SO₄^2--TiO₂及其NH₃-SCR脱硝性能[J]. 催化学报, 2018, 39(4): 771-778. doi: 10.1016/S1872-2067(18)63034-7 shu

Citation: Yexuan Wen, Shuang Cao, Xiaoqi Fei, Haiqiang Wang, Zhongbiao Wu. One-step synthesized SO₄^2--TiO₂ with exposed (001) facets and its application in selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2018, 39(4): 771-778. doi: 10.1016/S1872-2067(18)63034-7 shu

一步水热法合成具有(001)高能晶面的SO₄^2--TiO₂及其NH₃-SCR脱硝性能

a 浙江大学环境与资源学院污染环境修复与生态健康教育部重点实验室, 浙江杭州 310058;
b 浙江省工业锅炉炉窑烟气污染控制工程技术研究中心, 浙江杭州 310027
基金项目:
国家重点研发计划（2016YFC0204100）；浙江省"151"人才计划；浙江省重点科技创新团队计划（2013TD07）；长江学者奖励计划（教育部，2009）.

摘要: 氮氧化物（NO_x）是当今大气环境中的主要污染物之一，氨法选择性催化脱硝技术（NH₃-SCR）是最有前景的烟气脱硝技术之一.在众多的NH₃-SCR催化剂中，钛基催化剂由于其较好的热稳定性、抗硫性和环境友好性成为近年来研究的热点.
本文以SO₄^2-离子作为晶面导向剂，采用一步水热法合成了具有（001）高能晶面的SO₄^2--TiO₂，负载氧化铈后用于SCR反应，并以Ce/P25和Ce/P25-S（浸渍法硫酸化）作为参照对比.研究发现，Ce/TiO₂-001更适合于中、高温NH₃-SCR反应，在290℃时NO转化率已达99%，并且在290-480℃范围内均保持99%的脱硝效率.
利用X射线衍射、N₂吸附脱附、透射电子显微镜、X射线光电子能谱（XPS）、NH₃/O₂程序升温脱附（TPD）、傅里叶原位红外光谱等技术研究了上述催化剂的表面物化性质与脱硝性能的关系.相比于Ce/P25和Ce/P25-S，Ce/TiO₂-001具有更高的比表面积（107m²/g），形成了介孔TiO₂单晶，且晶粒尺寸更小.XPS和NH₃-TPD结果表明，Ce/TiO₂-001表面具有丰富的酸性位.硫酸化可以增加催化剂表面的Brönsted/Lewis酸性位；同时，（001）高能晶面有利于水分子的解离，从而促进酸性位的产生.O₂-TPD表明，Ce/TiO₂-001催化剂表面存在大量化学吸附氧，这与其一步合成中的硫酸化和（001）高能晶面密切相关，而化学吸附氧在中高温SCR反应中起着重要的作用.
通过原位红外分析可得，不同催化剂表面所形成的NO_x吸附物种有所差异，在30℃时，Ce/P25的NO_x吸附物种比较丰富，存在气相NO₂、双齿硝酸盐、线性硝酸盐、单齿硝酸盐和桥式硝酸盐，而Ce/P25-S和Ce/TiO₂-001上的NO_x吸附物种则以单齿硝酸盐/亚硝酸盐为主.随着温度的升高，以上催化剂表面的NO_x吸附物种逐渐变为以气相NO₂和双齿硝酸盐为主.但同种NO_x吸附物种（气相NO₂、双齿硝酸盐）在不同催化剂上的反应活性也有所不同，在250℃时，其顺序为：Ce/TiO₂-001 > Ce/P25-S > Ce/P25，与脱硝性能相符.由此可推测，催化剂表面硫酸化和（001）高能晶面的存在有利于提高NO_x中间产物的反应活性，增加反应速率，从而提高脱硝性能.
综上所述，硫酸化、高比表面积和（001）高能晶面是Ce/TiO₂-001具有很好脱硝活性的重要原因.硫酸化可以提供丰富的酸性位，增强氨的吸附性能；高比表面积不仅可以负载更多的活性组分，而且有利于活性组分的均匀分散，对降低活性中心的尺寸、防止活性组分烧结团聚有积极作用.而（001）高能晶面则可以促进中、强酸和化学吸附氧的形成，活化NO_x吸附物种，从而提高SCR催化活性.

关键词:

English

One-step synthesized SO₄^2--TiO₂ with exposed (001) facets and its application in selective catalytic reduction of NO by NH₃

a Key Laboratory of Environment Remediation and Ecological Health of Ministry of Education, College of Environmental & Resources Sciences, Zhejiang University, Hangzhou 310058, Zhejiang, China;
b Zhejiang Provincial Engineering Research Center of Industrial Boiler & Furnace Flue Gas Pollution Control, Hangzhou 310027, Zhejiang, China
Received Date: 22 December 2017
Revised Date: 23 January 2018
Fund Project:
This work was supported by the National Key R&D Program of China (2016YFC0204100), the Zhejiang Provincial "151" Talents Program, the Program for Zhejiang Leading Team of S&T Innovation (2013TD07), and the Changjiang Scholar Incentive Program (2009).

Abstract: A sample of sulfated anatase TiO₂ with high-energy (001) facets (TiO₂-001) was prepared by a simple one-step hydrothermal route using SO₄^2- as a morphology-controlling agent. After doping ceria, Ce/TiO₂-001 was used as the catalyst for selective catalytic reduction (SCR) of NO with NH₃. Compared with Ce/P25 (Degussa P25 TiO₂) and Ce/P25-S (sulfated P25) catalysts, Ce/TiO₂-001 was more suitable for medium-and high-temperature SCR of NO due to the high surface area, sulfation, and the excellent properties of the active-energy (001) facets. All of these facilitated the generation of abundant acidity, chemisorbed oxygen, and activated NO_x-adsorption species, which were the important factors for the SCR reaction.

Key words:

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一步水热法合成具有(001)高能晶面的SO₄^2--TiO₂及其NH₃-SCR脱硝性能

English

One-step synthesized SO₄^2--TiO₂ with exposed (001) facets and its application in selective catalytic reduction of NO by NH₃

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