CeO2表面分散态WO3的氨选择性催化还原性能

doi:10.1016/S1872-2067(17)62887-0

催化学报 ›› 2017, Vol. 38 ›› Issue (10): 1749-1758.DOI: 10.1016/S1872-2067(17)62887-0

CeO₂表面分散态WO₃的氨选择性催化还原性能

张雷^a, 孙敬方^b, 熊燕^c, 曾小清^a, 汤常金^b, 董林^b

a. 重庆三峡学院环境与化学工程学院, 重庆 404000;
b. 南京大学化学化工学院介观化学教育部重点实验室, 江苏南京 210093;
c. 南阳师范学院化学与制药工程学院, 河南南阳 473061

收稿日期:2017-05-31 修回日期:2017-07-06 出版日期:2017-10-18 发布日期:2017-10-28
通讯作者: 董林
基金资助:
国家自然科学基金（21607019，21503115）；江苏省机动车尾气污染控制重点实验室开放基金（OVEC013）；重庆三峡学院人才引进项目。

Catalytic performance of highly dispersed WO₃ loaded on CeO₂ in the selective catalytic reduction of NO by NH₃

Lei Zhang^a, Jingfang Sun^b, Yan Xiong^c, Xiaoqing Zeng^a, Changjin Tang^b, Lin Dong^b

a. School of Environmental and Chemical Engineering, Chongqing Three Gorges University, Chongqing 404000, China;
b. Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, Jiangsu, China;
c. College of Chemistry and Pharmaceutical Engineering, Nanyang Normal University, Nanyang 473061, Henan, China

Received:2017-05-31 Revised:2017-07-06 Online:2017-10-18 Published:2017-10-28
Contact: 10.1016/S1872-2067(17)62887-0
Supported by:
This work was supported by the National Natural Foundation of China (21607019, 21503115), the Open Project Program of Jiangsu Key Laboratory of Vehicle Emissions Control (OVEC013), and the Talent Introduction Project of Chongqing Three Gorges University.

摘要/Abstract

摘要：

铈基材料在氨选择性催化还原氮氧化物（NH₃-SCR）的研究中备受关注，亦被认为是潜在的新型环境友好型催化剂.CeO₂具有独特的氧化还原性能和优良的储释氧性能，易与其它金属氧化物发生协同催化而有利于提高催化剂的催化反应性能，而WO₃可以改善催化剂的表面酸性.研究亦报道了WO₃可以改善CeO₂的NH₃-SCR反应的高温活性和N₂选择性，其原因在于WO₃增加了铈基催化剂NH₃的吸附性能且抑制了NH₃非选择性氧化成NO_x.我们采用浸渍法制备了一系列负载型WO₃/CeO₂催化剂，并利用XRD，Raman，XPS，H₂-TPR，NH₃-TPD和in situ DRIFT对其理化性质进行了表征，系统研究了WO₃负载量对WO₃/CeO₂催化剂NH₃-SCR催化性能的影响，主要研究的内容包括：（1） WO₃/CeO₂催化剂中WO₃的状态与催化性能之间的关系；（2） WO₃负载量对WO₃/CeO₂催化剂的NH₃和NO吸附行为的影响.
NH₃-SCR反应测试表明WO₃负载量对WO₃/CeO₂催化剂有显著影响，优化的WO₃/CeO₂催化剂在200-450℃具有良好的脱硝性能，且在300℃通入SO₂+H₂O条件下依然保持优异的催化活性.XPS和H₂-TPR结果表明，WO₃分散在CeO₂表面抑制了CeO₂表面活性氧和表面晶格氧的氧化能力，这导致催化剂对NO的氧化以及对硝酸盐的吸附性能相比于纯CeO₂显著降低，同时，in situ DRIFT也证实，随着WO₃负载量的增加，WO₃/CeO₂催化剂表面吸附硝酸盐能力下降.因此，我们认为，由于低活性的晶相WO₃覆盖在催化剂表面，阻碍了催化剂的表面活性位，降低了催化剂的氧化还原能力和表面酸量，从而晶相WO₃抑制了WO₃/CeO₂催化剂的催化活性.同时，我们发现在70℃下采用氨水可以洗掉WO₃/CeO₂催化剂中的晶相WO₃，且洗涤后的样品催化活性有所提升，这进一步验证了晶相WO₃对催化活性的抑制作用.
In situ DRIFT结果表明WO₃/CeO₂催化剂上NH₃-SCR反应是通过Eley-Rideal机理进行，即吸附NH₃物种与气相NO之间发生反应.随着WO₃负载量的增加，WO₃/CeO₂催化剂中NH₃的吸附能力先增强后减弱，而NO吸附能力持续减弱，这有利于表面酸位在反应过程中不被硝酸盐阻碍，当WO₃负载量在分散容量附近时，这种吸附特性的效果发挥到最大，从而最大限度地促进NH₃-SCR反应按照Eley-Rideal机理顺利进行.

关键词: 氨选择性催化还原, WO₃/CeO₂催化剂, WO₃状态, 分散容量, 红外光谱

Abstract:

The influence of tungsten trioxide (WO₃) loading on the selective catalytic reduction (SCR) of nitric oxide (NO) by ammonia (NH₃) over WO₃/cerium dioxide (CeO₂) was investigated. The NO conversion first rose and then declined with increasing WO₃ loading. It was found that the crystalline WO₃ in the 1.6WO₃/CeO₂ sample could be removed in 25 wt% ammonium hydroxide at 70 ℃, which improved the catalytic activity of the sample. The obtained samples were characterized by X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, hydrogen (H₂) temperature programmed reduction, NH₃ temperature programmed desorption, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The results revealed that the dispersed WO₃ promoted the catalytic activity of WO₃/CeO₂ while the crystalline WO₃ inhibited catalytic activity. The oxygen activation of CeO₂ was inhibited by the coverage of WO₃, which weakened NO oxidation and adsorption of nitrate species over WO₃/CeO₂. In addition, the NH₃ adsorption performance on CeO₂ was improved by modification with WO₃. NH₃ was the most stable adsorbed species under NH₃ SCR reaction conditions. In situ DRIFT spectra suggested that the NH₃ SCR reaction proceeded via the Eley-Rideal mechanism over WO₃/CeO₂. Thus, when the loading of WO₃ was close to the dispersion capacity, the effects of NH₃ adsorption and activation were maximized to promote the reaction via the Eley-Rideal route.

Key words: NH₃ selective catalytic reduction, WO₃/CeO₂ catalyst_, WO₃ state, Dispersion capacity, Diffuse reflectance infrared Fourier transform spectroscopy

张雷, 孙敬方, 熊燕, 曾小清, 汤常金, 董林. CeO₂表面分散态WO₃的氨选择性催化还原性能[J]. 催化学报, 2017, 38(10): 1749-1758.

Lei Zhang, Jingfang Sun, Yan Xiong, Xiaoqing Zeng, Changjin Tang, Lin Dong. Catalytic performance of highly dispersed WO₃ loaded on CeO₂ in the selective catalytic reduction of NO by NH₃[J]. Chinese Journal of Catalysis, 2017, 38(10): 1749-1758.

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CeO₂表面分散态WO₃的氨选择性催化还原性能

Catalytic performance of highly dispersed WO₃ loaded on CeO₂ in the selective catalytic reduction of NO by NH₃

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