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The Absence of Oxygen in Sulfation Promotes the Performance of the Sulfated CeO2 Catalyst for Low-Temperature Selective Catalytic Reduction of NOx by NH3: Redox Property versus Acidity

  • Qin Wu
    Qin Wu
    State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China
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  • Xiaoping Chen
    Xiaoping Chen
    State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China
  • Jinxing Mi
    Jinxing Mi
    State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China
    More by Jinxing Mi
  • Sixiang Cai
    Sixiang Cai
    State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China
    More by Sixiang Cai
  • Lei Ma*
    Lei Ma
    School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China
    *Email: [email protected]
    More by Lei Ma
  • Weitao Zhao
    Weitao Zhao
    Laboratoire Catalyse et Spectrochimie, ENSICAEN, Université de Caen, CNRS, 6 bd du Maréchal Juin, 14050 Caen, France
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  • Jianjun Chen*
    Jianjun Chen
    State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China
    *Email: [email protected]
    More by Jianjun Chen
  • , and 
  • Junhua Li
    Junhua Li
    State Key Joint Laboratory of Environment Simulation and Pollution Control, National Engineering Laboratory for Multi Flue Gas Pollution Control Technology and Equipment, School of Environment, Tsinghua University, 30 Shuangqing Road, Beijing 100084, China
    More by Junhua Li
Cite this: ACS Sustainable Chem. Eng. 2021, 9, 2, 967–979
Publication Date (Web):January 5, 2021
https://doi.org/10.1021/acssuschemeng.0c08427
Copyright © 2021 American Chemical Society
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Abstract

Tuning surface acidity with SO2 sulfation is well established to enhance the catalytic performance of CeO2 for selective catalytic reduction of NOx by NH3 (NH3-SCR). However, the role of oxygen, which strongly affects the chemical potential of SO2 in sulfation, remains unclear. Herein, we found that anaerobic sulfation promotes the SCR rate of the sulfated CeO2 catalyst by 2.8-fold at 275 °C without detriment to selectivity and stability. More importantly, spectroscopies using different probes indicate that the anaerobic SO2 treatment hardly modifies the redox property of the sulfated CeO2 catalyst, but strongly enhances the number and strength of Lewis acid sites. Furthermore, sulfation followed by in situ infrared and density functional theory calculations suggest that the formed chelated bidentate sulfate species could contribute to the increased Lewis acidity through the electrophilic effect. This work provides a direct evidence of how the acidity rather than the redox property determines the performance of Ce-based SCR catalysts.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.0c08427.

  • Chemicals and reagents; synthesis of CeO2-rod; catalytic performance test (NH3-SCR reaction rate test; NH3 oxidation and NO oxidation); the details of characterization; computational details; table of reaction rate of different catalysts; table of activity comparison of CeO2-rod-SO2 catalysts and reported NH3-SCR catalysts, table of atomic ratio of different catalysts calculated from XPS; kinetic parameters of the NH3-SCR reaction over CeO2-rod-SO2 and CeO2-rod-SO2-O2 catalysts; the contents of cerium(III) sulfate and cerium(IV) sulfate over CeO2-rod-SO2 and CeO2-rod-SO2-O2 catalysts from TGA; HR-TEM images of the catalysts; N2 adsorption–desorption isotherms and pore size distributions of different catalysts; catalytic activity of NH3 oxidation and the selectivity of different products over CeO2-rod, CeO2-rod-SO2, and CeO2-rod-SO2-O2 catalysts; catalytic performance of NO oxidation to NO2; temperature-programmed IR spectra of pyridine adsorption on CeO2-rod catalysts; model of the (110) surface of CeO2; adsorption of SO2 on the (110) surface of CeO2; adsorption of O2 on the (110) surface of CeO2; and adsorption of SO2 on the (110) surface of CeO2 with O2 (PDF)

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Cited By


This article is cited by 6 publications.

  1. Renyi Xie, Lei Ma, Zihao Li, Zan Qu, Naiqiang Yan, Junhua Li. Review of Sulfur Promotion Effects on Metal Oxide Catalysts for NOx Emission Control. ACS Catalysis 2021, 11 (21) , 13119-13139. https://doi.org/10.1021/acscatal.1c02197
  2. Wei Wang, Zhibo Xiong, Jing Jin, Wei Lu, Huancong Shi. Influence of CS2 pretreatment on the NH3-SCR activity of CeO2: Synergistic promotional effect of sulfation and reduction. Journal of Environmental Chemical Engineering 2021, 9 (6) , 106836. https://doi.org/10.1016/j.jece.2021.106836
  3. Qi Liu, Jinxing Mi, Xiaoping Chen, Shihao Wang, Jianjun Chen, Junhua Li. Effects of phosphorus modification on the catalytic properties and performance of CuCeZr mixed metal catalyst for simultaneous removal of CO and NOx. Chemical Engineering Journal 2021, 423 , 130228. https://doi.org/10.1016/j.cej.2021.130228
  4. Renyi Xie, Lei Ma, Kai Sun, Gang Zhou, Zan Qu, Naiqiang Yan. Catalytic performance and mechanistic evaluation of sulfated CeO2 cubes for selective catalytic reduction of NOx with ammonia. Journal of Hazardous Materials 2021, 420 , 126545. https://doi.org/10.1016/j.jhazmat.2021.126545
  5. Jiawei Ji, Meizan Jing, Xiuwen Wang, Wei Tan, Kai Guo, Lulu Li, Xin Wang, Wang Song, Lijun Cheng, Jingfang Sun, Weiyu Song, Changjin Tang, Jian Liu, Lin Dong. Activating low-temperature NH3-SCR catalyst by breaking the strong interface between acid and redox sites: A case of model Ce2(SO4)3-CeO2 study. Journal of Catalysis 2021, 399 , 212-223. https://doi.org/10.1016/j.jcat.2021.05.001
  6. Wei Tan, Jin Wang, Yandi Cai, Lulu Li, Shaohua Xie, Fei Gao, Fudong Liu, Lin Dong. Molybdenum oxide as an efficient promoter to enhance the NH3-SCR performance of CeO2-SiO2 catalyst for NO removal. Catalysis Today 2021, 8 https://doi.org/10.1016/j.cattod.2021.07.007