MnOx–CeO2/t-ZrO2 catalyst was prepared by impregnation of nanotetragonal zirconia. The NO conversion of 5 wt% MnOx–CeO2/t-ZrO2 catalyst was 68.1% at 100 °C while that of 30 wt% MnOx–CeO2/t-ZrO2 catalyst was 97.4%. The x-ray diffraction, Brunner–Emmet–Teller measurements (BET), and H2-TPR showed surface properties of the prepared catalysts were good for selective catalytic reduction reactions. X-ray photoelectron spectroscopy analysis indicated that Mn4+ and Ce4+ oxidation states were predominant on the surface of the catalyst and so was lattice oxygen which was conducive to Lewis acid sites. NH3-TPD test results demonstrated that Lewis acid sites are predominant on the surface of catalyst. The presence of SO2 reduced the catalyst activity. The realized conversion dramatically decreased to 47% from nearly 100% after 8 h. Characterization of fresh and spent catalysts indicated the deterioration of active component and deposition of NH4HSO4 or (NH4)2SO4 contribute to SO2 poisoning.
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X-L. Tang, J-M. Hao, W-G. Xu, and J-H. Li: The United States and Europe NOx control policy for China’s reference. Chin. J. Catal. 27, 843 (2006).
Annual Statistic Report on Environment, Department of Pollution emission control, Ministry of Environment Protection of the People’s Republic of China, 2012, 02, 18. http://zls.mep.gov.cn/hjtj/nb/2012tjnb/.
G. Qi and R-T. Yang: Low-temperature selective catalytic reduction of NO with NH3 over iron and manganese oxides supposed on titania. Appl. Catal., B 44, 217 (2003).
J.A. Sullivan and J.A. Doherty: NH3 and urea in the selective catalytic reduction of NOx over oxide-supported copper catalysts. Appl. Catal., B 55, 185 (2005).
Z-P. Zhu, Z-Y. Liu, H-X. Niu, S-J Liu, T-D. Hu, T.L, and Y-N. Xie: Mechanism of SO2 promotion for NO reduction with NH3 over activated carbon-supposed vanadium oxide catalyst. J. Catal. 197, 6 (2001).
M. Yoshikawa, A. Yasutake, and I. Mochida: Regeneration of initial activity of a pitch-based ACF for NO-NH3 reaction at ambient temperature. Appl. Catal., A 173, 239 (1998).
G. Delahay, D. Valade, A. Guzmfin-Vargas, and B. Cop: Selective catalytic reduction of nitric oxide with ammonia on Fe-ZSM-5 catalysts prepared by different methods. Appl. Catal., B 55, 149 (2005).
C. Fan, J. Xiang, S. Su, P-Y. Wang, L-S. Sun, S. Hu, and S-Y. Lei: The activity and characterization of MnOx–CeO2–ZrO2/γ-Al2O3 catalysts for low temperature selective catalytic reduction of NO with NH3. Chem. Eng. J. 243 (2014).
Z-Y. Yan, J-F. Hu, and H. Xu: Denitrification property of catalyst CeO2/TiO2–ZrO2 with strong hydrothermal stability and sulfur tolerance. J. Chin. Soc. Power Eng. 31, 58 (2011).
N. Takahashi, A. Suda, and I. Hachisuka: Sulfur durability of NOx storage and reduction catalyst with supports of TiO2, ZrO2 and ZrO2–TiO2 mixed oxides. Appl. Catal., B 72, 187 (2007).
B.M. Reddy, A. Khan, Y. Yamada, T. Kobayashi, S. Loridant, and J.-C. Volta: Structural characterization of CeO2–TiO2 and V2O5/CeO2–TiO2 catalysts by Raman and XPS techniques. J. Phys. Chem. B 107, 5162 (2003).
Z-X. Song, N. Ping, Q-L. Zhang, H. Li, J-H. Zhang, Y-C. Wang, X. Liu, and Z-Z. Huang: Activity and hydrothermal stability of CeO2–ZrO2–WO3 for the selective catalytic reduction of NOx with NH3. J. Environ. Sci. 4, 42 (2015).
B-X. Shen, Y-Y. Wang, F-M. Wang, and T. Liu: The effect of Ce–Zr on NH3-SCR activity over MnOx(0.6)/Ce0.5Zr0.5O2 at low temperature. Chem. Eng. J. 2, 236 (2014).
W-Y. Zhen and C-D. Chen: The properties, uses and prospect of zirconium dioxide. Inorg. Chem. Ind. 32, 18 (2000).
H. Guan, X-J. Gong, R. Liu, and L. Yang: Preparation of stable nanosized ZrO2 particles with different crystallographic structures. Chin. J. Mater. Res. 28, 139 (2014).
R. Liu and Z-Q. Yang: Low-temperature catalytic reduction of NO over Fe–MnOx–CeO2/ZrO2 Catalyst. Environ. Sci. 33, 188 (2012).
S.M. Sager, D.I. Kondarides, and X.E. Verykios: Catalytic oxidation of toluene over binary mixtures of copper, manganese and cerium oxides supported on y-Al2O3. Appl. Catal., B 103, 275 (2011).
X. Zhang, L-Y. Ji, S-C. Zhang, and W-S. Yang: Synthesis of a novel polyaniline-intercalated layered manganese oxide nanocomposite as electrode material for electrochemical capacitor. J. Power Sources 173, 1017–1023 (2007).
D.A. Peña, B.S. Uphade, and P.G. Smirniotis: TiO2-supported metal oxide catalysts for low-temperature selective catalytic reduction of no with NH3: I. Evaluation and characterization of first row transition metals. J. Catal. 221, 421–431 (2004).
J-L. Xie, D. Fang, F. He, J-F. Chen, Z-B. Fu, and X-L. Chen: Performance and mechanism about MnOx species included in MnOx/TiO2 catalysts for SCR at low temperature. Catal. Commun. 28, 77 (2012).
B-J. Wu, X-Q. Liu, and S-G. Wang: Investigation and characterization on MnOx/TiO2 for low-temperature selective catalytic reduction of NOx with NH3. J. Combust. Sci. Technol. 14, 221 (2008).
W.R. Thompson and J.E. Pembeaon: Characterization of octadecylsilane and stearic-acid layers on Al2O3 surfaces by raman-spectroscopy. Langmuir 11, 1720 (1995).
M. Takagi, T. Kawai, M. Soma, et al.: Mechanism of catalytic reaction between nitric oxide and ammonia on vanadium pentoxide in the presence of oxygen. J. Phys. Chem. 80, 430 (1976).
J. Yu, F. Guo, Y-L. Wang, J-H. Zhu, Y-Y. Liu, F-B. Su, S-Q. Gao, and G-W. Xu: Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH3. Appl. Catal., B 95, 160 (2010).
Z-L. Wei, H-M. Li, X-Y. Zhang, S-H. Yan, Z. Lv, Y-Q. Chen, and M-C. Gong: Preparation and property investigation of CeO2–ZrO2–Al2O3 oxygen-storage compounds. J. Alloys Compd 455, 322 (2008).
L-J. Liu, Y. Chen, and L-H. Dong: In situ FT-infrared investigation of CO or/and NO interaction with CuO/Ce0.67Zr0.33O2 catalysts. Appl. Catal., B 90, 105 (2009).
Q-L. Zhang, C-T. Qiu, H-D. Xu, T. Lin, Z-E. Lin, M-C. Gong, and Y-Q. Chen: Low-temperature selective catalytic reduction of NO with NH3 over monolith catalyst of MnOx/CeO2–ZrO2–Al2O3. Catal. Today 175, 171 (2011).
W-Z. Li, H. Huang, H-J. Li, W. Zhang, and H-C. Liu: Facile synthesis of pure monoclinic and tetragonal zirconia nanoparticles and their phase effects on the behavior of supported molybdena catalysts for methanol-selective oxidation. Langmuir 24, 8358 (2008).
J-H. Li, J-J. Chen, R. Ke, C-K. Luo, and J-M. Hao: Effects of precursors on the surface Mn species and the activities for NO reduction over MnOx/TiO2 catalysts. Catal. Commun. 8, 1896 (2007).
This research was supported by the Jiangsu Provincial Environmental Protection Office Project (2013032) and a sponsored by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
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Liu, R., Ji, L., Xu, Y. et al. Catalytic performance and SO2 tolerance of tetragonal-zirconia-based catalysts for low-temperature selective catalytic reduction. Journal of Materials Research 31, 2590–2597 (2016). https://doi.org/10.1557/jmr.2016.283