Citation: LI Yuan-yuan, HUANG Yan, TANG Nan, YAN Run-hua, HU Zhen-yu, XIAO Rao, FU Qing, ZHAO Ling-kui, ZHANG Jun-feng, YANG Liu-chun. Study on the performance of low temperature NH₃-SCR over MnO₂ nano-catalyst with different crystal structures[J]. Journal of Fuel Chemistry and Technology, ;2018, 46(5): 578-584. shu

Study on the performance of low temperature NH₃-SCR over MnO₂ nano-catalyst with different crystal structures

College of Environment and Resources, Xiangtan University, Xiangtan 411105, China

Corresponding author: HUANG Yan, xtuhy@163.com
Received Date: 15 January 2018
Revised Date: 20 March 2018

Fund Project: the Platform Open Innovation Fund Project in Hunan Province Colleges and Universities 14K094The project was supported by the Platform Open Innovation Fund Project in Hunan Province Colleges and Universities (14K094)

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To investigate the relationship between the structure and catalytic activity, four types of MnO₂ nano-catalysts with various crystal structures (α-MnO₂, β-MnO₂, γ-MnO₂ and δ-MnO₂) were synthesized by hydrothermal method, and their low temperature NH₃-SCR activity were tested. The results indicated that catalysts with different structures showed various activities which followed the sequence of γ-MnO₂ > α-MnO₂ > β-MnO₂ > δ-MnO₂. It was found that γ-MnO₂ showed highest catalytic activity and its NO_x conversion rate surpassed 90% at the temperature range of 150-260℃. The catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy (SEM), N₂ adsorption-desorption, thermogravimetric(TG), infrared (FT-IR), temperature programmed reduction(H₂-TPR) and pyridine infrared spectroscopy (Py-FTIR). It was inferred that the morphology of the α-MnO₂ and β-MnO₂ were nanorods, while γ-MnO₂ and δ-MnO₂ with the structures of nanoneedles. The specific surface area of the catalyst was not the dominant factor affecting the NH₃-SCR activity at low temperature. The decent pore structure, strong redox property, abundant chemisorption oxygen and Lewis acid sites were responsible for high low temperature NH₃-SCR activity of γ-MnO₂ nano-catalyst.
- hydrothermal method,
- MnO₂ nano-catalyst,
- crystal structure,
- low temperature NH₃-SCR
1. [1]
  PÂRVULESCU V I, GRANGE P, DELMON B. Catalytic removal of NO[J]. Catal Today, 1998,46(4):233-316. doi: 10.1016/S0920-5861(98)00399-X
2. [2]
  ROY S, HEGDE MS, MADRAS G. Catalysis for NO_x abatement[J]. Appl Energy, 2009,86(11):2283-2297. doi: 10.1016/j.apenergy.2009.03.022
3. [3]
  LIU C, SHI J-W, GAO C, NIU C. Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NO_x with NH₃:A review[J]. Appl Catal A:Gen, 2016,522:54-69. doi: 10.1016/j.apcata.2016.04.023
4. [4]
  YANG Yong-li, XU Dong-yao, CHAO Chun-yan, GAO Ming. Research advance review on supported Mn-based catalysts at low-temperature selective catalytic reduction of NO_x with NH₃[J]. Chem Ind Eng Prog, 2016,35(4):1094-1100.
5. [5]
  LIU Ting, WANG Ting-chun, WU Rui-qing, SHEN Bo-xiong. Research advance review for low-temperature NH₃ -SCR catalysts[J]. J Saf Environ, 2012,19(6):42-44.
6. [6]
  KAPTEIJN F, SINGOREDJO L, ANDREINI A, MOULIJN J A. Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia[J]. Appl Catal B:Environ, 1994,3(2/3):173-189.
7. [7]
  LIU Lin-lin, TIAN Hua, HE Jun-hui, YANG Qiao-wen, WANG Dong. Progress in cryptomelane-and birnessite manganese oxides[J]. Chem Bull, 2011,74(4):000291-000297.
8. [8]
  THACKERAY M M. Manganese oxides for lithium batteries[J]. Prog Solid State Chem, 1997,25(1/2):1-71.
9. [9]
  LIANG S, TENG F, BULGAN G, RUILONG ZONG A, ZHU Y. Effect of phase structure of MnO₂ nanorod catalyst on the activity for CO oxidation[J]. J Phys Chem C, 2010,112(14):5307-5315.
10. [10]
  ZHANG J, LI Y, WANG L, ZHANG C, HE H. Catalytic oxidation of formaldehyde over manganese oxides with different crystal structures[J]. Catal Sci Technol, 2015,5(4):2305-2313. doi: 10.1039/C4CY01461H
11. [11]
  DAI Yun, LI Jun-hua, PENG Yue, TANG Xing-fu. Effects of MnO₂ crystal structure and surface property on the NH₃-SCR reaction at low temperature[J]. Acta Phys Chim Sin, 2012,28(7):1771-1776.
12. [12]
  LI Y, LI Y, WAN Y, ZHAN S, GUAN Q, TIAN Y. Structure-performance relationships of MnO₂nanocatalyst for the low-temperature SCR removal of NO_x under ammonia[J]. RSC Adv, 2016,6(60):54926-54937. doi: 10.1039/C6RA03108K
13. [13]
  SUN Meng-ting, HUANG Bi-chun, MA Jie-wen, LI Shi-hui, DONG Li-fu. Morphological effects of manganese dioxide on catalytic reactions for low-temperature NH₃-SCR[J]. Acta Phys Chim Sin, 2016,32(6):1501-1510. doi: 10.3866/PKU.WHXB201603171
14. [14]
  SUN M, LAN B, YU L, YE F, SONG W, HE J, DIAO G, ZHENG Y. Manganese oxides with different crystalline structures:Facile hydrothermal synthesis and catalytic activities[J]. Mater Lett, 2012,86:18-20. doi: 10.1016/j.matlet.2012.07.011
15. [15]
  WANG Yan-cai, LIU Xin, NING Ping, ZHANG Qiu-lin, ZHANG Jin-hui, XU Li-si, TANG Xiao-su, WANG Ming-zhi. Effect of preparation methods on selective catalytic reduction of NO_x with NH₃ over manganese oxide octahedral molecular sieves[J]. J Fuel Chem Technol, 2014,42(11):1357-1364. doi: 10.3969/j.issn.0253-2409.2014.11.013
16. [16]
  SU Qian, HUANG Yan, ZHANG Yin, LI Yuan-yuan, TANG Nan, ZHANG Jun-fen, YANG Liu-chun. Effects of copper sources on selective catalytic reduction of NO with NH₃ of Cu-SAPO-34[J]. J Mol Catal, 2016,30(2):151-158.
17. [17]
  GIOVANOLI R. Thermogravimetry of manganese dioxides[J]. Thermochim Acta, 1994,234(94):303-313.
18. [18]
  WANG C, SUN L, CAO Q, HU B, HUANG Z, TANG X. Surface structure sensitivity of manganese oxides for low-temperature selective catalytic reduction of NO with NH₃[J]. Appl Catal B:Environ, 2011,101(3/4):598-605.
19. [19]
  WANG ZM, KANOH H. Calorimetric study on NH₃ insertion reaction into microporous manganese oxides with (2×2) tunnel and (2×∞) layered structures[J]. Thermochim Acta, 2001,379(1):7-14.
20. [20]
  GUO Xue-yi, LIU Hai-han, LI Dong, TIAN Qing-hua, XU Gang. Influence of thermal treatment on the crystal phase transformation of MnO₂[J]. Min Metal Eng, 2007,27(1):50-53.
21. [21]
  AND S D, MUNICHANDRAIAH N. Effect of crystallographic structure of MnO₂ on its electrochemical capacitance properties[J]. J Phys Chem C, 2008,112(11):4406-4417. doi: 10.1021/jp7108785
22. [22]
  LI Y, FAN Z, SHI J, LIU Z, ZHOU J, SHANGGUAN W. Modified manganese oxide octahedral molecular sieves M'-OMS-2(M'=Co, Ce, Cu) as catalysts in post plasma-catalysis for acetaldehyde degradation[J]. Catal Today, 2015,256:178-185. doi: 10.1016/j.cattod.2015.02.003
23. [23]
  XIE J, CHEN L, ZHOU W F, AU C T, YIN S F. Selective oxidation of p-chlorotoluene to p-chlorobenzaldehyde over metal-modified OMS-2 molecular sieves[J]. J Mol Catal A:Chem, 2016,425:110-115. doi: 10.1016/j.molcata.2016.09.038
24. [24]
  XIN Qin, LUO Meng-fei. The Modern Catalytic Research Method[M]. Beijing:Science Press, 2009.
25. [25]
  WU Z, JIANG B, LIU Y, WANG H, JIN R. DRIFT study of manganese/titania-based catalysts for low-temperature selective catalytic reduction of NO with NH₃[J]. Environ Sci Technol, 2007,41(16):5812-5817. doi: 10.1021/es0700350
26. [26]
  YU C, HUANG B, DONG L, CHEN F, LIU X. In situ FT-IR study of highly dispersed MnO_x/SAPO-34 catalyst for low-temperature selective catalytic reduction of NO_x by NH₃[J]. Catal Today, 2017,281:610-620. doi: 10.1016/j.cattod.2016.06.025
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Study on the performance of low temperature NH₃-SCR over MnO₂ nano-catalyst with different crystal structures