Journal of Sol-Gel Science and Technology

, Volume 81, Issue 2, pp 576–585 | Cite as

Novel hollow microspheres MnxCo3−xO4 (x = 1, 2) with remarkable performance for low-temperature selective catalytic reduction of NO with NH3

  • Yi Li
  • Yanping Li
  • Qiang Shi
  • Mingying Qiu
  • Sihui Zhan
Original Paper: Sol-gel and hybrid materials for energy, environment and building applications


Hollow microspheres MnCo2O4 and CoMn2O4 have been synthesized by a facile solvothermal route followed by pyrolysis of the carbonate counterparts and carbon microspheres, using carbon microspheres as the template. The NH3-selective catalytic reduction reaction was used to test the catalytic activity. The obtained hollow microspheres are composed of numerous primary particles with sizes of tens of nanometers, giving a porous shell. The obtained CoMn2O4 microsphere shows better low-temperature catalytic activity and N2 selectivity than MnCo2O4 microsphere in the NH3-selective catalytic reduction reaction. The X-ray photoelectron spectroscopy results demonstrate that CoMn2O4 microsphere has a relatively higher number content of Mn3+ and chemisorbed oxygen species. The temperature-programmed desorption by ammonia and in situ diffuse reflectance infrared Fourier transform spectroscopy results indicate that the CoMn2O4 microsphere possesses stronger Lewis acid strength than the MnCo2O4 microsphere. Additionally, the CoMn2O4 microsphere also presented outstanding stability, H2O resistance and SO2 tolerance.

Graphical Abstract

The NH3-SCR reaction mechanism is proposed that NH3(g) is adsorbed on the surface of Lewis acid sites and Brønsted acid sites in the shape of NH4 + ions and gaseous NH3. Besides, the adsorption of NO could exist in the form of gaseous or oxide ions NO2 on the surface of catalysts.The adsorbed NH3 species could react with NO2 species easily to produce NH4NO2, which subsequently to produce the innocuous N2 and H2O. Open image in new window


CoMn2O4 Hollow microspheres SCR Low temperature 



This work was supported by the National Natural Science Foundtion of China (Grant No. 21377061, 81270041), Independent Innovation fund of Tianjin University (2015XRG-0020 and 2016XJ-0006), and by Natural Science Foundation of Tianjin (Grant No. 15JCYBJC48400, 16YFZCSF00300 and 15JCZDJC41200).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10971_2016_4208_MOESM1_ESM.docx (218 kb)
Supplementary Information


  1. 1.
    Liu ZM, Lua YN, Yua L, Ma LL, Zheng LR, Zhang J, Hu TD (2016) Appl Catal B: Environ 188:189–197CrossRefGoogle Scholar
  2. 2.
    Tang CJ, Zhang HL, Dong L (2016) Catal Sci Technol 6:1248–1264CrossRefGoogle Scholar
  3. 3.
    Liu F, Asakurab K, He H, Liu Y, Shan W, Shi X, Zhang C (2011) Catal Today 164:520–530CrossRefGoogle Scholar
  4. 4.
    Gao X, Liu S, Zhang Y, Luo Z, Cen K (2011) J Hazard Mater 188:58–64CrossRefGoogle Scholar
  5. 5.
    Chang HZ, Jong MT, Wang CZ, Qu RY, Du Y, Li JH, Hao JM (2013) Environ Sci Technol 47:11692–11699CrossRefGoogle Scholar
  6. 6.
    Maqbool MS, Pullur AK, Ha HP (2014) Appl Catal B: Environ 152-153:28–35CrossRefGoogle Scholar
  7. 7.
    Hea YY, Forda ME, Zhu MH, Liu QC, Wu ZL, Wach IE (2016) Appl Catal B: Environ 188:123–133CrossRefGoogle Scholar
  8. 8.
    Wu Z, Jiang B, Liu Y (2008) Appl Catal B 79:347–354CrossRefGoogle Scholar
  9. 9.
    Chen L, Li JH, Ge M (2010) Environ Sci Technol 44:9590–9596CrossRefGoogle Scholar
  10. 10.
    Liu F, He H, Zhang C, Shan W, Shi X (2011) Catal Today 175:18–26CrossRefGoogle Scholar
  11. 11.
    Li X, Li JH, Peng Y, Chang HZ, Zhang T, Zhao S, Si WZ, Hao JM (2016) Appl Catal B 184:246–257CrossRefGoogle Scholar
  12. 12.
    He CH, Kohler K (2011) J Phys Chem C 115:1248–1254CrossRefGoogle Scholar
  13. 13.
    Bin F, Song CL, Lv G, Song J, Cao XF, Pang HT, Wang KP (2012) J Phys Chem C 116:26262–26274CrossRefGoogle Scholar
  14. 14.
    Wallin M, Forser S, Thormahlen P, Skoglundh M (2004) Ind Eng Chem Res 43:7723–7731CrossRefGoogle Scholar
  15. 15.
    Pietrzyk P, Dujardin C, Marek KG, Granger P, Sojkaa Z (2012) Phys Chem Chem Phys 14:2203–2215CrossRefGoogle Scholar
  16. 16.
    Shu Z, Huang WM, Hua ZL, Zhang LX, Cui XZ, Chen Y, Chen HR, Wei CY, Wang YX, Fan XQ, Yao HL, He DN, Shi JL (2013) J Mater Chem A 1:10218–10227CrossRefGoogle Scholar
  17. 17.
    Mihaylov M, Hadjiivanov K (2004) Chem Commun 5:2200–2209CrossRefGoogle Scholar
  18. 18.
    Fang C, Zhang DS, Cai SJ, Zhang L, Huang L, Li HR, Maitarad P, Shi LY, Gao RH, Zhang JP (2013) Nanoscale 5:9199–9207CrossRefGoogle Scholar
  19. 19.
    Chang HZ, Chen XY, Li JH, Ma L, Wang CZ, Liu CX, Schwank JW, Hao JM (2013) Environ Sci Technol 47:5294–5301CrossRefGoogle Scholar
  20. 20.
    Tian W, Yang HS, Fan XY, Zhang XB (2011) J Hazard Mater 188:105–109CrossRefGoogle Scholar
  21. 21.
    Wan Y, Zhao W, Tang Y, Li L, Wang H, Cui Y, Gu J, Li Y, Shi J (2014) Appl Catal B 148-149:114–121CrossRefGoogle Scholar
  22. 22.
    Meng B, Zhao ZB, Wang XZ, Liang JJ, Qiu JS (2013) Appl Catal B: Environ 129:491–500CrossRefGoogle Scholar
  23. 23.
    Yang S, Wanga C, Li J, Yan N, Ma L, Chang H (2013) Appl Catal B 110:71–79CrossRefGoogle Scholar
  24. 24.
    Zhang L, Zhang DS, Zhang JP, Cai SX, Fang C, Huang L, Li HR, Gao RH, Shi LY (2013) Nanoscale 5:9821–9829CrossRefGoogle Scholar
  25. 25.
    Zhang DS, Zhang L, Fang C, Gao R, Qian YL, Shi LY, Zhang JP (2013) RSC Adv 3:8811–8819CrossRefGoogle Scholar
  26. 26.
    Aguilera DA, Perez A, Molina R, Moreno S (2011) Appl Catal B: Environ 104:144–150CrossRefGoogle Scholar
  27. 27.
    Shi C, Wang Y, Zhu A, Chen BB, Au C (2012) Catal Commun 28:18–22CrossRefGoogle Scholar
  28. 28.
    Zhang L, Shi LY, Huang L, Zhang JP, Gao RH, Zhang DS (2014) ACS Catal 4:1753–1763CrossRefGoogle Scholar
  29. 29.
    Gao RH, Zhang DS, Maitarad P, Shi LY, Rungrotmongkol T, Li HR, Zhang JP, Cao WG (2013) J Phys Chem C 117:10502–10511CrossRefGoogle Scholar
  30. 30.
    Li J, Wang J, Liang X, Zhang Z, Liu H, Qian Y, Xiong S (2014) ACS Appl Mater Interfaces 6:24–31CrossRefGoogle Scholar
  31. 31.
    Sun XM, Li YD (2004) Angew Chem Int Ed 43:597–604CrossRefGoogle Scholar
  32. 32.
    Wang LZ, Tang FQ, Ozawa K, Chen ZG, Mukherj A, Zhu YC, Zou J, Cheng HM, Lu GQ (2009) Angew Chem Int Ed 48:7048–7056CrossRefGoogle Scholar
  33. 33.
    Zhou L, Zhao DY, Lou XW (2012) Adv Mater 24:745–748CrossRefGoogle Scholar
  34. 34.
    Li J, Xiong S, Li X, Qian Y (2013) Nanoscale 5:2045–2053CrossRefGoogle Scholar
  35. 35.
    Tang XF, Li JH, Sun L, Hao JM (2010) Appl Catal B: Environ 99:156–162CrossRefGoogle Scholar
  36. 36.
    Shi C, Wang Y, Zhu A, Chen B, Au C (2012) Catal Commun 28:18–26CrossRefGoogle Scholar
  37. 37.
    Aguilera DA, Perez A, Molina R, Moreno S (2011) Appl Catal B: Environ 104:144–152CrossRefGoogle Scholar
  38. 38.
    Yang SJ, Wang CZ, Li JH, Yan NQ, Ma L, Chang HZ (2011) Appl Catal B: Environ 110:71–80CrossRefGoogle Scholar
  39. 39.
    Chen L, Li J, Ge M (2010) Environ Sci Technol 44:9590–9598CrossRefGoogle Scholar
  40. 40.
    Qi GS, Yang RT (2004) Phys Chem B 108:15738–15746CrossRefGoogle Scholar
  41. 41.
    Liu F, He H (2004) Catal Today 153:70–76CrossRefGoogle Scholar
  42. 42.
    Si Z, Weng D, Wu X, Li J, Li G (2010) J Catal 271:43–51CrossRefGoogle Scholar
  43. 43.
    Gu T, Jin R, Liu Y, Liu H, Weng X, Wu Z (2013) Appl Catal B: Environ 129:30–38CrossRefGoogle Scholar
  44. 44.
    Casapu M, Kröcher O, Mehring M, Nachtegaal M, Borca C, Harfouche M, Grolimund D (2010) J Phys Chem C 114:9791CrossRefGoogle Scholar
  45. 45.
    Hadjiivanov KI (2004) Catal Rev 42:71–79CrossRefGoogle Scholar
  46. 46.
    Yao X, Zhang L, Li L, Liu L, Cao Y, Dong X, Gao F, Deng Y, Tang C, Chen Z, Dong L, Chen Y (2014) Appl Catal B: Environ 150-151:315–322CrossRefGoogle Scholar
  47. 47.
    Kijlstra WS, Brands DS, Smit HI, Poels EK, Bliek A (1997) J Catal 171:219–227CrossRefGoogle Scholar
  48. 48.
    Wang LZ, Tang FQ, Ozawa K, Chen ZG, Mukherj A, Zhu YC, Zou J, Cheng HM, Lu GQ (2009) Angew Chem Int Ed 48:7048–7051CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Yi Li
    • 1
  • Yanping Li
    • 1
  • Qiang Shi
    • 2
  • Mingying Qiu
    • 2
  • Sihui Zhan
    • 2
  1. 1.Department of ChemistryTianjin UniversityTianjinPeople’s Republic of China
  2. 2.College of Environmental Science and EngineeringNankai UniversityTianjinPeople’s Republic of China

Personalised recommendations