Journal of Materials Science

, Volume 54, Issue 9, pp 6943–6960 | Cite as

Selective catalytic reduction of NOx with NH3 over Mn–Zr–Ti mixed oxide catalysts

  • Bolin Zhang
  • Michael Liebau
  • Bo Liu
  • Lin Li
  • Shengen ZhangEmail author
  • Roger GläserEmail author
Chemical routes to materials


Mixed oxide catalysts yMn–Zr–Ti (y/10/10 with y = 1, 3, 5, 7 and 9) for the selective catalytic reduction (SCR) of NOx with NH3 in the presence of oxygen were synthesized by co-precipitation. The catalyst 5Mn–Zr–Ti exhibited a catalytic activity higher than 87% above 160 °C and N2 selectivity above 92% at 100–300 °C. The SCR performance was quite stable at 180 and 200 °C for 15 h. Mn species are shown to improve the catalytic activity by providing more surface labile oxygen, while a synergistic effect among Mn, Zr and Ti species suppressed the generation of N2O. According to in situ DRIFT analysis, NOx was primarily reduced by the reaction of bidentate nitrate and monodentate nitrito species with adsorbed NH3. Subsequently, a comprehensive reaction mechanism was proposed. Accordingly, the formation of NH species was inhibited, and hence, the N2O formation by the reaction of NH and bidentate nitrate was suppressed. Furthermore, the investigation of the deactivation mechanism by SO2 indicated that both the deposition of ammonium sulfates and the sulfation of Mn active sites resulted in the deactivation of the catalyst 5Mn–Zr–Ti. The deposition of ammonium sulfates at 180 °C was more pronounced than that at 220 °C.



This work is sponsored by the National Natural Science Foundation of China (Grants U1360202, 51672024, 51472030 and 51502014) and the Fundamental Research Funds for the Central Universities (2302017FRF-IC-17-005 and 2302017FRF-BR-17-005A).

Supplementary material

10853_2019_3369_MOESM1_ESM.docx (82 kb)
Supplementary material 1 (DOCX 81 kb)


  1. 1.
    Li Y, Li Y, Wang P et al (2017) Low-temperature selective catalytic reduction of NOx with NH3 over MnFeOx nanorods. Chem Eng J 330:213–222. CrossRefGoogle Scholar
  2. 2.
    Xiong Z, Wu C, Hu Q et al (2016) Promotional effect of microwave hydrothermal treatment on the low-temperature NH3-SCR activity over iron-based catalyst. Chem Eng J 286:459–466. CrossRefGoogle Scholar
  3. 3.
    Kong M, Liu Q, Zhu B et al (2015) Synergy of KCl and Hgel on selective catalytic reduction of NO with NH3 over V2O5–WO3/TiO2 catalysts. Chem Eng J 264:815–823. CrossRefGoogle Scholar
  4. 4.
    Arfaoui J, Ghorbel A, Petitto C, Delahay G (2018) Novel V2O5–CeO2–TiO2–SO4 2− nanostructured aerogel catalyst for the low temperature selective catalytic reduction of NO by NH3 in excess O2. Appl Catal B 224:264–275. CrossRefGoogle Scholar
  5. 5.
    Guo R, Sun X, Liu J et al (2018) Enhancement of the NH3-SCR catalytic activity of MnTiOx catalyst by the introduction of Sb. Appl Catal A 558:1–8. CrossRefGoogle Scholar
  6. 6.
    Zhang S, Zhang B, Liu B, Sun S (2017) A review of Mn-containing oxide catalysts for low temperature selective catalytic reduction of NOx with NH3: reaction mechanism and catalyst deactivation. RSC Advances 7:26226–26242. CrossRefGoogle Scholar
  7. 7.
    Kim Y, Kwon H, Nam I et al (2010) High deNOx performance of Mn/TiO2 catalyst by NH3. Catal Today 151:244–250. CrossRefGoogle Scholar
  8. 8.
    Jiang B, Deng B, Zhang Z et al (2014) Effect of Zr addition on the low-temperature SCR activity and SO2 tolerance of Fe–Mn/Ti catalysts. J Phys Chem C 118:14866–14875. CrossRefGoogle Scholar
  9. 9.
    Liu T, Yao Y, Wei L et al (2017) Preparation and evaluation of Copper–Manganese oxide as a high-efficiency catalyst for CO oxidation and NO reduction by CO. J Phys Chem C 121:12757–12770. CrossRefGoogle Scholar
  10. 10.
    Wang P, Chen S, Gao S, Zhang J, Wang H, Wu Z (2018) Niobium oxide confined by ceria nanotubes as a novel SCR catalyst with excellent resistance to potassium, phosphorus, and lead. Appl Catal B 231:299–309. CrossRefGoogle Scholar
  11. 11.
    Sun C, Liu H, Chen W et al (2018) Insights into the Sm/Zr co-doping effects on N2 selectivity and SO2 resistance of a MnOx–TiO2 catalyst for the NH3-SCR reaction. Chem Eng J 347:27–40. CrossRefGoogle Scholar
  12. 12.
    Liu Z, Zhou Z, Qi G, Zhu T (2019) Selective catalytic reduction of NOx with NH3 over MoO3/Mn–Zr composite oxide catalyst. Appl Surf Sci 466:459–465. CrossRefGoogle Scholar
  13. 13.
    Wu X, Feng Y, Du Y, Liu X, Zou C, Li Z (2019) Enhancing DeNOx performance of CoMnAl mixed metal oxides in low-temperature NH3–SCR by optimizing layered double hydroxides (LDHs) precursor template. Appl Surf Sci 467–468:802–810. CrossRefGoogle Scholar
  14. 14.
    Jin R, Liu Y, Wang Y et al (2014) The role of cerium in the improved SO2 tolerance for NO reduction with NH3 over Mn–Ce/TiO2 catalyst at low temperature. Appl Catal B 148–149:582–588. CrossRefGoogle Scholar
  15. 15.
    Zhang D, Yang R (2017) NH3-SCR of NO over one-pot Cu-SAPO-34 catalyst: performance enhancement by doping Fe and MnCe and insight into N2O formation. Appl Catal A 543:247–256. CrossRefGoogle Scholar
  16. 16.
    You Y, Chang H, Zhu T, Zhang T, Li X, Li J (2017) The poisoning effects of phosphorus on CeO2–MoO3/TiO2 DeNOx catalysts: nH3-SCR activity and the formation of N2O. Mol Catal 439:15–24. CrossRefGoogle Scholar
  17. 17.
    Kim M, Park S (2016) Selective reduction of NO by NH3 over Fe-zeolite-promoted V2O5–WO3/TiO2-based catalysts: great suppression of N2O formation and origin of NO removal activity loss. Catal Commun 86:82–85. CrossRefGoogle Scholar
  18. 18.
    France L, Yang Q, Li W et al (2017) Ceria modified FeMnOx—Enhanced performance and sulphur resistance for low-temperature SCR of NOx. Appl Catal B 206:203–215. CrossRefGoogle Scholar
  19. 19.
    Zhang B, Zhang S, Liu B, Shen H, Li L (2018) High N2 selectivity in selective catalytic reduction of NO with NH3 over Mn/Ti–Zr catalysts. RSC Advances 8:12733–12741. CrossRefGoogle Scholar
  20. 20.
    Xie C, Yang S, Shi J, Li B, Gao C, Niu C (2017) MnOx–TiO2 and Sn doped MnOx–TiO2 selective reduction catalysts prepared using MWCNTs as the pore template. Chem Eng J 327:1–8. CrossRefGoogle Scholar
  21. 21.
    Andreoli S, Deorsola F, Galletti C, Pirone R (2015) Nanostructured MnOx catalysts for low-temperature NOx SCR. Chem Eng J 278:174–182. CrossRefGoogle Scholar
  22. 22.
    Huang L, Zha K, Namuangruk S et al (2016) Promotional effect of the TiO2(001) facet in the selective catalytic reduction of NO with NH3: in situ DRIFTS and DFT studies. Catal Sci Technol 6:8516–8524. CrossRefGoogle Scholar
  23. 23.
    Thommes M, Kaneko K, Neimark Alexander V et al (2015) Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl Chem 87:1051–1069. CrossRefGoogle Scholar
  24. 24.
    Xin Y, Li H, Zhang N et al (2018) Molecular-level insight into selective catalytic reduction of NOx with NH3 to N2 over a highly efficient bifunctional Va–MnOx catalyst at low temperature. ACS Catalysis 8:4937–4949. CrossRefGoogle Scholar
  25. 25.
    Huang X, Zhao G, Chang Y, Wang G, Irvine JTS (2018) Nanocrystalline CeO2−δ coated β-MnO2 nanorods with enhanced oxygen transfer property. Appl Surf Sci 440:20–28. CrossRefGoogle Scholar
  26. 26.
    Hu H, Cai S, Li H, Huang L, Shi L, Zhang D (2015) Mechanistic aspects of deNOx processing over TiO2 supported Co–Mn oxide catalysts: structure-activity relationships and in situ DRIFTs analysis. ACS Catal 5:6069–6077. CrossRefGoogle Scholar
  27. 27.
    Stanciulescu M, Caravaggio G, Dobri A et al (2012) Low-temperature selective catalytic reduction of NOx with NH3 over Mn-containing catalysts. Appl Catal B 123–124:229–240. CrossRefGoogle Scholar
  28. 28.
    Zhao X, Huang L, Li H et al (2016) Promotional effects of zirconium doped CeVO4 for the low-temperature selective catalytic reduction of NOx with NH3. Appl Catal B 183:269–281. CrossRefGoogle Scholar
  29. 29.
    Zuo J, Chen Z, Wang F, Yu Y, Wang L, Li X (2014) low-temperature selective catalytic reduction of NOx with NH3 over novel Mn–Zr Mixed oxide catalysts. Ind Eng Chem Res 53:2647–2655. CrossRefGoogle Scholar
  30. 30.
    Yao X, Zhang L, Li L et al (2014) Investigation of the structure, acidity, and catalytic performance of CuO/Ti0.95Ce0.05O2 catalyst for the selective catalytic reduction of NO by NH3 at low temperature. Appl Catal B 150–151:315–329. CrossRefGoogle Scholar
  31. 31.
    Huang L, Hu X, Yuan S et al (2017) Photocatalytic preparation of nanostructured MnO2–(Co3O4)/TiO2 hybrids: the formation mechanism and catalytic application in SCR deNOx reaction. Appl Catal B 203:778–788. CrossRefGoogle Scholar
  32. 32.
    Yao X, Zhao R, Chen L et al (2017) Selective catalytic reduction of NOx by NH3 over CeO2 supported on TiO2: comparison of anatase, brookite, and rutile. Appl Catal B 208:82–93. CrossRefGoogle Scholar
  33. 33.
    Liu J, Li X, Zhao Q et al (2017) Mechanistic investigation of the enhanced NH3-SCR on cobalt-decorated Ce–Ti mixed oxide: in situ FTIR analysis for structure-activity correlation. Appl Catal B 200:297–308. CrossRefGoogle Scholar
  34. 34.
    Yu L, Zhong Q, Deng Z, Zhang S (2016) Enhanced NOx removal performance of amorphous Ce–Ti catalyst by hydrogen pretreatment. J Mol Catal A Chem 423:371–378. CrossRefGoogle Scholar
  35. 35.
    Xue Y, Sun W, Wang Q, Cao L, Yang J (2018) Sparsely loaded Pt/MIL-96(Al) MOFs catalyst with enhanced activity for H2-SCR in a gas diffusion reactor under 80° C. Chem Eng J 335:612–620. CrossRefGoogle Scholar
  36. 36.
    Pappas DK, Boningari T, Boolchand P, Smirniotis PG (2016) Novel manganese oxide confined interweaved titania nanotubes for the low-temperature selective catalytic reduction (SCR) of NOx by NH3. J Catal 334:1–13. CrossRefGoogle Scholar
  37. 37.
    Li B, Xiong S, Liao Y et al (2016) Why the low-temperature selective catalytic reduction performance of Cr/TiO2 is much less than that of Mn/TiO2: a mechanism study. J Phys Chem C 120:23511–23522. CrossRefGoogle Scholar
  38. 38.
    Guo R, Wang S, Pan W et al (2017) Different poisoning effects of K and Mg on the Mn/TiO2 catalyst for selective catalytic reduction of NOx with NH3: a mechanistic study. J Phys Chem C 121:7881–7891. CrossRefGoogle Scholar
  39. 39.
    Atribak I, Bueno-Lopez A, Garcia-Garcia A (2008) Combined removal of diesel soot particulates and NOx over CeO2–ZrO2 mixed oxides. J Catal 259:123–132. CrossRefGoogle Scholar
  40. 40.
    Bendrich M, Scheuer A, Hayes R, Votsmeier M (2018) Unified mechanistic model for standard SCR, fast SCR, and NO2 SCR over a copper chabazite catalyst. Appl Catal B 222:76–87. CrossRefGoogle Scholar
  41. 41.
    Joshi S, Kumar A, Luo J, Kamasamudram K, Currier NW, Yezerets A (2018) New insights into the mechanism of NH3-SCR over Cu- and Fe-zeolite catalyst: apparent negative activation energy at high temperature and catalyst unit design consequences. Appl Catal B 226:565–574. CrossRefGoogle Scholar
  42. 42.
    Yang S, Qi F, Xiong S et al (2016) MnOx supported on Fe–Ti spinel: a novel Mn based low temperature SCR catalyst with a high N2 selectivity. Appl Catal B 181:570–580. CrossRefGoogle Scholar
  43. 43.
    Xu H, Zhang Q, Qiu C, Lin T, Gong M, Chen Y (2012) Tungsten modified MnOx–CeO2/ZrO2 monolith catalysts for selective catalytic reduction of NOx with ammonia. Chem Eng Sci 76:120–128. CrossRefGoogle Scholar
  44. 44.
    Lu X, Song C, Jia S, Tong Z, Tang X, Teng Y (2015) Low-temperature selective catalytic reduction of NOx with NH3 over cerium and manganese oxides supported on TiO2–graphene. Chem Eng J 260:776–784. CrossRefGoogle Scholar
  45. 45.
    Zhang X, Shen B, Shen F, Zhang X, Si M, Yuan P (2017) The behavior of the manganese–cerium loaded metal-organic framework in elemental mercury and NO removal from flue gas. Chem Eng J 326:551–560. CrossRefGoogle Scholar
  46. 46.
    Chen H, Xia Y, Huang H et al (2017) Highly dispersed surface active species of Mn/Ce/TiW catalysts for high performance at low temperature NH3-SCR. Chem Eng J 330:1195–1202. CrossRefGoogle Scholar
  47. 47.
    Tang X, Li C, Yi H et al (2018) Facile and fast synthesis of novel Mn2CoO4@rGO catalysts for the NH3-SCR of NOx at low temperature. Chem Eng J 333:467–476. CrossRefGoogle Scholar
  48. 48.
    Zhang Y, Huang T, Xiao R, Xu H, Shen K, Zhou C (2018) A comparative study on the Mn/TiO2–M(M = Sn, Zr or Al)Ox catalysts for NH3-SCR reaction at low temperature. Environ Technol 39:1284–1294. CrossRefGoogle Scholar
  49. 49.
    Yu J, Guo F, Wang Y et al (2010) Sulfur poisoning resistant mesoporous Mn-base catalyst for low-temperature SCR of NO with NH3. Appl Catal B 95:160–168. CrossRefGoogle Scholar
  50. 50.
    Lin F, He Y, Wang Z et al (2016) Catalytic oxidation of NO by O2 over CeO2–MnOx: SO2 poisoning mechanism. RSC Advances 6:31422–31430. CrossRefGoogle Scholar
  51. 51.
    Abdulhamid H, Fridell E, Dawody J, Skoglundh M (2006) In situ FTIR study of SO2 interaction with Pt/BaCO3/Al2O3 NOx storage catalysts under lean and rich conditions. J Catal 241:200–210. CrossRefGoogle Scholar
  52. 52.
    Yamamoto A, Teramura K, Hosokawa S, Tanaka T (2015) Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst. Sci Technol Adv Mater 16:024901. CrossRefGoogle Scholar
  53. 53.
    Yu C, Huang B, Dong L et al (2017) Effect of Pr/Ce addition on the catalytic performance and SO2 resistance of highly dispersed MnOx/SAPO-34 catalyst for NH3-SCR at low temperature. Chem Eng J 316:1059–1068. CrossRefGoogle Scholar
  54. 54.
    Zhang A, Zhang Z, Lu H et al (2015) Effect of promotion with Ru addition on the activity and SO2 resistance of MnOx–TiO2 Adsorbent for Hg0 removal. Ind Eng Chem Res 54:2930–2939. CrossRefGoogle Scholar
  55. 55.
    Chang H, Chen X, Li J et al (2013) Improvement of activity and SO2 tolerance of Sn-modified MnOx–CeO2 catalysts for NH3-SCR at low temperatures. Environ Sci Technol 47:5294–5301. CrossRefGoogle Scholar
  56. 56.
    Kim Y, Kwon H, Heo I et al (2012) Mn–Fe/ZSM5 as a low-temperature SCR catalyst to remove NOx from diesel engine exhaust. Appl Catal B 126:9–21. CrossRefGoogle Scholar
  57. 57.
    Wu Z, Jin R, Wang H, Liu Y (2009) Effect of ceria doping on SO2 resistance of Mn/TiO2 for selective catalytic reduction of NO with NH3 at low temperature. Catal Commun 10:935–939. CrossRefGoogle Scholar
  58. 58.
    Kwon D, Nam K, Hong S (2015) The role of ceria on the activity and SO2 resistance of catalysts for the selective catalytic reduction of NOx by NH3. Appl Catal B 166–167:37–44. CrossRefGoogle Scholar
  59. 59.
    Liu Z, Zhang S, Li J, Ma L (2014) Promoting effect of MoO3 on the NOx reduction by NH3 over CeO2/TiO2 catalyst studied with in situ DRIFTS. Appl Catal B 144:90–95. CrossRefGoogle Scholar
  60. 60.
    Chen L, Li J, Ge M (2010) DRIFT study on Cerium–Tungsten/Titiania catalyst for selective catalytic reduction of NOx with NH3. Environ Sci Technol 44:9590–9596. CrossRefGoogle Scholar
  61. 61.
    Zhan S, Qiu M, Yang S, Zhu D, Yu H, Li Y (2014) Facile preparation of MnO2 doped Fe2O3 hollow nanofibers for low temperature SCR of NO with NH3. J Mater Chem A 2:20486–20493. CrossRefGoogle Scholar
  62. 62.
    Gao G, Shi J, Fan Z, Gao C, Niu C (2017) MnM2O4 microspheres (M = Co, Cu, Ni) for selective catalytic reduction of NO with NH3: comparative study on catalytic activity and reaction mechanism via in situ diffuse reflectance infrared Fourier transform spectroscopy. Chem Eng J 325:91–100. CrossRefGoogle Scholar
  63. 63.
    Zhang L, Shi L, Huang L, Zhang J, Gao R, Zhang D (2014) Rational design of high-performance DeNOx catalysts based on MnxCo3–xO4 nanocages derived from metal-organic frameworks. ACS Catalysis 4:1753–1763. CrossRefGoogle Scholar
  64. 64.
    Hadjiivanov K (2000) Identification of neutral and charged NxOy surface species by IR spectroscopy. Catal Rev 42:71–144. CrossRefGoogle Scholar
  65. 65.
    Fan J, Ning P, Song Z et al (2018) Mechanistic aspects of NH-SCR reaction over CeO2/TiO2–ZrO2–SO4 2− catalyst: in situ DRIFTS investigation. Chem Eng J 334:855–863. CrossRefGoogle Scholar
  66. 66.
    Zhang R, Yang W, Luo N, Li P, Lei Z, Chen B (2014) Low-temperature NH3-SCR of NO by lanthanum manganite perovskites: effect of A-/B-site substitution and TiO2/CeO2 support. Appl Catal B 146:94–104. CrossRefGoogle Scholar
  67. 67.
    Wang X, Li X, Zhao Q, Sun W, Tade M, Liu S (2016) Improved activity of W-modified MnOx–TiO2 catalysts for the selective catalytic reduction of NO with NH3. Chem Eng J 288:216–222. CrossRefGoogle Scholar
  68. 68.
    Wu Z, Jiang B, Liu Y (2008) Effect of transition metals addition on the catalyst of manganese/titania for low-temperature selective catalytic reduction of nitric oxide with ammonia. Appl Catal B 79:347–355. CrossRefGoogle Scholar
  69. 69.
    Ettireddy P, Ettireddy N, Boningari T, Pardemann R, Smirniotis P (2012) Investigation of the selective catalytic reduction of nitric oxide with ammonia over Mn/TiO2 catalysts through transient isotopic labeling and in situ FT-IR studies. J Catal 292:53–63. CrossRefGoogle Scholar
  70. 70.
    Zha K, Cai S, Hu H et al (2017) In situ DRIFTs investigation of promotional effects of Tungsten on MnOx–CeO2/meso-TiO2 catalysts for NOx reduction. J Phys Chem C 121:25243–25254. CrossRefGoogle Scholar
  71. 71.
    Peng Y, Wang C, Li J (2014) Structure-activity relationship of VOx/CeO2 nanorod for NO removal with ammonia. Appl Catal B 144:538–546. CrossRefGoogle Scholar
  72. 72.
    Liu F, He H, Ding Y, Zhang C (2009) Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH3. Appl Catal B 93:194–204. CrossRefGoogle Scholar
  73. 73.
    Geng Y, Shan W, Yang S, Liu F (2018) W-Modified Mn–Ti mixed oxide catalyst for the selective catalytic reduction of NO with NH3. Ind Eng Chem Res 57:9112–9119. CrossRefGoogle Scholar
  74. 74.
    Chen L, Li R, Li Z, Yuan F, Niu X, Zhu Y (2017) Effect of Ni doping in NixMn1−xTi10 (x = 0.1 − 0.5) on activity and SO2 resistance for NH3-SCR of NO studied with in situ DRIFTS. Catal Sci Technol 7:3243–3257CrossRefGoogle Scholar
  75. 75.
    Hu W, Zhang Y, Liu S et al (2017) Improvement in activity and alkali resistance of a novel V–Ce(SO4)2/Ti catalyst for selective catalytic reduction of NO with NH3. Appl Catal B 206:449–460. CrossRefGoogle Scholar
  76. 76.
    Chen Z, Wang F, Li H, Yang Q, Wang L, Li X (2011) Low-temperature selective catalytic reduction of NOx with NH3 over Fe–Mn mixed-oxide catalysts containing Fe3Mn3O8 phase. Ind Eng Chem Res 51:202–212. CrossRefGoogle Scholar
  77. 77.
    Meng D, Xu Q, Jiao Y et al (2018) Spinel structured CoaMnbOx mixed oxide catalyst for the selective catalytic reduction of NOx with NH3. Appl Catal B 221:652–663. CrossRefGoogle Scholar
  78. 78.
    Zheng H, Song W, Zhou Y et al (2017) Mechanistic study of selective catalytic reduction of NOx with NH3 over Mn-TiO2: a combination of experimental and DFT study. J Phys Chem C 121:19859–19871. CrossRefGoogle Scholar
  79. 79.
    Xiong S, Weng J, Liao Y et al (2016) Alkali metal deactivation on the low temperature selective catalytic reduction of NOx with NH3 over MnOx–CeO2: a mechanism study. J Phys Chem C 120:15299–15309. CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Institute for Advanced Materials and TechnologyUniversity of Science and Technology BeijingBeijingChina
  2. 2.Institute of Chemical TechnologyLeipzig UniversityLeipzigGermany

Personalised recommendations