Advertisement

Journal of Materials Science

, Volume 54, Issue 23, pp 14414–14430 | Cite as

Adsorption mechanism of NH3, NO, and O2 molecules over MnxOy/Ni (111) surface: a density functional theory study

  • Qilong Fang
  • Baozhong ZhuEmail author
  • Yunlan SunEmail author
  • Weiyi Song
  • Chaoyue Xie
  • Minggao Xu
Computation & theory
  • 79 Downloads

Abstract

Selective catalytic reduction of NOx with NH3 is one of the most effective ways to reduce NOx emissions. Manganese-based deNOx catalysts have attracted much attention owing to their unstable valence states. Nickel-foam-supported manganese-based catalysts show excellent low-temperature deNOx activities. However, the detailed deNOx mechanism is still unclear. In this paper, the adsorption mechanism of NH3, NO, and O2 molecules over nickel-foam-supported manganese-based catalysts was studied by a density functional theory. The model of MnO2, Mn2O3, and Mn3O4 clusters loading on the Ni (111) surface was chosen. The results show that MnO2, Mn2O3, and Mn3O4 clusters can be stably adsorbed on the Ni (111) surface accompanied by charge redistributions, which provide a large number of stable adsorption sites for gas molecules. NH3 molecule can be adsorbed on the Ni-top and Mn sites as the coordinated NH3. For MnO2, Mn2O3, and Mn3O4 clusters, Mn3O4 clusters are the most favorable for NH3 adsorption, indicating that they can promote NH3-SCR reaction. NO exists in three adsorption states on the MnxOy/Ni (111) surface and forms different nitrite or nitrate species. Interestingly, NO molecule tends to adsorb on the hollow site of Ni (111) surface. O2 molecule has various adsorption states on the MnxOy/Ni (111) surface. NO molecule is more likely to be adsorbed on the Mn site of the O2–MnxOy/Ni (111) surface to form nitrosyl structure, and some of NO molecules can react with adsorbed oxygen to form the adsorbed NO2 spices, which can facilitate the SCR deNOx reaction. The catalytic activity of Mn3O4/Ni (111) surface is higher than those of MnO2/Ni (111) and Mn2O3/Ni (111) surfaces by comparing the work functions and adsorption properties of NH3, NO, and O2 molecules.

Notes

Acknowledgements

We greatly appreciate the financial support provided by the National Natural Science Foundation of China (Nos. 51676001 and 51376007) and the Project of Jiangsu Provincial Six Talent Peak (No. JNHB-097).

Compliance with ethical standards

Conflicts of interest

The authors declare there is no conflict of interest.

Supplementary material

10853_2019_3929_MOESM1_ESM.docx (2.9 mb)
Supplementary material 1 (DOCX 2960 kb)

References

  1. 1.
    Skalska K, Miller JS, Ledakowicz S (2010) Trends in NO(x) abatement: a review. Sci Total Environ 408:3976–3989CrossRefGoogle Scholar
  2. 2.
    Beirle S, Boersma KF, Platt U, Lawrence MG, Wagner T (2011) Megacity emissions and lifetimes of nitrogen oxides probed from space. Science 333:1737–1739CrossRefGoogle Scholar
  3. 3.
    Forzatti P, Nova I, Tronconi E (2009) Enhanced NH3 selective catalytic reduction for NOx abatement. Angew Chem Int Ed 48:8366–8368CrossRefGoogle Scholar
  4. 4.
    Wang XQ, Shi AJ, Duan YF, Wang J, Shen MQ (2012) Catalytic performance and hydrothermal durability of CeO2-V2O5-ZrO2/WO3-TiO2 based NH3-SCR catalysts. Catal Sci Technol 2:1386CrossRefGoogle Scholar
  5. 5.
    Kompio PGWA, Brückner A, Hipler F, Auer G, Löffler E, Grünert W (2012) A new view on the relations between tungsten and vanadium in V2O5-WO3/TiO2 catalysts for the selective reduction of NO with NH3. J Catal 286:237–247CrossRefGoogle Scholar
  6. 6.
    Cheng K, Liu J, Zhang T, Li JM, Zhao Z, Wei YC, Jiang GY, Duan AJ (2014) Effect of Ce doping of TiO2 support on NH3-SCR activity over V2O5-WO3/CeO2-TiO2 catalyst. J Environ Sci 26:2106–2113CrossRefGoogle Scholar
  7. 7.
    Lai JK, Wachs IE (2018) A perspective on the selective catalytic reduction (SCR) of NO with NH3 by supported V2O5-WO3/TiO2 catalysts. ACS Catal 8:6537–6551CrossRefGoogle Scholar
  8. 8.
    Guo RT, Wang QS, Pan WG, Zhen WL, Chen QL, Ding HL, Yang NZ, Lu CZ (2014) The poisoning effect of Na and K on Mn/TiO2 catalyst for selective catalytic reduction of NO with NH3: a comparative study. Appl Surf Sci 317:111–116CrossRefGoogle Scholar
  9. 9.
    Nicosia D, Czekaj I, Kröcher O (2008) Chemical deactivation of V2O5/WO3-TiO2 SCR catalysts by additives and impurities from fuels, lubrication oils and urea solution Part II Characterization study of the effect of alkali and alkaline earth metals. Appl Catal B: Environ 77:228–236CrossRefGoogle Scholar
  10. 10.
    Thirupathi B, Smirniotis PG (2011) Co-doping a metal (Cr, Fe Co, Ni, Cu, Zn, Ce, and Zr) on Mn/TiO2 catalyst and its effect on the selective reduction of NO with NH3 at low-temperatures. Appl Catal B: Environ 110:195–206CrossRefGoogle Scholar
  11. 11.
    Yang SJ, Fu YW, Liao Y, Xiong SC, Qu Z, Yan NQ, Li JH (2014) Competition of selective catalytic reduction and non selective catalytic reduction over MnOx/TiO2 for NO removal: the relationship between gaseous NO concentration and N2O selectivity. Catal Sci Technol 4:224–232CrossRefGoogle Scholar
  12. 12.
    Peña DA, Uphade BS, Reddy EP, Smirniotis PG (2004) Identification of surface species on titania-supported manganese, chromium, and copper oxide low-temperature SCR catalysts. J Phys Chem B 108:9927–9936CrossRefGoogle Scholar
  13. 13.
    Zhang RD, Yang W, Luo N, Li PX, Lei ZG, Chen BH (2014) Low-temperature NH3-SCR of NO by lanthanum manganite perovskites: effect of A-/B-site substitution and TiO2/CeO2 support. Appl Catal B: Environ 146:94–104CrossRefGoogle Scholar
  14. 14.
    Thirupathi B, Smirniotis PG (2012) Nickel-doped Mn/TiO2 as an efficient catalyst for the low-temperature SCR of NO with NH3: catalytic evaluation and characterizations. J Catal 288:74–83CrossRefGoogle Scholar
  15. 15.
    Ettireddy PR, Ettireddy N, Mamedov S, Boolchand P, Smirniotis PG (2007) Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl Catal B: Environ 76:123–134CrossRefGoogle Scholar
  16. 16.
    Tang XL, Hao JM, Xu WG, Li JH (2007) Low temperature selective catalytic reduction of NOx with NH3 over amorphous MnOx catalysts prepared by three methods. Catal Commun 8:329–334CrossRefGoogle Scholar
  17. 17.
    Xu KB, Li WY, Liu Q, Li B, Liu XJ, An L, Chen ZG, Zou RJ, Hu JQ (2014) Hierarchical mesoporous NiCo2O4@MnO2 core-shell nanowire arrays on nickel foam for aqueous asymmetric supercapacitors. J Mater Chem A 2:4795CrossRefGoogle Scholar
  18. 18.
    Yu L, Zhang GQ, Yuan CZ, Lou XW (2013) Hierarchical NiCo2O4@MnO2 core-shell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes. Chem Commun 49:137–139CrossRefGoogle Scholar
  19. 19.
    Luo YS, Luo JS, Jiang J, Zhou WW, Yang HP, Qi XY, Zhang H, Fan HJ, Yu DYW, Li CM, Yu T (2012) Seed-assisted synthesis of highly ordered TiO2@α-Fe2O3 core/shell arrays on carbon textiles for lithium-ion battery applications. Energ Environ Sci 5:6559CrossRefGoogle Scholar
  20. 20.
    Li Y, Shen WJ (2014) Morphology-dependent nanocatalysts: rod-shaped oxides. Chem Soc Rev 43:1543–1574CrossRefGoogle Scholar
  21. 21.
    Ren Z, Guo YB, Zhang ZH, Liu CH, Gao PX (2013) Nonprecious catalytic honeycombs structured with three dimensional hierarchical Co3O4 nano-arrays for high performance nitric oxide oxidation. J Mater Chem A 1:9897CrossRefGoogle Scholar
  22. 22.
    Liu Y, Xu J, Li HR, Cai SX, Hu H, Fang C, Shi L, Zhang DS (2015) Rational design and in situ fabrication of MnO2@NiCo2O4 nanowire arrays on Ni foam as high-performance monolith de-NOx catalysts. J Mater Chem A 3:11543–11553CrossRefGoogle Scholar
  23. 23.
    Zhu BZ, Li GB, Sun YL, Yin SL, Fang QL, Zi ZH, Zhu ZC, Li JX, Mao KK (2018) De-NOx performance and mechanism of Mn-based low-temperature SCR catalysts supported on foamed metal nickel. J Brazil Chem Soc 29:1680–1689Google Scholar
  24. 24.
    Li GB, Zhu BZ, Sun YL, Yin SL, Zi ZH, Fang QL, Ge TT, Li JX (2018) Study of the alkali metal poisoning resistance of a Co-modified Mn/Ni foam catalyst in low-temperature flue gas SCR DeNOx. J Mater Sci 53:9674–9689.  https://doi.org/10.1007/s10853-018-2234-3 CrossRefGoogle Scholar
  25. 25.
    Marbán G, Valdés-Solís T, Fuertes AB (2004) Mechanism of low-temperature selective catalytic reduction of NO with NH3 over carbon-supported Mn3O4 Role of surface NH3 species: SCR mechanism. J Catal 226:138–155CrossRefGoogle Scholar
  26. 26.
    Yuan RM, Fu G, Xu X, Wan HL (2011) Mechanisms for selective catalytic oxidation of ammonia over vanadium oxides. J Phys Chem C 115:21218–21229CrossRefGoogle Scholar
  27. 27.
    Song WY, Liu J, Zheng HL, Ma SC, Wei YC, Duan AJ, Jiang GY, Zhao Z, Hensen EJM (2016) A mechanistic DFT study of low temperature SCR of NO with NH3 on MnCe1-xO2(111). Catal Sci Technol 6:2120–2128CrossRefGoogle Scholar
  28. 28.
    Zhu BZ, Fang QL, Sun YL, Yin SL, Li GB, Zi ZH, Ge TT, Zhu ZC, Zhang MX, Li JX (2018) Adsorption properties of NO, NH3, and O2 over β-MnO2(110) surface. J Mater Sci 53:11500–11511.  https://doi.org/10.1007/s10853-018-2437-7 CrossRefGoogle Scholar
  29. 29.
    Maitarad P, Namuangruk S, Zhang DS, Shi LY, Li HR, Huang L, Boekfa B, Ehara M (2014) Metal-porphyrin: a potential catalyst for direct decomposition of N2O by theoretical reaction mechanism investigation. Environ Sci Technol 48:7101–7110CrossRefGoogle Scholar
  30. 30.
    Fang QL, Zhu BZ, Sun YL, Zhu ZC, Xu MG, Ge TT (2019) Mechanistic insight into the selective catalytic reduction of NO by NH3 over α-Fe2O3(001): a density functional theory study. Catal Sci Technol 9:116–124CrossRefGoogle Scholar
  31. 31.
    Wan YP, Zhao WR, Tang Y, Li L, Wang HJ, Cui YL, Gu JL, Li YS, Shi JL (2014) Ni-Mn bi-metal oxide catalysts for the low temperature SCR removal of NO with NH3. Appl Catal B: Environ 148–149:114–122CrossRefGoogle Scholar
  32. 32.
    Jampaiah D, Tur KM, Venkataswamy P, Ippolito SJ, Sabri YM, Tardio J, Bhargava SK, Reddy BM (2015) Catalytic oxidation and adsorption of elemental mercury over nanostructured CeO2-MnOx catalyst. RSC Adv 5:30331–30341CrossRefGoogle Scholar
  33. 33.
    Peng Y, Li JH, Chen L, Chen JH, Han J, Zhang H, Han W (2012) Alkali metal poisoning of a CeO2-WO3 catalyst used in the selective catalytic reduction of NOx with NH3: an experimental and theoretical study. Environ Sci Technol 46:2864–2869CrossRefGoogle Scholar
  34. 34.
    Gao G, Shi JW, Liu C, Gao C, Fan ZY, Niu CM (2017) Mn/CeO2 catalysts for SCR of NO x with NH3: comparative study on the effect of supports on low-temperature catalytic activity. Appl Surf Sci 411:338–346CrossRefGoogle Scholar
  35. 35.
    Jiang BQ, Deng BY, Zhang ZQ, Wu ZL, Tang XJ, Yao SL, Lu H (2014) Effect of Zr addition on the low-temperature SCR activity and SO2 tolerance of Fe-Mn/Ti catalysts. J Phys Chem C 118:14866–14875CrossRefGoogle Scholar
  36. 36.
    Li W, Guo RT, Wang SX, Pan WG, Chen QL, Li MY, Sun P, Liu SM (2016) The enhanced Zn resistance of Mn/TiO2 catalyst for NH3-SCR reaction by the modification with Nb. Fuel Process Technol 154:235–242CrossRefGoogle Scholar
  37. 37.
    Chen QL, Guo RT, Wang QS, Pan WG, Yang NZ, Lu CZ, Wang SX (2016) The promotion effect of Co doping on the K resistance of Mn/TiO2 catalyst for NH3-SCR of NO. J Taiwan Inst Chem E 64:116–123CrossRefGoogle Scholar
  38. 38.
    Han J, Meeprasert J, Maitarad P, Nammuangruk S, Shi LY, Zhang DS (2016) Investigation of the facet-dependent catalytic performance of Fe2O3/CeO2 for the selective catalytic reduction of NO with NH3. J Phys Chem C 120:1523–1533CrossRefGoogle Scholar
  39. 39.
    Cao F, Su S, Xiang J, Sun LS, Hu S, Zhao QS, Wang PY, Lei SY (2012) Density functional study of adsorption properties of NO and NH3 over CuO/γ-Al2O3 catalyst. Appl Surf Sci 261:659–664CrossRefGoogle Scholar
  40. 40.
    Wei L, Cui SP, Guo HX, Zhang LJ (2018) The effect of alkali metal over Mn/TiO2 for low-temperature SCR of NO with NH3 through DRIFT and DFT. Comp Mater Sci 144:216–222CrossRefGoogle Scholar
  41. 41.
    Wei L, Cui SP, Guo HX, Ma XY, Zhang LJ (2016) DRIFT and DFT study of cerium addition on SO2 of manganese-based catalysts for low temperature SCR. J Mol Catal A: Chem 421:102–108CrossRefGoogle Scholar
  42. 42.
    Xiang J, Wang LL, Cao F, Qian K, Su S, Hu S, Wang Y, Liu LJ (2016) Adsorption properties of NO and NH3 over MnOx based catalyst supported on γ-Al2O3. Chem Eng J 302:570–576CrossRefGoogle Scholar
  43. 43.
    Dong W, Kresse G, Furthmüller J, Hafner J (1996) Chemisorption of H on Pd(111): an ab initio approach with ultrasoft pseudopotentials. Phys Rev B 54:2157–2166CrossRefGoogle Scholar
  44. 44.
    Kresse G, Furthmiiller J (1996) Efficiency of ab initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp Mater Sci 6:15–50CrossRefGoogle Scholar
  45. 45.
    Rohrbach A, Hafner J, Kresse G (2003) Electronic correlation effects in transition-metal sulfides. J Phys: Condens Matter 15:979–996Google Scholar
  46. 46.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868CrossRefGoogle Scholar
  47. 47.
    Mohsenzadeh A, Richards T, Bolton K (2016) DFT study of the water gas shift reaction on Ni(111), Ni(100) and Ni(110) surfaces. Surf Sci 644:53–63CrossRefGoogle Scholar
  48. 48.
    Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758–1775CrossRefGoogle Scholar
  49. 49.
    Monkhorst HJ, Pack JD (1976) Special points for Brillouin-zone integrations. Phys Rev B 13:5188–5192CrossRefGoogle Scholar
  50. 50.
    Li JD, Croiset E, Ricardez-Sandoval L (2014) Effect of carbon on the Ni catalyzed methane cracking reaction: a DFT study. Appl Surf Sci 311:435–442CrossRefGoogle Scholar
  51. 51.
    Ren J, Guo HL, Yang JZ, Qin ZF, Lin JY, Li Z (2015) Insights into the mechanisms of CO2 methanation on Ni(111) surfaces by density functional theory. Appl Surf Sci 351:504–516CrossRefGoogle Scholar
  52. 52.
    Bengtsson L (1999) Dipole correction for surface supercell calculations. Phys Rev B 59:12301–12304CrossRefGoogle Scholar
  53. 53.
    Zhao WW, Li CT, Lu P, Wen QB, Zhao YP, Zhang X, Fan CZ, Tao SS (2013) Iron, lanthanum and manganese oxides loaded on γ-AI2O3 for selective catalytic reduction of NO with NH3 at low temperature. Environ Technol 34:81–90CrossRefGoogle Scholar
  54. 54.
    Iwasaki M, Shinjoh H (2010) A comparative study of “standard”, “fast” and “NO2” SCR reactions over Fe/zeolite catalyst. Appl Catal A: Gen 390:71–77CrossRefGoogle Scholar
  55. 55.
    Huang HY, Long RQ, Yang RT (2002) Kinetics of selective catalytic reduction of NO with NH3 on Fe-ZSM-5 catalyst. Appl Catal A: Gen 235:241–251CrossRefGoogle Scholar
  56. 56.
    Aylor AW, Lobree LJ, Reimer JA, Bell AT (1997) NO adsorption, desorption, and reduction by CH4 over Mn-ZSM-5. J Catal 170:390–401CrossRefGoogle Scholar
  57. 57.
    Hadjiivanov KI (2000) Identification of neutral and charged NxOy surface species by IR spectroscopy. Catal Rev 42:71–144CrossRefGoogle Scholar
  58. 58.
    Centeno MA, Carrizosa I, Odriozola JA (1998) In situ DRIFTS study of the SCR reaction of NO with NH3 in the presence of O2 over lanthanide doped V2O5/Al2O3 catalysts. Appl Catal B: Environ 19:67–73CrossRefGoogle Scholar
  59. 59.
    Shen YS, Su Y, Ma YF (2015) Transition metal ions regulate the catalytic performance of Ti08M02Ce02O2+x for the NH3-SCR of NO: the acidic mechanism. RSC Adv 5:7597–7603CrossRefGoogle Scholar
  60. 60.
    Zhao QS, Sun LS, Liu Y, Su S, Xiang J, Hu S (2011) Adsorption of NO and NH3 over CuO/γ-Al2O3 catalyst. J Cent South Univ Technol 18:1883–1890CrossRefGoogle Scholar
  61. 61.
    Zhang MH, Huang XW, Chen YF (2016) DFT insights into the adsorption of NH3-SCR related small gases in Mn-MOF-74. Phys Chem Chem Phys 18:28854–28863CrossRefGoogle Scholar
  62. 62.
    Chen LQ, Niu XY, Li ZB, Dong YL, Zhang ZP, Yuan FL, Zhu YJ (2016) Promoting catalytic performances of Ni-Mn spinel for NH3-SCR by treatment with SO2 and H2O. Catal Commun 85:48–51CrossRefGoogle Scholar
  63. 63.
    Chen LQ, Li R, Li ZB, Yuan FL, Niu XY, Zhu YJ (2017) Effect of Ni doping in NixMn1-xTi10 (x = 01–05) on activity and SO2 resistance for NH3-SCR of NO studied with in situ DRIFTS. Catal Sci Technol 7:3243–3257CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.School of Petroleum EngineeringChangzhou UniversityChangzhouPeople’s Republic of China
  2. 2.School of Energy and EnvironmentAnhui University of TechnologyMaanshanPeople’s Republic of China
  3. 3.Center for Advanced Combustion and EnergyUniversity of Science and Technology of ChinaHefeiPeople’s Republic of China

Personalised recommendations