Structural Chemistry

, Volume 30, Issue 5, pp 1647–1657 | Cite as

A comparative DFT study about surface reactivity and catalytic activity of Pd- and Ni-doped BN nanosheets: NO reduction by CO molecule

  • Mehdi D. EsrafiliEmail author
  • Safa Heydari
  • Leila Dinparast
Original Research


Today, the emission of poisonous gases in the atmosphere has caused many serious health and environmental problems. So, the finding of efficient methods for reducing or removing these toxic gases from the atmosphere is of great interest. The main goal of this study is to compare catalytic activity of Pd- and Ni-doped boron nitrite nanosheets (Pd-/Ni-BNNS) for the reduction of nitric oxide (NO) by CO molecule. To this aim, density functional theory (DFT) calculations are performed to calculate adsorption energies, geometric parameters, charge-transfer values, and reaction barriers. The results of DFT calculations show that the reduction of NO proceeds through a dimer mechanism. At first, two NO molecules are attached together to form (NO)2 dimer. Next, (NO)2 is decomposed into N2O and Oads species. The Oads is then removed by CO molecule: CO + Oads → CO2. All other possible reactions over these surfaces are studied in details. Our findings demonstrate that the catalytic activity of Pd-BNNS for the reduction of NO is higher than that of Ni-BNNS.


Surface reactivity NO reduction BNNS DFT Catalysis 



The authors would like to thank the “Computational Center of University of Maragheh” for its technical support of this work.

Compliance with ethical standards

Conflict of interest

The authors declare they have no conflict of interest.

Supplementary material

11224_2019_1355_MOESM1_ESM.doc (4 mb)
ESM 1 (DOC 4069 kb)


  1. 1.
    Brandenberger S, Kröcher O, Tissler A, Althoff R (2008) The state of the art in selective catalytic reduction of NOx by ammonia using metal-exchanged zeolite catalysts. Catal Rev 50:492–531CrossRefGoogle Scholar
  2. 2.
    Roy S, Baiker A (2009) NOx storage− reduction catalysis: from mechanism and materials properties to storage− reduction performance. Chem Rev 109:4054–4091CrossRefGoogle Scholar
  3. 3.
    Yokomichi Y, Yamabe T, Kakumoto T, Okada O, Ishikawa H, Nakamura Y, Kimura H, Yasuda I (2000) Theoretical and experimental study on metal-loaded zeolite catalysts for direct NO x decomposition. Appl Catal B Environ 28:1–12CrossRefGoogle Scholar
  4. 4.
    Liu Z-P, Hu P (2004) CO oxidation and NO reduction on metal surfaces: density functional theory investigations. Top Catal 28:71–78CrossRefGoogle Scholar
  5. 5.
    Baidya T, Marimuthu A, Hegde M, Ravishankar N, Madras G (2007) Higher catalytic activity of nano-Ce1-x-yTixPdyO2-δ compared to nano-Ce1-xPdxO2-δ for CO oxidation and N2O and NO reduction by CO: role of oxide ion vacancy. J Phys Chem C 111:830–839CrossRefGoogle Scholar
  6. 6.
    Ilieva L, Pantaleo G, Ivanov I, Nedyalkova R, Venezia AM, Andreeva D (2008) NO reduction by CO over gold based on ceria, doped by rare earth metals. Catal Today 139:168–173CrossRefGoogle Scholar
  7. 7.
    Li J, Luo G, Chu Y, Wei F (2012) Experimental and modeling analysis of NO reduction by CO for a FCC regeneration process. Chem Eng J 184:168–175CrossRefGoogle Scholar
  8. 8.
    Yao X, Gao F, Yu Q, Qi L, Tang C, Dong L, Chen Y (2013) NO reduction by CO over CuO–CeO2 catalysts: effect of preparation methods. Catal Sci Technol 3:1355–1366CrossRefGoogle Scholar
  9. 9.
    Bourges P, Lunati S, Mabilon G (1998), in Stud Surf Sci Catal Elsevier vol. 116, pp. 213:222.Google Scholar
  10. 10.
    Eichler A, Hafner J (2001) NO reduction by CO on the Pt (100) surface: a density functional theory study. J Catal 204:118–128CrossRefGoogle Scholar
  11. 11.
    Wang Y, Zhang D, Yu Z, Liu C (2010) Mechanism of N2O formation during NO reduction on the Au (111) surface. J Phys Chem C 114:2711–2716CrossRefGoogle Scholar
  12. 12.
    Fajín JL, Cordeiro MND, Gomes JR (2012) Unraveling the mechanism of the NO reduction by CO on gold based catalysts. J Catal 289:11–20CrossRefGoogle Scholar
  13. 13.
    Frank B, Renken A (1999) Kinetics and deactivation of the NO reduction by CO on Pt-supported catalysts. Chem Eng Technol 22:490–494CrossRefGoogle Scholar
  14. 14.
    Ding W-C, Gu X-K, Su H-Y, Li W-X (2014) Single Pd atom embedded in CeO2 (111) for NO reduction with CO: a first-principles study. J Phys Chem C 118:12216–12223CrossRefGoogle Scholar
  15. 15.
    Deng J, Liu J, Song W, Zhao Z, Zhao L, Zheng H, Lee AC, Chen Y, Liu J (2017) Selective catalytic reduction of NO with NH 3 over Mo–Fe/beta catalysts: the effect of Mo loading amounts. RSC Adv 7:7130–7139CrossRefGoogle Scholar
  16. 16.
    Zhang X, Lu Z, Tang Y, Fu Z, Ma D, Yang Z (2014) A density function theory study on the NO reduction on nitrogen doped graphene. Phys Chem Chem Phys 16:20561–20569CrossRefGoogle Scholar
  17. 17.
    Lin Y, Williams TV, Connell JW (2009) Soluble, exfoliated hexagonal boron nitride nanosheets. J Phys Chem Lett 1:277–283CrossRefGoogle Scholar
  18. 18.
    Nag A, Raidongia K, Hembram KP, Datta R, Waghmare UV, Rao C (2010) Graphene analogues of BN: novel synthesis and properties. ACS Nano 4:1539–1544CrossRefGoogle Scholar
  19. 19.
    Cho H-B, Tokoi Y, Tanaka S, Suematsu H, Suzuki T, Jiang W, Niihara K, Nakayama T (2011) Modification of BN nanosheets and their thermal conducting properties in nanocomposite film with polysiloxane according to the orientation of BN. Compos Sci Technol 71:1046–1052CrossRefGoogle Scholar
  20. 20.
    Yao Y, Lin Z, Li Z, Song X, Moon K-S, Wong C (2012) Large-scale production of two-dimensional nanosheets. J Mater Chem 22:13494–13499CrossRefGoogle Scholar
  21. 21.
    Huang C, Chen C, Zhang M, Lin L, Ye X, Lin S, Antonietti M, Wang X, (2015) Carbon-doped BN nanosheets for metal-free photoredox catalysis Nat Commun, 6Google Scholar
  22. 22.
    Grad G, Blaha P, Schwarz K, Auwärter W, Greber T (2003) Density functional theory investigation of the geometric and spintronic structure of h-BN/Ni (111) in view of photoemission and STM experiments. Phys Rev B 68:085404CrossRefGoogle Scholar
  23. 23.
    Lin Y, Bunker CE, Fernando KS, Connell JW (2012) Aqueously dispersed silver nanoparticle-decorated boron nitride nanosheets for reusable, thermal oxidation-resistant surface enhanced Raman spectroscopy (SERS) devices. ACS Appl Mater Interfaces 4:1110–1117CrossRefGoogle Scholar
  24. 24.
    Li XM, Tian WQ, Huang X-R, Sun C-C, Jiang L (2009) Adsorption of hydrogen on novel Pt-doped BN nanotube: a density functional theory study. J Mol Struct THEOCHEM 901:103–109CrossRefGoogle Scholar
  25. 25.
    Sajjad M, Feng P (2014) Study the gas sensing properties of boron nitride nanosheets. Mater Res Bull 49:35–38CrossRefGoogle Scholar
  26. 26.
    Ren J, Zhang N, Zhang H, Peng X (2015) First-principles study of hydrogen storage on Pt (Pd)-doped boron nitride sheet. Struct Chem 26:731–738CrossRefGoogle Scholar
  27. 27.
    Beiranvand R, Valedbagi S (2015) Electronic and optical properties of h-BN nanosheet: a first principles calculation. Diam Relat Mater 58:190–195CrossRefGoogle Scholar
  28. 28.
    Beiranvand R, Valedbagi S (2016) Electronic and optical properties of advance semiconductor materials: BN, AlN and GaN nanosheets from first principles. Optik 127:1553–1560CrossRefGoogle Scholar
  29. 29.
    Jiang X-F, Weng Q, Wang X-B, Li X, Zhang J, Golberg D, Bando Y (2015) Recent progress on fabrications and applications of boron nitride nanomaterials: a review. J Mater Sci Technol 31:589–598CrossRefGoogle Scholar
  30. 30.
    Lu Z, Lv P, Xue J, Wang H, Wang Y, Huang Y, He C, Ma D, Yang Z (2015) Pd 1/BN as a promising single atom catalyst of CO oxidation: a dispersion-corrected density functional theory study. RSC Adv 5:84381–84388CrossRefGoogle Scholar
  31. 31.
    L-y F, Y-j L, J-x Z (2015) Iron-embedded boron nitride nanosheet as a promising electrocatalyst for the oxygen reduction reaction (ORR): a density functional theory (DFT) study. J Power Sources 287:431–438CrossRefGoogle Scholar
  32. 32.
    Deng D, Novoselov K, Fu Q, Zheng N, Tian Z, Bao X (2016) Catalysis with two-dimensional materials and their heterostructures. Nat Nanotechnol 11:218–230CrossRefGoogle Scholar
  33. 33.
    Lin S, Ye X, Johnson RS, Guo H (2013) First-principles investigations of metal (Cu, Ag, Au, Pt, Rh, Pd, Fe, Co, and Ir) doped hexagonal boron nitride nanosheets: stability and catalysis of CO oxidation. J Phys Chem C 117:17319–17326CrossRefGoogle Scholar
  34. 34.
    Zhou Y, Yang P, Sun X, Wang Z, Zu XT, Gao F (2011) First-principles study of the noble metal-doped BN layer. J Appl Phys 109:084308CrossRefGoogle Scholar
  35. 35.
    Liu X, Duan T, Sui Y, Meng C, Han Y (2014) Copper atoms embedded in hexagonal boron nitride as potential catalysts for CO oxidation: a first-principles investigation. RSC Adv 4:38750–38760CrossRefGoogle Scholar
  36. 36.
    Lu Z, Lv P, Liang Y, Ma D, Zhang Y, Zhang W, Yang X, Yang Z (2016) CO oxidation catalyzed by the single Co atom embedded hexagonal boron nitride nanosheet: a DFT-D study. Phys Chem Chem Phys 18:21865–21870CrossRefGoogle Scholar
  37. 37.
    Esrafili MD, Asadollahi S (2018) A single Pd atom stabilized on boron-vacancy of h-BN nanosheet: a promising catalyst for CO oxidation. ChemistrySelect 3:9181–9188Google Scholar
  38. 38.
    Meyer N, Devillers M, Hermans S (2015) Boron nitride supported Pd catalysts for the hydrogenation of lactose. Catal Today 241:200–207CrossRefGoogle Scholar
  39. 39.
    Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery Jr. JA, Peralta JE, Ogliaro F, Bearpark MJ, Heyd J, Brothers EN, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell AP, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam NJ, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ö, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09, Revision A. 02, Gaussian. Inc.Google Scholar
  40. 40.
    Zhao Y, Truhlar DG (2008) The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Accounts 120:215–241CrossRefGoogle Scholar
  41. 41.
    Jin C, Lin F, Suenaga K, Iijima S (2009) Fabrication of a freestanding boron nitride single layer and its defect assignments. Phys Rev Lett 102:195505CrossRefGoogle Scholar
  42. 42.
    Du A, Chen Y, Zhu Z, Amal R, Lu GQ, Smith SC (2009) Dots versus antidots: computational exploration of structure, magnetism, and half-metallicity in boron− nitride nanostructures. J Am Chem Soc 131:17354–17359CrossRefGoogle Scholar
  43. 43.
    Chau T-D, De Bocarmé TV, Kruse N (2004) Formation of N2O and (NO)2 during NO adsorption on Au 3D crystals. Catal Lett 98:85–87CrossRefGoogle Scholar
  44. 44.
    Liu Z-P, Jenkins SJ, King DA (2004) Why is silver catalytically active for NO reduction? A unique pathway via an inverted (NO)2 dimer. J Am Chem Soc 126:7336–7340CrossRefGoogle Scholar
  45. 45.
    Chen Y, Y-j L, Wang H-x, J-x Z, Q-h C, Wang X-z, Y-h D (2013) Silicon-doped graphene: an effective and metal-free catalyst for NO reduction to N2O? ACS Appl Mater Interfaces 5:5994–6000CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of Basic SciencesUniversity of MaraghehMaraghehIran
  2. 2.Biotechnology Research CenterTabriz University of Medical SciencesTabrizIran

Personalised recommendations