Skip to main content
SpringerLink
Log in

Stability and electronic properties of IrnV (n = 2–10) nanoclusters and their reactivity toward N2H4 molecule

  • Original Research
  • Published:
Structural Chemistry Aims and scope Submit manuscript

Abstract

DFT calculations have been carried out over the IrnV (n = 2–10) clusters in order to predict their stability, electronic, and catalytic properties. Based on the fragmentation energy (ΔEf) and the second-order difference energy (Δ2E), the results show that the V-doped iridium clusters with sizes of n = 5 and 7 were found more stable than their neighboring clusters. Our results also exhibit that the calculated energy gaps (Eg) for these clusters are in the range 0.074–0.603 eV, suggesting that the metallic character can manifest in these binary clusters. Therefore, the IrnV clusters can be utilized as catalysts in several catalytic reactions. MEP analysis exhibits that the highest positive charge resides on the V atom, thus the V atom in the binary clusters can be considered as the most active site for the nucleophilic attack. So, it represents a favorable electrophilic adsorption site that can strongly interact with the electron-rich molecules. The influence of the N2H4 adsorption over the electronic properties of IrnV clusters was also investigated. The results show that the adsorption energies (Eads) vary between − 21.3 and − 46.6 kcal mol−1, suggesting a chemisorption process. The change in enthalpy (ΔHads) is in the range of − 24.6 to − 51.0 kcal mol−1, indicating that the interaction between the IrnV clusters and the N2H4 molecule is very strong, and the formed complexes by chemisorption between the clusters and the N2H4 molecule are thermodynamically stable at standard conditions. The energy gaps of clusters are sharply changed upon adsorption of hydrazine onto the surface of the clusters, implying a great sensitivity of these clusters toward N2H4 molecule. The calculated dipole moments were also largely increased after chemisorption of the N2H4 molecule over the clusters.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  1. Palpant B, Prevel B, Lerme J, Cottancin E, Pellarin M, Treilleux M, Perez A, Vialle JL, Broyer M (1998) Optical properties of gold clusters in the size range 2-4 nm. Phys Rev B 57:1963

    CAS  Google Scholar 

  2. Chettibi M, Boudjahem A, Bettahar M (2011) Synthesis of Ni/SiO2 nanoparticles for catalytic benzene hydrogenation. Transit Met Chem 36:163–169

    CAS  Google Scholar 

  3. Zhang JY, Fang Q, Kenyon AJ, Boyd IW (2003) Visible photoluminescence from nanocrystalline Ge grown at room temperature by photo-oxidation of SiGe using a 126 nm lamp. Appl Surf Sci 208–209:364–368

    Google Scholar 

  4. Dong CD, Gong XG (2008) Magnetism enhanced layer-like structure of small cobalt clusters. Phys Rev B 78:020409

    Google Scholar 

  5. Gopidas KR, Whitesell JM, Fox MA (2003) Synthesis, characterization and catalytic applications of a palladium-nanoparticles-cored dendrimer. Nano Lett 3:1757–1760

    CAS  Google Scholar 

  6. Mokrane T, Boudjahem A, Bettahar M (2016) Benzene hydrogenation over alumina-supported nickel nanoparticles prepared by polyol method. RSC Adv 6:59858–59864

    CAS  Google Scholar 

  7. Alexeev O, Li F, Amiridis MD, Gates B (2005) Effects of Adsorbates on supported platinum and iridium clusters: characterization in reactive atmospheres and during alkene hydrogenation catalysis by X-ray absorption spectroscopy. J Phys Chem B 109:2338–2349

    CAS  PubMed  Google Scholar 

  8. Cho S, Lee J, Lee YS, Kim D (2006) Characterization of iridium catalyst for decomposition of hydrazine hydrate for hydrogen generation. Catal Lett 109:181–186

    CAS  Google Scholar 

  9. Contour JP, Pannetier G (1972) Hydrazine decomposition over a supported iridium catalyst. J Catal 24:434–445

    CAS  Google Scholar 

  10. Jang Y, Kim T, Sun M, Lee J, Cho SJ (2009) Preparation of iridium catalyst and its catalytic activity over hydrazine hydrate decomposition for hydrogen production and storage. Catal Today 146:196–201

    CAS  Google Scholar 

  11. Wang L, Zhao X, Zheng M, Cheng R, Zhou L, Zhang T (2005) Microcalorimetric studies of the iridium catalyst for hydrazine decomposition reaction. Thermochim Acta 434:119–124

    Google Scholar 

  12. Siang J, Lee C, Wang C-H, Wang W-T, Deng C-Y, Yeh C, Wang C-B (2010) Hydrogen production from steam reforming of ethanol using a ceria-supported iridium catalyst: effect of different ceria supports. Int J Hydrog Energy 35:3456–3462

    CAS  Google Scholar 

  13. Himeda Y (2009) Highly efficient hydrogen evolution by decomposition of formic acid using an iridium catalyst with 4,4-dihydroxy-2,2-bipyridine. Green Chem 11:2018–2022

    CAS  Google Scholar 

  14. Alexeev O, Gates BC (1998) Iridium clusters supported on γ-Al2O3: structural characterization and catalysis of toluene hydrogenation. J Catal 176:310–320

    CAS  Google Scholar 

  15. Singh SK, Xu Q (2010) Bimetallic nickel-iridium nanocatalysts for hydrogen generation by decomposition of hydrous hydrazine. Chem Commun 46:6545–6547

    CAS  Google Scholar 

  16. Tandon PK, Srivastava M, Singh SB, Singh S (2008) Liquid-phase and microwave assisted oxidation of some hydrocarbons, aromatic aldehydes and phenols by cerium (IV) catalyzed by iridium (III) in acidic medium. Synth Commun 38(208):2125–2137

    CAS  Google Scholar 

  17. Tandon PK, Dwivedi PB, Singh S (2009) Liquid-phase oxidation of some aromatic aldehydes, hydrocarbons, and alcohols by cerium (IV) catalyzed by iridium (III) in acidic medium. Synth Commun 39:1920–1928

    CAS  Google Scholar 

  18. Sakurai Y, Suzaki T, Ikenaga N, Suzuki T (2000) Dehydrogenation of ethylbenzene with an activated carbon-supported vanadium catalyst. Appl Catal A 192:281–288

    CAS  Google Scholar 

  19. Jorge FE, Venancio JR (2018) Structure, stability catalytic activity and polarizability of small iridium clusters. Chin Phys B 27:063102

    Google Scholar 

  20. Du J, Sun X, Chen J, Jiang G (2010) A theoretical study on small iridium clusters: structural evolution, electronic and magnetic properties and reactivity predictors. J Phys Chem A 114:12825–12833

    CAS  PubMed  Google Scholar 

  21. Pawluk T, Hirata Y, Wang L (2005) Studies of iridium nanoparticles using density functional theory calculations. J Phys Chem B 109:20817–20823

    CAS  PubMed  Google Scholar 

  22. Okumura M, Irie Y, Kitagawa Y, Fujitani T, Maeda Y (2006) DFT studies of interaction of Ir cluster with O2, CO and NO. Catal Today 111:311–315

    CAS  Google Scholar 

  23. Feng J-N, Huang X-R, Li Z-S (1997) A theoretical study on the clusters Irn with n = 4,6, 8, 10. Chem Phys Lett 276:334–338

    CAS  Google Scholar 

  24. He L, Huang Y, Liu X, Li L, Wang A, Wang X, Mou C-Y, Zhang T (2014) Structural and catalytic properties of supported Ni-Ir alloy catalysts for H2 generation via hydrous hydrazine decomposition. Appl Catal B 147:779–788

    CAS  Google Scholar 

  25. Davis J, Horswell S, Piccolo L, Johnston R (2015) Computational study of the adsorption of benzene and hydrogen on palladium-iridium nanoalloys. J Organomet Chem 792:190–193

    CAS  Google Scholar 

  26. Estejab A, Botte G (2016) DFT calculations of ammonia oxidation reactions on bimetallic clusters of platinum and iridium. Comput Theor Chem 1091:31–40

    CAS  Google Scholar 

  27. Bouderbala W, Boudjahem A, Soltani A (2014) Geometries, stabilities, electronic and magnetic properties of small PdnIr (n = 1-8) clusters from first-principles calculations. Mol Phys 112:1789–1798

    CAS  Google Scholar 

  28. Becke AD (1988) Density-functional exchange-energy approximation with correct asymptotic behavior. Phys Rev A 38:3098–3100

    CAS  Google Scholar 

  29. Lee C, Yang W, Parr RG (1988) Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys Rev B 37:785–789

    CAS  Google Scholar 

  30. 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, Jr JA, Montgomery JE, Peralta F, Ogliaro M, Bearpark JJ, Heyd E, Brothers KN, Kudin VN, Staroverov T, Keith R, Kobayashi J, Normand K, Raghavachari A, Rendell JC, Burant SS, Iyengar J, Tomasi M, Cossi N, Rega JM, Millam M, Klene JE, Knox JB, Cross V, Bakken C, Adamo J, Jaramillo R, Gomperts RE, Stratmann O, Yazyev AJ, Austin R, Cammi C, Pomelli JW, Ochterski RL, Martin K, Morokuma VG, Zakrzewski GA, Voth P, Salvador JJ, Dannenberg S, Dapprich AD, Daniels O, Farkas JB, Foresman JV, Ortiz J, Cioslowski DJ (2013) Fox, Gaussian 09, Revision D.01. Gaussian, Inc., Wallingford

    Google Scholar 

  31. Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg. J Chem Phys 82:270–283

    CAS  Google Scholar 

  32. Hay PJ, Wadt WR (1985) Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals. J Chem Phys 82:299–310

    CAS  Google Scholar 

  33. Krishnan RBJS, Binkley JS, Seeger R, Pople JA (1980) Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions. J Chem Phys 72:650–654

    CAS  Google Scholar 

  34. Boulbazine M, Boudjahem A, Bettahar M (2017) Stabilities, electronic and magnetic properties of Cu-doped nickel clusters: a DFT investigation. Mol Phys 115:2495–2507

    CAS  Google Scholar 

  35. Soltani A, Boudjahem A, Bettahar M (2016) Electronic and magnetic properties of small RhnCa (n = 1-9) clusters: a DFT study. Int J Quantum Chem 116:346–356

    CAS  Google Scholar 

  36. Jules JL, Lombardi JR (2003) Transition metal dimer internuclear distances from measured force constants. J Phys Chem A 107:1268–1273

    CAS  Google Scholar 

  37. Miedema AR, Gingerich KA (1979) On the formation enthalpy of metallic dimers. J Phys B 12:2081

    CAS  Google Scholar 

  38. Morse MD (1986) Clusters of transition-metal atoms. Chem Rev 86:1049–1109

    CAS  Google Scholar 

  39. Spain EM, Morse MD (1992) Bond strengths of transition-metal dimers: titanium-vanadium (TiV), vanadium dimer, titanium-cobalt (TiCo), and vanadium-nickel (VNi). J Phys Chem 96:2479–2486

    CAS  Google Scholar 

  40. Langridge-Smith PRR, Morse MD, Hansen GP, Smalley RE, Merer AJ (1983) The bond length and electronic structure of V2. J Chem Phys 80:593–600

    Google Scholar 

  41. Jena P, Rao BK, Nieminen RM (1986) Fragmentation channels and their relationship to magic number studies of microclusters. Solid State Commun 59:509–512

    CAS  Google Scholar 

  42. Xiong R, Die D, Xiao L, Xu YG, Shen XY (2017) Probing the structural, electronic, and magnetic properties of Ag n V (n = 1–12) clusters. Nanoscale Res Lett 12:625

    PubMed  PubMed Central  Google Scholar 

  43. Devi AAS (2014) Structural, magnetic and electronic properties of Fex Coy Irz (x+ y+ z = 5, 6) clusters: an ab initio study. Eur Phys J D 68:120

    Google Scholar 

  44. Wu G, Yang M, Guo X, Wang J (2012) Comparative DFT study of N2 and NO adsorption on vanadium clusters Vn (n = 2–13). J Comput Chem 33:1854–1861

    CAS  PubMed  Google Scholar 

  45. Boulbazine M, Boudjahem A (2019) Stability, electronic and magnetic properties of Mn-doped copper clusters: a Meta-GGA functional investigation. J Clust Sci 30:31–44

    CAS  Google Scholar 

  46. Boudjahem A, Boulbazine M, Chettibi M (2018) Electronic and magnetic properties of Os-doped rhodium clusters: a theoretical study. J Supercond Nov Magn 31:3119–3131

    CAS  Google Scholar 

  47. Soltani A, Boudjahem A (2014) Stabilities, electronic and magnetic properties of small Rhn (n = 2–12) clusters: a DFT approach. Comput Theor Chem 1047:6–14

    CAS  Google Scholar 

  48. Bouderbala W, Boudjahem A (2014) First-principles calculations of small PdnAlm (n + m ≤ 6) clusters. Phys B 454:217–223

    CAS  Google Scholar 

  49. Wang BR, Han HY, Xie Z (2014) Structural andmagnetic properties of small NinMn clusters. J Mol Struct 1062:174–178

    CAS  Google Scholar 

  50. Lee S, Fan C, Wu T, Anderson SL (2005) Hydrazine decomposition over Irn/Al2O3 model catalysts prepared by size-selected cluster deposition. J Phys Chem B 109:381–388

    CAS  PubMed  Google Scholar 

  51. Gupta M, Kaska WC, Jensen CM (1997) Catalytic dehydrogenation of ethylbenzene and tetrahydrofuran by a dihydrido iridium P-C-P pincer complex. Chem Commun 5:461–462

    Google Scholar 

  52. Behr A, Kamper A, Nickel M, Franke R (2015) Crucial role of additives in iridium-catalyzed hydroformylation. App Catal A 505:243–248

    CAS  Google Scholar 

  53. Baei MT, Soltani A, Hashemian S (2016) Adsorption properties of hydrazine on pristine and Si-doped Al12N12 nano-cage. Phosphorus Sulfur 191:702–708

    CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Computational Catalysis Group, Laboratory of Applied Chemistry, University of Guelma, Box 401, 24000, Guelma, Algeria

    Abdelhak Karaman, Abdel-Ghani Boudjahem & Mouhssin Boulbazine

  2. Laboratoire sciences et techniques de l’eau et environnement, Université de Souk-Ahras, 41000, Souk-Ahras, Algeria

    Abdelhak Karaman & Abdelhak Gueid

Authors
  1. Abdelhak Karaman
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Abdel-Ghani Boudjahem
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mouhssin Boulbazine
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Abdelhak Gueid
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Abdel-Ghani Boudjahem.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOCX 47 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Karaman, A., Boudjahem, AG., Boulbazine, M. et al. Stability and electronic properties of IrnV (n = 2–10) nanoclusters and their reactivity toward N2H4 molecule. Struct Chem 31, 203–214 (2020). https://doi.org/10.1007/s11224-019-01391-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11224-019-01391-0

Keywords

Search

Navigation