Skip to main content
SpringerLink
Log in

Investigation of CHx (x = 2–4) Adsorption on Mo2C and Mo4C2 Sites Incorporated in ZSM-5 Zeolite Using Periodic-DFT Approach

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

One of the major challenges of methane dehydroaromatization technology development is rapid deactivation of the catalyst due to the coke formation. The coke formation depends on the stability of CHx species formed during the stage of CH4 activation. In the present computational study, we have employed periodic-DFT approach to investigate the adsorption behavior of the CHx (x = 2–4) species on Mo2C and Mo4C2 clusters incorporated at three different Al substitutions viz. T8–T8, T8–T12 and T8–T7. The results indicate that the Mo2C cluster is responsible for weaker CH4 adsorption compared to Mo4C2. However, the CH3 and CH2 species are chemisorbed on the Mo2C cluster. Interestingly, in the case of Mo4C2 cluster we found two chemisorbed states of CH2 species. From this analysis, we propose that the relatively weaker chemisorbed state of CH2 in the top-site would be responsible for the formation of C2 intermediate leading to desired aromatics, while the strongly chemisorbed CH2 state will lead to undesired C formation.

Graphical Abstract

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
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Horn R, Schlögl R (2015) Cat Lett 145:23

    Article  CAS  Google Scholar 

  2. Olivos-Suarez AI, Szécsényi À, Hensen EJM, Ruiz-Martinez J, Pidko EA, Gascon J (2016) ACS Catal 6:2965

    Article  CAS  Google Scholar 

  3. Ismagilov ZR, Matus EV, Tsikoza LT (2008) Energy Environ Sci 1:526

    Article  CAS  Google Scholar 

  4. Spivey JJ, Hutchings G (2014) Chem Soc Rev 43:792

    Article  CAS  Google Scholar 

  5. Lunsford JH (2000) Catal Today 63:165

    Article  CAS  Google Scholar 

  6. Weckhuysen BM, Wang DJ, Roseynek MP, Lunsford JH (1998) J Catal 175:338

    Article  CAS  Google Scholar 

  7. Xu Y, Bao X, Lin L (2003) J Catal 216:386

    Article  CAS  Google Scholar 

  8. Choudhary VR, Kinage AK, Choudhary TV (1997) Science 275:1286

    Article  CAS  Google Scholar 

  9. Ma S, Guo X, Zhao L, Scott S, Bao X (2013) J Energy Chem 22:1

    Article  Google Scholar 

  10. Ma D, Shu Y, Bao X, Xu Y (2000) J Catal 189:314

    Article  CAS  Google Scholar 

  11. Teresa Portilla M, Tempelman CHL, Martínez C, Hensen EJM (2015) New trends in catalyst design for methane dehydroaromatization, small-scale gas to liquid fuel. Synthesis Edited by Nick Kanellopoulos, CRC Press, Boca Raton, pp 263–291

  12. Ding W, Li S, Meitzner GD, Iglesia E (2001) J Phys Chem B 105:506

    Article  CAS  Google Scholar 

  13. Solymosi F, Csere´nyi J, Szo¨ke A, Ba´nsa´gi T, Oszko A (1997) J Catal 165:150

    Article  CAS  Google Scholar 

  14. Solymosi F, Nemeth R, Ovari L, Egri L (2000) J Catal 195:316

    Article  CAS  Google Scholar 

  15. Solymosi F, Szechenyi A (2004) Appl Catal A 278:111

    Article  CAS  Google Scholar 

  16. Li W, Meitzner GD, Borry RW, Iglesia E (2000) J Catal 191:373

    Article  CAS  Google Scholar 

  17. Liu H, Bao X, Xu Y (2006) J Catal 239:441

    Article  CAS  Google Scholar 

  18. Wang D, Lunsford JH, Rosynek MP (1996) Top Catal 3:289

    Article  CAS  Google Scholar 

  19. Zheng H, Ma D, Bao X, Jian ZH, Ja HK, Wang Y, Peden CHF (2008) J Am Chem Soc 130:3722

    Article  CAS  Google Scholar 

  20. Lezcano-González I, Oord R, Rovezzi M, Glatzel P, Botchway SW, Weckhuysen BM, Beale AM (2016) Angew Chem Int Ed 55:5215

    Article  Google Scholar 

  21. Gao J, Zheng Y, Jehng J-M, Tang Y, Wachs IE, Podkolzin SG (2015) Science 348:686

    Article  CAS  Google Scholar 

  22. Fadeeva EV, Mamonov NA, Kustov LM, Mikhailo MN (2013) Russ Chem Bull Int Ed 62:1967

    Article  CAS  Google Scholar 

  23. Zhou D, Zhang Y, Zhu H, Ma D, Bao X (2007) J Phys Chem C 111:2081

    Article  CAS  Google Scholar 

  24. Zhou D, Ma D, Wang Y, Liu X, Bao X (2003) Chem Phys Lett 373:46

    Article  CAS  Google Scholar 

  25. Gao J, Zheng Y, Fitzgerald GB, de Joannis J, Tang Y, Wachs IE, Podkolzin SG (2014) J Phys Chem C 118:4670

    Article  CAS  Google Scholar 

  26. Zhou D, Zuo S, Xing S (2012) J Phys Chem C 116:4060

    Article  CAS  Google Scholar 

  27. Kosinov N, Coumans FJAG, Uslamin E, Kapteijn F, Hensen EJM (2016) Angew Chem Int Ed 55:15086

    Article  CAS  Google Scholar 

  28. Kosinov N, Coumans FJAG, Li G, Uslamin E, Mezari B, Wijpkema ASG, Pidko EA, Hensen EJM (2017) J Catal 346:125

    Article  CAS  Google Scholar 

  29. Chinta S, Choudhary TV, Daemen LL, Eckert J, Goodman DW (2002) Angew Chem Int Ed 41:144–146

    Article  Google Scholar 

  30. Medea -VASP From Materials Design®. Licensed to SABIC

  31. Kresse G, Furthmuller J (1996) Comput Mater Sci (1996) 6:15

  32. Kresse G, Furthmuller J (1996) Phys. Rev. B 54:11169

    Article  CAS  Google Scholar 

  33. Kresse G, Hafner J (1993) Phys. Rev. B 47:558

    Article  CAS  Google Scholar 

  34. Grimme S (2006) J. Comput Chem 27:1787

    Article  CAS  Google Scholar 

  35. Stave MS, Nicholas JB (1995) J Phys Chem 99:15046

    Article  CAS  Google Scholar 

  36. Chatterjee A, Chandra AK (1997) J Mol Catal A 119:51

    Article  CAS  Google Scholar 

  37. Ghorbanpour A, Rimer JD, Grabow LC (2014) Catal Commun 52:98–102

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. SABIC Research and Technology Pvt. Ltd., Bengaluru, Karnataka, 562125, India

    Sharankumar Shetty, S. Sivakumar, Suman Kumar Jana & G. Sreenivasarao

Authors
  1. Sharankumar Shetty
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. S. Sivakumar
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Suman Kumar Jana
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. G. Sreenivasarao
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sharankumar Shetty.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 6828 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Shetty, S., Sivakumar, S., Jana, S.K. et al. Investigation of CHx (x = 2–4) Adsorption on Mo2C and Mo4C2 Sites Incorporated in ZSM-5 Zeolite Using Periodic-DFT Approach. Catal Lett 148, 68–78 (2018). https://doi.org/10.1007/s10562-017-2199-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-017-2199-x

Keywords

Search

Navigation