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Ethane dehydrogenation over Co-based MOR zeolites

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Abstract

Cobalt-based catalysts supported on MOR zeolites with various degree of dealumination were prepared and characterized by XRD, N2 adsorption, SEM, UV–vis, XPS, H2-TPR and FTIR. Their catalytic performance for ethane dehydrogenation was compared. More Co(II) species were found on the surface of dealuminated zeolites, leading to an enhancement in dehydrogenation activity. An ethane conversion of 53.4% with 92.1% selectivity to ethylene can be obtained over optimal catalyst. Characterization results indicate the increasing Co(II) species may derive from the increased silanol nest of MOR support via dealumination, which can interact with cobalt precursor to enhance its dispersion.

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Data availability

The datasets of current study are available from the corresponding author on reasonable request.

References

  1. Fairuzov D, Gerzeliev I, Maximov A, Naranov E (2021) Catalytic dehydrogenation of ethane: a mini review of recent advances and perspective of chemical looping technology. Catalysts 11(7):833

    Article  CAS  Google Scholar 

  2. Guo H, Miao C, Hua W, Yue Y, Gao Z (2021) Cobaltous oxide supported on MFI zeolite as an efficient ethane dehydrogenation catalyst. Micropor Mesopor Mater 312:110791

    Article  CAS  Google Scholar 

  3. Xu Y, Yu W, Zhang H, Xin J, He X, Liu B, Jiang F, Liu X (2021) Suppressing C–C bond dissociation for efficient ethane dehydrogenation over the isolated Co(II) sites in SAPO-34. ACS Catal 11(21):13001–13019

    Article  CAS  Google Scholar 

  4. Dai Y, Gao X, Wang Q, Wan X, Zhou C, Yang Y (2021) Recent progress in heterogeneous metal and metal oxide catalysts for direct dehydrogenation of ethane and propane. Chem Soc Rev 50(9):5590–5630

    Article  CAS  Google Scholar 

  5. Bhasin M, McCain J, Vora B, Imai T, Pujadó P (2001) Dehydrogenation and oxydehydrogenation of paraffins to olefins. Appl Catal A 221(1–2):397–419

    Article  CAS  Google Scholar 

  6. Llorca J, Homs N, Sales J, Ramı́rezde la Piscina P (2002) Efficient production of hydrogen over supported cobalt catalysts from ethanol steam reforming. J Catal 209(2):306–317

    Article  CAS  Google Scholar 

  7. Varga E, Pusztai P, Ovari L, Oszkó A, Erdőhelyi A, Papp C, Steinruck HP, Konya Z, Kiss J (2015) Probing the interaction of Rh, Co and bimetallic Rh–Co nanoparticles with the CeO2 support: catalytic materials for alternative energy generation. Phys Chem Chem Phys 17:27154–27166

    Article  CAS  Google Scholar 

  8. Varga E, Ferencz Z, Oszkó A, Erdőhelyi A, Kiss J (2015) Oxidation states of active catalytic centers in ethanol steam reforming reaction on ceria based Rh promoted Co catalysts: an XPS study. J Mol Catal A 397:127–133

    Article  CAS  Google Scholar 

  9. Dewangan N, Ashok J, Sethia M, Das S, Pati S, Kus H, Kawi S (2019) Cobalt-based catalyst supported on different morphologies of alumina for non-oxidative propane dehydrogenation: effect of metal support interaction and Lewis acidic sites. ChemCatChem 11(19):4923–4934

    Article  CAS  Google Scholar 

  10. Estes DP (2017) Mechanistic investigations of C-H activations on silica-supported Co(II) sites in catalytic propane dehydrogenation. Chimia (Aarau) 71(4):177–180

    Article  CAS  Google Scholar 

  11. Yu SY, Yu GJ, Li W, Iglesia E (2002) Kinetics and reaction pathways for propane dehydrogenation and aromatization on Co/H-ZSM5 and H-ZSM5. J Phys Chem 106(18):4714–4720

    Article  CAS  Google Scholar 

  12. Estes DP, Siddiqi G, Allouche F, Kovtunov KV, Safonova OV, Trigub AL, Koptyug IV, Coperet C (2016) C-H activation on Co, O sites: isolated surface sites versus molecular analogs. J Am Chem Soc 138(45):14987–14997

    Article  CAS  Google Scholar 

  13. Koirala R, Buechel R, Pratsinis SE, Baiker A (2016) Silica is preferred over various single and mixed oxides as support for CO2-assisted cobalt-catalyzed oxidative dehydrogenation of ethane. Appl Catal A 527:96–108

    Article  CAS  Google Scholar 

  14. Koirala R, Safonova OV, Pratsinis SE, Baiker A (2018) Effect of cobalt loading on structure and catalytic behavior of CoOx/SiO2 in CO2-assisted dehydrogenation of ethane. Appl Catal A 552:77–85

    Article  CAS  Google Scholar 

  15. Wu L, Ren Z, He Y, Yang M, Yu Y, Liu Y, Tan L, Tang Y (2021) Atomically dispersed Co2+ sites incorporated into a silicalite-1 zeolite framework as a high-performance and coking-resistant catalyst for propane nonoxidative dehydrogenation to propylene. ACS Appl Mater Interfaces 13(41):48934–48948

    Article  CAS  Google Scholar 

  16. Song S, Li J, Wu Z, Zhang P, Sun Y, Song W, Li Z, Liu J (2021) In situ encapsulated subnanometric CoO clusters within silicalite-1 zeolite for efficient propane dehydrogenation. AIChE J 68(2):e17451

    Google Scholar 

  17. Cheng Y, Miao C, Hua W, Yue Y, Gao Z (2017) Cr/ZSM-5 for ethane dehydrogenation: enhanced catalytic activity through surface silanol. Appl Catal A 532:111–119

    Article  CAS  Google Scholar 

  18. Guo H, Miao C, Hua W, Yue Y, Gao Z (2020) Enhanced catalytic performance of Cr/MOR for ethane dehydrogenation through dealumination. Catal Lett 151(5):1499–1507

    Article  Google Scholar 

  19. Hu B, Kim WG, Sulmonetti TP, Sarazen ML, Tan S, So J, Liu Y, Dixit RS, Nair S, Jones CW (2017) A mesoporous cobalt aluminate spinel catalyst for nonoxidative propane dehydrogenation. ChemCatChem 9:3330–3337

    Article  CAS  Google Scholar 

  20. Liu Y, Zhao N, Xian H, Cheng Q, Tan Y, Tsubaki N, Li X (2015) Facilely synthesized H-mordenite nanosheet assembly for carbonylation of dimethyl ether. ACS Appl Mater Interfaces 7(16):8398–8403

    Article  CAS  Google Scholar 

  21. Brik Y, Kacimi M, Ziyad M, Bozon-Verduraz F (2001) Titania-supported cobalt and cobalt–phosphorus catalysts: characterization and performances in ethane oxidative dehydrogenation. J Catal 202(1):118–128

    Article  CAS  Google Scholar 

  22. Zhao Y, Sohn H, Hu B, Niklas J, Poluektov OG, Tian J, Delferro M, Hock AS (2018) Zirconium modification promotes catalytic activity of a single-site cobalt heterogeneous catalyst for propane dehydrogenation. ACS Omega 3(9):11117–11127

    Article  CAS  Google Scholar 

  23. Bian Z, Dewangan N, Wang Z, Pati S, Xi S, Borgna A, Kus H, Kawi S (2021) Mesoporous-silica-stabilized cobalt(II) oxide nanoclusters for propane dehydrogenation. ACS Appl Nano Mater 4(2):1112–1125

    Article  CAS  Google Scholar 

  24. Ji L, Lin J, Zeng HC (2000) Metal−support interactions in Co/Al2O3 catalysts: a comparative study on reactivity of support. J Phys Chem B 104(8):1783–1790

    Article  CAS  Google Scholar 

  25. Riva R, Miessner H, Vitali R, Piero G (2000) Metal–support interaction in Co/SiO2 and Co/TiO2. Appl Catal A 196(1):111–123

    Article  CAS  Google Scholar 

  26. Mo S, He H, Ren Q, Li S, Zhang W, Fu M, Chen L, Wu J, Chen Y, Ye D (2019) Macroporous Ni foam-supported Co3O4 nanobrush and nanomace hybrid arrays for high-efficiency CO oxidation. J Environ Sci (China) 75:136–144

    Article  Google Scholar 

  27. Dai Y, Gu J, Tian S, Wu Y, Chen J, Li F, Du Y, Peng L, Ding W, Yang Y (2020) γ-Al2O3 sheet-stabilized isolate Co2+ for catalytic propane dehydrogenation. J Catal 381:482–492

    Article  CAS  Google Scholar 

  28. Martono E, Vohs JM (2011) Active sites for the reaction of ethanol to acetaldehyde on Co/YSZ(100) model steam reforming catalysts. ACS Catal 1:1414–1420

    Article  CAS  Google Scholar 

  29. Ferencz Z, Erdőhelyi A, Baán K, Oszkó A, Óvári L, Kónya Z, Papp C, Steinrück HP, Kiss J (2014) Effects of support and Rh additive on Co-based catalysts in the ethanol steam reforming reaction. ACS Catal 4:1205–1218

    Article  CAS  Google Scholar 

  30. Li X, Wang P, Wang H, Li C (2018) Effects of the state of Co species in Co/Al2O3 catalysts on the catalytic performance of propane dehydrogenation. Appl Surf Sci 441:688–693

    Article  CAS  Google Scholar 

  31. Chen C, Zhang S, Wang Z, Yuan Z-Y (2020) Ultrasmall Co confined in the silanols of dealuminated beta zeolite: a highly active and selective catalyst for direct dehydrogenation of propane to propylene. J Catal 383:77–87

    Article  CAS  Google Scholar 

  32. Ren L, Wang B, Lu K, Peng R, Guan Y, Jiang J-g, Xu H, Wu P (2021) Selective conversion of methanol to propylene over highly dealuminated mordenite: Al location and crystal morphology effects. Chin J Catal 42(7):1147–1159

    Article  CAS  Google Scholar 

  33. Wang M, Huang S, Lü J, Cheng Z, Li Y, Wang S, Ma X (2016) Modifying the acidity of H-MOR and its catalytic carbonylation of dimethyl ether. Chin J Catal 37(9):1530–1537

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was funded by the National Natural Science Foundation of China (Grant No. 22072027), National Key R&D Program of Ministry of Science and Technology (Grant No. 2017YFB0602204) and the Science & Technology Commission of Shanghai Municipality (Grant No. 19DZ2270100).

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Authors and Affiliations

  1. Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, People’s Republic of China

    Huan He, Hongyao Guo, Weiming Hua, Yinghong Yue & Zi Gao

  2. Shanghai Research Institute of Petrochemical Technology, Shanghai, 201208, People’s Republic of China

    Changxi Miao

Authors
  1. Huan He
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  2. Changxi Miao
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  3. Hongyao Guo
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  4. Weiming Hua
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  5. Yinghong Yue
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  6. Zi Gao
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Contributions

Conceptualization: YY, CM; Methodology: CM, HG; Formal analysis and investigation, HH; HG: Writing—original draft preparation: HH; Writing—review and editing: YY, WH; Supervision: YY, ZG.

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Correspondence to Yinghong Yue.

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He, H., Miao, C., Guo, H. et al. Ethane dehydrogenation over Co-based MOR zeolites. Reac Kinet Mech Cat 135, 2045–2058 (2022). https://doi.org/10.1007/s11144-022-02231-9

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  • DOI: https://doi.org/10.1007/s11144-022-02231-9

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