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Quantitative production of butenes from biomass-derived γ-valerolactone catalysed by hetero-atomic MFI zeolite


The efficient production of light olefins from renewable biomass is a vital and challenging target to achieve future sustainable chemical processes. Here we report a hetero-atomic MFI-type zeolite (NbAlS-1), over which aqueous solutions of γ-valerolactone (GVL), obtained from biomass-derived carbohydrates, can be quantitatively converted into butenes with a yield of >99% at ambient pressure under continuous flow conditions. NbAlS-1 incorporates simultaneously niobium(v) and aluminium(iii) centres into the framework and thus has a desirable distribution of Lewis and Brønsted acid sites with optimal strength. Synchrotron X-ray diffraction and absorption spectroscopy show that there is cooperativity between Nb(v) and the Brønsted acid sites on the confined adsorption of GVL, whereas the catalytic mechanism for the conversion of the confined GVL into butenes is revealed by in situ inelastic neutron scattering, coupled with modelling. This study offers a prospect for the sustainable production of butene as a platform chemical for the manufacture of renewable materials.

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Fig. 1: Physical characterization of catalysts.
Fig. 2: Catalyst stability.
Fig. 3: Nb K-edge XAS for Nb-containing zeolites.
Fig. 4: Views of crystal structures of GVL-loaded HZSM-5(0.04/1), NbS-1(0.027/1) and NbAlS-1(0.027/0.04/1).
Fig. 5: INS spectra for NbAlS-1(0.027/0.04/1) on the adsorption and catalytic conversion of GVL and the proposed reaction mechanisms.

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All the relevant data are available from the authors, and/or are included with the manuscript.


  1. Torres Galvis, H. M. & de Jong, K. P. Catalysts for production of lower olefins from synthesis gas: a review. ACS Catal. 3, 2130–2149 (2013).

    CAS  Google Scholar 

  2. Bender, M. An overview of industrial processes for the production of olefins—C4 hydrocarbons. ChemBioEng Rev. 1, 136–147 (2014).

    CAS  Google Scholar 

  3. Galvis, H. M. T. et al. Supported iron nanoparticles as catalysts for sustainable production of lower olefins. Science 335, 835–838 (2012).

    Google Scholar 

  4. Amghizar, I., Vandewalle, L. A., Van Geem, K. M. & Marin, G. B. New trends in olefin production. Engineering 3, 171–178 (2017).

    CAS  Google Scholar 

  5. Jiao, F. et al. Selective conversion of syngas to light olefins. Science 351, 1065–1068 (2016).

    CAS  Google Scholar 

  6. Zacharopoulou, V. & Lemonidou, A. A. Olefins from biomass intermediates: a review. Catalysts 8, 2 (2018).

    Google Scholar 

  7. Tuck, C. O., Pérez, E., Horváth, I. T., Sheldon, R. A. & Poliakoff, M. Valorization of biomass: deriving more value from waste. Science 337, 695–699 (2012).

    CAS  Google Scholar 

  8. Bozell, J. J. Connecting biomass and petroleum processing with a chemical bridge. Science 329, 522–523 (2010).

    CAS  Google Scholar 

  9. Bond, J. Q., Alonso, D. M., Wang, D., West, R. M. & Dumesic, J. A. Integrated catalytic conversion of γ-valerolactone to liquid alkenes for transportation fuels. Science 327, 1110–1114 (2010).

    CAS  Google Scholar 

  10. Jing, Y., Guo, Y., Xia, Q., Liu, X. & Wang, Y. Catalytic production of value-added chemicals and liquid fuels from lignocellulosic biomass. Chem 5, 2520–2546 (2019).

    CAS  Google Scholar 

  11. Corma, A., Iborra, S. & Velty, A. Chemical routes for the transformation of biomass into chemicals. Chem. Rev. 107, 2411–2502 (2007).

    CAS  Google Scholar 

  12. Yan, K., Yang, Y., Chai, J. & Lu, Y. Catalytic reactions of gamma-valerolactone: a platform to fuels and value-added chemicals. Appl. Catal. B 179, 292–304 (2015).

    CAS  Google Scholar 

  13. Lin, L. et al. Acid strength controlled reaction pathways for the catalytic cracking of 1-butene to propene over ZSM-5. J. Catal. 309, 136–145 (2014).

    CAS  Google Scholar 

  14. Hong, E., Park, J.-H. & Shin, C.-H. Oxidative dehydrogenation of n-butenes to 1,3-butadiene over bismuth molybdate and ferrite catalysts: a review. Catal. Surv. Asia 20, 23–33 (2016).

    CAS  Google Scholar 

  15. Ye, L. et al. Decarboxylation of lactones over Zn/ZSM-5: elucidation of the structure of the active site and molecular interactions. Angew. Chem. Int. Ed. 56, 10711–10716 (2017).

    CAS  Google Scholar 

  16. Shao, H., Lv, Z., Sun, Z., Liu, C. & He, A. Synthesis of spherical polyethylene/poly(1-butene) reactor blends with two-stage sequence polymerization technology. Polymer 144, 72–79 (2018).

    CAS  Google Scholar 

  17. Kim, M. S., Park, M. S., Seo, H. J. & Lee, S. H. Method for preparing polybutene. US Patent 9683060B2 (2017).

  18. Kellicutt, A. B., Salary, R., Abdelrahman, O. A. & Bond, J. Q. An examination of the intrinsic activity and stability of various solid acids during the catalytic decarboxylation of γ-valerolactone. Catal. Sci. Technol. 4, 2267–2279 (2014).

    CAS  Google Scholar 

  19. Bond, J. Q., Wang, D., Alonso, D. M. & Dumesic, J. A. Interconversion between γ-valerolactone and pentenoic acid combined with decarboxylation to form butene over silica/alumina. J. Catal. 281, 290–299 (2011).

    CAS  Google Scholar 

  20. Bond, J. Q., Martin Alonso, D., West, R. M. & Dumesic, J. A. γ-Valerolactone ring-opening and decarboxylation over SiO2/Al2O3 in the presence of water. Langmuir 26, 16291–16298 (2010).

    CAS  Google Scholar 

  21. Bond, J. Q., Jungong, C. S. & Chatzidimitriou, A. Microkinetic analysis of ring opening and decarboxylation of γ-valerolactone over silica alumina. J. Catal. 344, 640–656 (2016).

    CAS  Google Scholar 

  22. Yun, G.-N., Ahn, S.-J., Takagaki, A., Kikuchi, R. & Oyama, S. T. Hydrodeoxygenation of γ-valerolactone on bimetallic NiMo phosphide catalysts. J. Catal. 353, 141–151 (2017).

    CAS  Google Scholar 

  23. Lin, W.-C. et al. Zinc-incorporated microporous molecular sieve for mild catalytic hydrolysis of γ-valerolactone: a new selective route for biomass conversion. ChemSusChem 11, 4214–4218 (2018).

    CAS  Google Scholar 

  24. Serrano-Ruiz, J. C., Braden, D. J., West, R. M. & Dumesic, J. A. Conversion of cellulose to hydrocarbon fuels by progressive removal of oxygen. Appl. Catal. B 100, 184–189 (2010).

    CAS  Google Scholar 

  25. Okuhara, T. Water-tolerant solid acid catalysts. Chem. Rev. 102, 3641–3666 (2002).

    CAS  Google Scholar 

  26. Nakajima, K. et al. Nb2O5·nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites. J. Am. Chem. Soc. 133, 4224–4227 (2011).

    CAS  Google Scholar 

  27. Zhang, Y. et al. Direct conversion of biomass-derived carbohydrates to 5-hydroxymethylfurfural over water-tolerant niobium-based catalysts. Fuel 139, 301–307 (2015).

    CAS  Google Scholar 

  28. Zhang, Y. et al. Mesoporous niobium phosphate: an excellent solid acid for the dehydration of fructose to 5-hydroxymethylfurfural in water. Catal. Sci. Technol. 2, 2485–2491 (2012).

    CAS  Google Scholar 

  29. Takagaki, A., Tagusagawa, C. & Domen, K. Glucose production from saccharides using layered transition metal oxide and exfoliated nanosheets as a water-tolerant solid acid catalyst. Chem. Commun. 14, 5363–5365 (2008).

    Google Scholar 

  30. Carniti, P., Gervasini, A., Biella, S. & Auroux, A. Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium: fructose dehydration reaction. Catal. Today 118, 373–378 (2006).

    CAS  Google Scholar 

  31. Carniti, P., Gervasini, A., Bossola, F. & Dal Santo, V. Cooperative action of Brønsted and Lewis acid sites of niobium phosphate catalysts for cellobiose conversion in water. Appl. Catal. B 193, 93–102 (2016).

    CAS  Google Scholar 

  32. Nowak, I. & Ziolek, M. Niobium compounds: preparation, characterization, and application in heterogeneous catalysis. Chem. Rev. 99, 3603–3624 (1999).

    CAS  Google Scholar 

  33. Serrano-Ruiz, J. C., Wang, D. & Dumesic, J. A. Catalytic upgrading of levulinic acid to 5-nonanone. Green. Chem. 12, 574–577 (2010).

    CAS  Google Scholar 

  34. Xia, Q. et al. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes. Nat. Commun. 7, 11162 (2016).

    Google Scholar 

  35. Shao, Y. et al. Selective production of arenes via direct lignin upgrading over a niobium-based catalyst. Nat. Commun. 8, 16104 (2017).

    Google Scholar 

  36. Prakash, A. M. & Kevan, L. Synthesis of niobium silicate molecular sieves of the MFI structure: evidence for framework incorporation of the niobium ion. J. Am. Chem. Soc. 120, 13148–13155 (1998).

    CAS  Google Scholar 

  37. Wichterlová, B., Nováková, J. & Prášil, Z. Structure of defects in γ-irradiated ZSM-5 and Y zeolites: an ESR study. Zeolites 8, 117–121 (1988).

    Google Scholar 

  38. Corma, A., Llabrés i Xamena, F. X., Prestipino, C., Renz, M. & Valencia, S. Water resistant, catalytically active Nb and Ta isolated Lewis acid sites, homogeneously distributed by direct synthesis in a beta zeolite. J. Phys. Chem. C 113, 11306–11315 (2009).

    CAS  Google Scholar 

  39. Duereh, A., Sato, Y., Smith, R. L. & Inomata, H. Analysis of the cybotactic region of two renewable lactone–water mixed-solvent systems that exhibit synergistic Kamlet–Taft basicity. J. Phys. Chem. B 120, 4467–4481 (2016).

    CAS  Google Scholar 

  40. Lemishko, T., Valencia, S., Rey, F., Jiménez-Ruiz, M. & Sastre, G. Inelastic neutron scattering study on the location of Brønsted acid sites in high silica LTA zeolite. J. Phys. Chem. C 120, 24904–24909 (2016).

    CAS  Google Scholar 

  41. Lemishko, T. et al. Inelastic neutron scattering study of the aluminum and Brønsted site location in aluminosilicate LTA zeolites. J. Phys. Chem. C 122, 11450–11454 (2018).

    CAS  Google Scholar 

  42. Hawkins, A. P. et al. Investigation of the dynamics of 1-octene adsorption at 293 K in a ZSM-5 catalyst by inelastic and quasielastic neutron scattering. J. Phys. Chem. C 123, 417–425 (2019).

    CAS  Google Scholar 

  43. Thompson, S. P. et al. Beamline I11 at Diamond: a new instrument for high resolution powder diffraction. Rev. Sci. Instrum. 80, 075107 (2009).

    CAS  Google Scholar 

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We thank EPSRC (EP/P011632/1), the Royal Society and the University of Manchester for funding. We thank the EPSRC National Service for EPR Spectroscopy at the University of Manchester. A.M.S. thanks the Russian Science Foundation (Grant no. 17–73–10320) and Royal Society of Chemistry for funding. We are grateful to Oak Ridge National Laboratory (ORNL), the ISIS Facility and Diamond Light Source (DLS) for access to the beamlines VISION, TOSCA and I11, respectively. We acknowledge DLS for the provision of beamtime at B18 (UK Catalysis Hub SP15151, SP24726) and G. Cibin and V. Celorrio for help at B18 beamline. We acknowledge the support of The University of Manchester’s Dalton Cumbrian Facility (DCF), a partner in the National Nuclear User Facility, the EPSRC UK National Ion Beam Centre and the Henry Royce Institute. We recognize R. Edge and K. Warren for their assistance during the 60Co γ-irradiation processes. We thank A. Jentys from the Technical University of Munich and ISIS Facility for the measurement of the INS spectrum of isobutene as part of RB20053 experimental proposal. We thank C. Webb for help with GC–MS, D. Moulding for help with Raman spectroscopy and M. Kibble for help at the TOSCA beamline. The computing resources were made available through the VirtuES and the ICE-MAN projects, funded by the Laboratory Directed Research and Development programme and by Compute and Data Environment for Science (CADES) at ORNL.

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Authors and Affiliations



L.L. and M.F carried out the syntheses and characterization of the zeolite samples. L.L. and X.H. carried out the catalytic tests. L.L., A.M.S., F.T. and E.J.L.M. collected and analysed the EPR data. L.L. and C.M.A.P. collected and analysed the XAS data. L.L., J.H.C., I.D.S. and C.C.T. collected and analysed the synchrotron X-ray diffraction data. Z.T. and Y.L. collected and analysed the Py-IR data. L.L., Y.C., L.L.D., S.R. and A.J.R.-C. collected and analysed the neutron scattering data and carried out the DFT modelling. S.Y. was responsible for the overall direction of the project and preparation of the manuscript, with contributions from all authors.

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Correspondence to Sihai Yang.

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S.Y. and L.L. are inventors of a patent based on this work.

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Supplementary information

Supplementary Information

Supplementary Methods, Notes, Figs. 1–24, 1–16 and references.

Crystallographic Data 1

Crystallographic data of NbAlS-1.

Crystallographic Data 2

Crystallographic data of NbAlS-1_GVL.

Crystallographic Data 3

Crystallographic data of NbS-1_GVL.

Crystallographic Data 4

Crystallographic data of ZSM-5_GVL.

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Lin, L., Sheveleva, A.M., da Silva, I. et al. Quantitative production of butenes from biomass-derived γ-valerolactone catalysed by hetero-atomic MFI zeolite. Nat. Mater. 19, 86–93 (2020).

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