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.

Data availability

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


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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.

Author information

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.

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) doi:10.1038/s41563-019-0562-6

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