Control of zeolite microenvironment for propene synthesis from methanol

Longfei Lin; Mengtian Fan; Alena M. Sheveleva; Xue Han; Zhimou Tang; Joseph H. Carter; Ivan da Silva; Christopher M.A. Parlett; Floriana Tuna; Eric J.L. McInnes; German Sastre; Svemir Rudić; Hamish Cavaye; Stewart F. Parker; Yongqiang Cheng; Luke L. Daemen; Anibal J. Ramirez-Cuesta; Martin P. Attfield; Yueming Liu; Chiu C. Tang; Buxing Han; Sihai Yang

doi:10.1038/s41467-021-21062-1

Control of zeolite microenvironment for propene synthesis from methanol

Longfei Lin, Mengtian Fan, Alena M. Sheveleva, Xue Han, Zhimou Tang, Joseph H. Carter, Ivan da Silva, Christopher M.A. Parlett, Floriana Tuna, Eric J.L. McInnes, German Sastre, Svemir Rudić, Hamish Cavaye, Stewart F. Parker, Yongqiang Cheng, Luke L. Daemen, Anibal J. Ramirez-Cuesta, Martin P. Attfield, Yueming Liu, Chiu C. TangBuxing Han, Sihai Yang

Chemical Spectroscopy

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

Original language	English
Article number	822
Journal	Nature Communications
Volume	12
Issue number	1
DOIs	https://doi.org/10.1038/s41467-021-21062-1
State	Published - Dec 1 2021

Funding

We thank EPSRC (EP/P011632/1), the Royal Society, National Natural Science Foundation of China (21733011, 21890761, 21673076), and the University of Manchester for funding. We thank EPSRC for funding and the EPSRC National Service for EPR Spectroscopy at Manchester. A.M.S. is supported by a Royal Society Newton International Fellowship. We are grateful to the STFC/ISIS Facility, Oak Ridge National Laboratory (ORNL) and Diamond Light Source (DLS) for access to the beamlines TOSCA/MAPS, VISION and I11/I20, respectively. We acknowledge Dr. L. Keenan for help at I20 beamline (SP23594-1). UK Catalysis Hub is kindly thanked for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC grant: EP/R026939/1, EP/ R026815/1, EP/R026645/1, EP/R027129/1 or EP/M013219/1 (biocatalysis). 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 recognise Dr. R. Edge and Dr. K. Warren for their assistance during the 60Co γ-irradiation processes. We thank Prof. A. Jentys from the Technical University of Munich for the measurement of the INS spectrum of iso-butene. We thank C. Webb, E. Enston and G. Smith for help with GC–MS; Dr. L. Hughes for help with SEM and EDX; M. Kibble for help at TOSCA/MAPS beamlines. Computing resources (time on the SCARF compute cluster for some of the CASTEP calculations) was provided by STFC’s e-Science facility. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by ORNL. The computing resources at ORNL were made available through the VirtuES and the ICE-MAN projects, funded by Laboratory Directed Research and Development programme and Compute and Data Environment for Science (CADES).

Funders	Funder number
Compute and Data Environment for Science
University of Manchester’s Dalton Cumbrian Facility
Laboratory Directed Research and Development
Davies Charitable Foundation
Henry Royce Institute
Engineering and Physical Sciences Research Council	EP/P011632/1
Engineering and Physical Sciences Research Council
Royal Society
University of Manchester	EP/M013219/1, EP/R026645/1, EP/R027129/1, EP/R026939/1, EP/ R026815/1
University of Manchester
National Natural Science Foundation of China	21733011, 21890761, 21673076
National Natural Science Foundation of China
UK National Ion Beam Centre

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1038/s41467-021-21062-1

Cite this

Lin, L., Fan, M., Sheveleva, A. M., Han, X., Tang, Z., Carter, J. H., da Silva, I., Parlett, C. M. A., Tuna, F., McInnes, E. J. L., Sastre, G., Rudić, S., Cavaye, H., Parker, S. F., Cheng, Y., Daemen, L. L., Ramirez-Cuesta, A. J., Attfield, M. P., Liu, Y., ... Yang, S. (2021). Control of zeolite microenvironment for propene synthesis from methanol. Nature Communications, 12(1), Article 822. https://doi.org/10.1038/s41467-021-21062-1

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abstract = "Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Br{\o}nsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.",

author = "Longfei Lin and Mengtian Fan and Sheveleva, {Alena M.} and Xue Han and Zhimou Tang and Carter, {Joseph H.} and {da Silva}, Ivan and Parlett, {Christopher M.A.} and Floriana Tuna and McInnes, {Eric J.L.} and German Sastre and Svemir Rudi{\'c} and Hamish Cavaye and Parker, {Stewart F.} and Yongqiang Cheng and Daemen, {Luke L.} and Ramirez-Cuesta, {Anibal J.} and Attfield, {Martin P.} and Yueming Liu and Tang, {Chiu C.} and Buxing Han and Sihai Yang",

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Lin, L, Fan, M, Sheveleva, AM, Han, X, Tang, Z, Carter, JH, da Silva, I, Parlett, CMA, Tuna, F, McInnes, EJL, Sastre, G, Rudić, S, Cavaye, H, Parker, SF, Cheng, Y, Daemen, LL, Ramirez-Cuesta, AJ, Attfield, MP, Liu, Y, Tang, CC, Han, B & Yang, S 2021, 'Control of zeolite microenvironment for propene synthesis from methanol', Nature Communications, vol. 12, no. 1, 822. https://doi.org/10.1038/s41467-021-21062-1

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T1 - Control of zeolite microenvironment for propene synthesis from methanol

AU - Lin, Longfei

AU - Fan, Mengtian

AU - Sheveleva, Alena M.

AU - Han, Xue

AU - Tang, Zhimou

AU - Carter, Joseph H.

AU - da Silva, Ivan

AU - Parlett, Christopher M.A.

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Sastre, German

AU - Rudić, Svemir

AU - Cavaye, Hamish

AU - Parker, Stewart F.

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Ramirez-Cuesta, Anibal J.

AU - Attfield, Martin P.

AU - Liu, Yueming

AU - Tang, Chiu C.

AU - Han, Buxing

AU - Yang, Sihai

PY - 2021/12/1

Y1 - 2021/12/1

N2 - Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

AB - Optimising the balance between propene selectivity, propene/ethene ratio and catalytic stability and unravelling the explicit mechanism on formation of the first carbon–carbon bond are challenging goals of great importance in state-of-the-art methanol-to-olefin (MTO) research. We report a strategy to finely control the nature of active sites within the pores of commercial MFI-zeolites by incorporating tantalum(V) and aluminium(III) centres into the framework. The resultant TaAlS-1 zeolite exhibits simultaneously remarkable propene selectivity (51%), propene/ethene ratio (8.3) and catalytic stability (>50 h) at full methanol conversion. In situ synchrotron X-ray powder diffraction, X-ray absorption spectroscopy and inelastic neutron scattering coupled with DFT calculations reveal that the first carbon–carbon bond is formed between an activated methanol molecule and a trimethyloxonium intermediate. The unprecedented cooperativity between tantalum(V) and Brønsted acid sites creates an optimal microenvironment for efficient conversion of methanol and thus greatly promotes the application of zeolites in the sustainable manufacturing of light olefins.

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SN - 2041-1723

VL - 12

JO - Nature Communications

JF - Nature Communications

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ER -

Control of zeolite microenvironment for propene synthesis from methanol

Abstract

Funding

UN SDGs

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