Control of zeolite microenvironment for propene synthesis from methanol

Longfei Lin; Mengtian Fan; Alena Sheveleva; Xue Han; Zhimou Tang; Joseph Carter; Ivan Da Silva; Christopher Parlett; Floriana Tuna; Eric Mcinnes; Germán Sastre; Svemir Rudic; Hamish Cavaye; Stewart F. Parker; Yongqiang Cheng; Luke L Daemen; Anibal J. Ramirez-Cuesta; Martin 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 Sheveleva, Xue Han, Zhimou Tang, Joseph Carter, Ivan Da Silva, Christopher Parlett, Floriana Tuna, Eric Mcinnes, Germán Sastre, Svemir Rudic, Hamish Cavaye, Stewart F. Parker, Yongqiang Cheng, Luke L Daemen, Anibal J. Ramirez-Cuesta, Martin Attfield, Yueming Liu, Chiu C. TangBuxing Han, Sihai Yang

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Abstract

Optimising the balance in “propene selectivity-propene/ethene ratio-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 pore 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 hours) 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
DOIs	https://doi.org/10.1038/s41467-021-21062-1
Publication status	Published - 5 Feb 2021

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10.1038/s41467-021-21062-1Licence: CC BY

s41467-021-21062-1Final published version, 2.08 MBLicence: CC BY

UoMaH: The University of Manchester at Harwell
Lawrence, J. (PI), Burnett, T. (PI), Baker, M. (Researcher), Eastwood, D. (Researcher), Falkowska, M. (Researcher), Freitas, D. (Researcher), Hunt, S. (Researcher), Khan, A. (Researcher), Lane, H. (Researcher), Lezcano Gonzalez, I. (Researcher), Ma, L. (Researcher), Mirihanage, W. (Researcher), Parlett, C. (Researcher), Yan, K. (Researcher), Reinhard, C. (Support team), Duggins, D. (Technical team), Lewis-Fell, J. (Technical team), Nonni, S. (Technical team), Rollings, B. (Technical team), Sinclair, L. (Technical team) & Batts, S. (Support team)
1/01/18 → …
Project: Other

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

@article{173a70fbfdc44652af7c77b607770654,

title = "Control of zeolite microenvironment for propene synthesis from methanol",

abstract = "Optimising the balance in “propene selectivity-propene/ethene ratio-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 pore 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 hours) 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 Alena Sheveleva and Xue Han and Zhimou Tang and Joseph Carter and {Da Silva}, Ivan and Christopher Parlett and Floriana Tuna and Eric Mcinnes and Germ{\'a}n Sastre and Svemir Rudic and Hamish Cavaye and Parker, {Stewart F.} and Yongqiang Cheng and Daemen, {Luke L} and Ramirez-Cuesta, {Anibal J.} and Martin Attfield and Yueming Liu and Tang, {Chiu C.} and Buxing Han and Sihai Yang",

note = "Funding Information: 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{\textquoteright}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{\textquoteright}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). Publisher Copyright: {\textcopyright} 2021, The Author(s).",

year = "2021",

month = feb,

day = "5",

doi = "10.1038/s41467-021-21062-1",

language = "English",

volume = "12",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Springer Nature",

}

Lin, L, Fan, M, Sheveleva, A, Han, X, Tang, Z, Carter, J, Da Silva, I, Parlett, C , Tuna, F , Mcinnes, E, Sastre, G, Rudic, S, Cavaye, H, Parker, SF, Cheng, Y, Daemen, LL, Ramirez-Cuesta, AJ, Attfield, M, Liu, Y, Tang, CC, Han, B & Yang, S 2021, 'Control of zeolite microenvironment for propene synthesis from methanol', Nature Communications, vol. 12, 822. https://doi.org/10.1038/s41467-021-21062-1

TY - JOUR

T1 - Control of zeolite microenvironment for propene synthesis from methanol

AU - Lin, Longfei

AU - Fan, Mengtian

AU - Sheveleva, Alena

AU - Han, Xue

AU - Tang, Zhimou

AU - Carter, Joseph

AU - Da Silva, Ivan

AU - Parlett, Christopher

AU - Tuna, Floriana

AU - Mcinnes, Eric

AU - Sastre, Germán

AU - Rudic, Svemir

AU - Cavaye, Hamish

AU - Parker, Stewart F.

AU - Cheng, Yongqiang

AU - Daemen, Luke L

AU - Ramirez-Cuesta, Anibal J.

AU - Attfield, Martin

AU - Liu, Yueming

AU - Tang, Chiu C.

AU - Han, Buxing

AU - Yang, Sihai

N1 - Funding Information: 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). Publisher Copyright: © 2021, The Author(s).

PY - 2021/2/5

Y1 - 2021/2/5

N2 - Optimising the balance in “propene selectivity-propene/ethene ratio-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 pore 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 hours) 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 in “propene selectivity-propene/ethene ratio-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 pore 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 hours) 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.

U2 - 10.1038/s41467-021-21062-1

DO - 10.1038/s41467-021-21062-1

M3 - Article

C2 - 33547288

SN - 2041-1723

VL - 12

JO - Nature Communications

JF - Nature Communications

M1 - 822

ER -

Control of zeolite microenvironment for propene synthesis from methanol

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UoMaH: The University of Manchester at Harwell

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