Longfei Lin1, Mengtian Fan1, Alena M Sheveleva1,2, Xue Han1, Zhimou Tang3, Joseph H Carter1,4, Ivan da Silva5, Christopher M A Parlett4,6,7,8, Floriana Tuna1,2, Eric J L McInnes1,2, German Sastre9, Svemir Rudić5, Hamish Cavaye5, Stewart F Parker5,8, Yongqiang Cheng10, Luke L Daemen10, Anibal J Ramirez-Cuesta10, Martin P Attfield1, Yueming Liu3, Chiu C Tang4, Buxing Han11, Sihai Yang12. 1. Department of Chemistry, University of Manchester, Manchester, UK. 2. Photon Science Institute, University of Manchester, Manchester, UK. 3. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, China. 4. Diamond Light Source, Harwell Science and Innovation Campus, Didcot, Oxfordshire, UK. 5. ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire, UK. 6. Department of Chemical Engineering and Analytical Science, University of Manchester, Manchester, UK. 7. University of Manchester at Harwell, Diamond Light Source, Didcot, Oxfordshire, UK. 8. UK Catalysis Hub, Research Complex at Harwell, Didcot, Oxfordshire, UK. 9. Instituto de Tecnologia Quimica, UPV-CSIC Universidad Politecnica de Valencia, Valencia, Spain. 10. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA. 11. Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interface and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Science, Beijing, China. 12. Department of Chemistry, University of Manchester, Manchester, UK. Sihai.Yang@manchester.ac.uk.
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.
Optimising tpan class="Chemical">he 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 commercialMFI-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.
Authors: Alexander J O'Malley; Stewart F Parker; Arunabhiram Chutia; Matthew R Farrow; Ian P Silverwood; Victoria García-Sakai; C Richard A Catlow Journal: Chem Commun (Camb) Date: 2016-02-18 Impact factor: 6.222
Authors: Unni Olsbye; Stian Svelle; Morten Bjørgen; Pablo Beato; Ton V W Janssens; Finn Joensen; Silvia Bordiga; Karl Petter Lillerud Journal: Angew Chem Int Ed Engl Date: 2012-04-18 Impact factor: 15.336
Authors: J T Grant; C A Carrero; F Goeltl; J Venegas; P Mueller; S P Burt; S E Specht; W P McDermott; A Chieregato; I Hermans Journal: Science Date: 2016-12-01 Impact factor: 47.728
Authors: Abhishek Dutta Chowdhury; Klaartje Houben; Gareth T Whiting; Mohamed Mokhtar; Abdullah M Asiri; Shaeel A Al-Thabaiti; Suliman N Basahel; Marc Baldus; Bert M Weckhuysen Journal: Angew Chem Int Ed Engl Date: 2016-11-02 Impact factor: 15.336
Authors: Simon Bailleul; Irina Yarulina; Alexander E J Hoffman; Abhay Dokania; Edy Abou-Hamad; Abhishek Dutta Chowdhury; Giovanni Pieters; Julianna Hajek; Kristof De Wispelaere; Michel Waroquier; Jorge Gascon; Veronique Van Speybroeck Journal: J Am Chem Soc Date: 2019-09-09 Impact factor: 15.419