Induced active sites by adsorbate in zeotype materials
There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are general...
| Main Authors: | , , , , , , , , , , , , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2021
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| _version_ | 1797106907958214656 |
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| author | Li, G Foo, C Yi, X Chen, W Zhao, P Gao, P Yoskamtorn, T Xiao, Y Day, S Tang, CC Hou, G Zheng, A Tsang, SCE |
| author_facet | Li, G Foo, C Yi, X Chen, W Zhao, P Gao, P Yoskamtorn, T Xiao, Y Day, S Tang, CC Hou, G Zheng, A Tsang, SCE |
| author_sort | Li, G |
| collection | OXFORD |
| description | There has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are generally believed to be the extra-framework Al species and residue anion (OH–) species formed at fixed crystallographic positions after their synthesis. However, the dynamic interactions of adsorbates/reactants with pristine zeotype materials to “create” sites during real conditions remain largely unexplored. Herein, direct experimental observation of the establishment of induced active sites in silicoaluminophosphate (SAPO) by an adsorbate is for the first time made, which contradicts the traditional view of the fixed active sites in zeotype materials. Evidence shows that an induced frustrated Lewis pair (FLP, three-coordinated framework Al as LAS and SiO (H) as LBS) can be transiently favored for heterolytic molecular binding/reactions of competitive polar adsorbates due to their ineffective orbital overlap in the rigid framework. High-resolution magic-angle-spinning solid-state NMR, synchrotron X-ray diffraction, neutron powder diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy, and ab initio molecular dynamics demonstrate the transformation of a typical Brønsted acid site (Al(OH)Si) in SAPO zeolites to new induced FLP structure for hetereolytic binding upon adsorption of a strong polar adsorbate. Our unprecedented finding opens up a new avenue to understanding the dynamic establishment of active sites for adsorption or chemical reactions under molecular bombardment of zeolitic structures. |
| first_indexed | 2024-03-07T07:09:10Z |
| format | Journal article |
| id | oxford-uuid:663d7834-7949-4922-a3f3-7d545c546cca |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T07:09:10Z |
| publishDate | 2021 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:663d7834-7949-4922-a3f3-7d545c546cca2022-06-06T10:57:46ZInduced active sites by adsorbate in zeotype materialsJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:663d7834-7949-4922-a3f3-7d545c546ccaEnglishSymplectic ElementsAmerican Chemical Society2021Li, GFoo, CYi, XChen, WZhao, PGao, PYoskamtorn, TXiao, YDay, STang, CCHou, GZheng, ATsang, SCEThere has been a long debate on how and where active sites are created for molecular adsorption and catalysis in zeolites, which underpin many important industrial applications. It is well accepted that Lewis acidic sites (LASs) and basic sites (LBSs) as active sites in pristine zeolites are generally believed to be the extra-framework Al species and residue anion (OH–) species formed at fixed crystallographic positions after their synthesis. However, the dynamic interactions of adsorbates/reactants with pristine zeotype materials to “create” sites during real conditions remain largely unexplored. Herein, direct experimental observation of the establishment of induced active sites in silicoaluminophosphate (SAPO) by an adsorbate is for the first time made, which contradicts the traditional view of the fixed active sites in zeotype materials. Evidence shows that an induced frustrated Lewis pair (FLP, three-coordinated framework Al as LAS and SiO (H) as LBS) can be transiently favored for heterolytic molecular binding/reactions of competitive polar adsorbates due to their ineffective orbital overlap in the rigid framework. High-resolution magic-angle-spinning solid-state NMR, synchrotron X-ray diffraction, neutron powder diffraction, in situ diffuse reflectance infrared Fourier transform spectroscopy, and ab initio molecular dynamics demonstrate the transformation of a typical Brønsted acid site (Al(OH)Si) in SAPO zeolites to new induced FLP structure for hetereolytic binding upon adsorption of a strong polar adsorbate. Our unprecedented finding opens up a new avenue to understanding the dynamic establishment of active sites for adsorption or chemical reactions under molecular bombardment of zeolitic structures. |
| spellingShingle | Li, G Foo, C Yi, X Chen, W Zhao, P Gao, P Yoskamtorn, T Xiao, Y Day, S Tang, CC Hou, G Zheng, A Tsang, SCE Induced active sites by adsorbate in zeotype materials |
| title | Induced active sites by adsorbate in zeotype materials |
| title_full | Induced active sites by adsorbate in zeotype materials |
| title_fullStr | Induced active sites by adsorbate in zeotype materials |
| title_full_unstemmed | Induced active sites by adsorbate in zeotype materials |
| title_short | Induced active sites by adsorbate in zeotype materials |
| title_sort | induced active sites by adsorbate in zeotype materials |
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