Loading…
Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy
Treatment of Ziegler-Natta (ZN) catalysts with BCl improves their activity by increasing the number of active sites. Here we show how Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-...
Saved in:
| Published in: | The journal of physical chemistry letters 2024-03, Vol.15 (11), p.3178-3184 |
|---|---|
| Main Authors: | , , , , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| cited_by | cdi_FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23 |
|---|---|
| cites | cdi_FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23 |
| container_end_page | 3184 |
| container_issue | 11 |
| container_start_page | 3178 |
| container_title | The journal of physical chemistry letters |
| container_volume | 15 |
| creator | Yakimov, Alexander V Kaul, Christoph J Kakiuchi, Yuya Sabisch, Sebastian Bolner, Felipe Morais Raynaud, Jean Monteil, Vincent Berruyer, Pierrick Copéret, Christophe |
| description | Treatment of Ziegler-Natta (ZN) catalysts with BCl
improves their activity by increasing the number of active sites. Here we show how
Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of
Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit
Ti NMR signatures (δ
= -170 ppm;
= 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl
support, formed upon post-treatment with BCl
and removal of the alkoxo ligands, paralleling the increased polymerization activity. |
| doi_str_mv | 10.1021/acs.jpclett.3c03119 |
| format | article |
| fullrecord | <record><control><sourceid>pubmed_hal_p</sourceid><recordid>TN_cdi_hal_primary_oai_HAL_hal_04782066v1</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>38478985</sourcerecordid><originalsourceid>FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23</originalsourceid><addsrcrecordid>eNpNkE1LAzEQhoMotn78AkFy9bBtstnsJsdSPyrUKrYieFnS7GxN2e4uSSr04m83tbV4mmF4n2HmQeiKkh4lMe0r7XrLVlfgfY9pwiiVR6hLZSKijAp-_K_voDPnloSkkojsFHWYSDIhBe-i73eoqugWSlNDgWcGT9e2VBrw1Hhw2NT4w8CiAhtNlPcKv1iIhsqrauO8w6VtVjjJ-on8RZvKFNHUKw94sg6HKYuf1KIGbzR-BdfUqt5ubkF72zjdtJsLdFKqysHlvp6jt_u72XAUjZ8fHoeDcaQppzyS4ZE5iUXBlMx0KiUUSRnHhebhbSnSkkudMCZixmmRZHpOOU-zWIUsTaSO2Tm62e39VFXeWrNSdpM3yuSjwTjfzkgQEpM0_aIhy3ZZHY50FsoDQEm-NZ8H8_nefL43H6jrHdWu5ysoDsyfavYDusiAwg</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Yakimov, Alexander V ; Kaul, Christoph J ; Kakiuchi, Yuya ; Sabisch, Sebastian ; Bolner, Felipe Morais ; Raynaud, Jean ; Monteil, Vincent ; Berruyer, Pierrick ; Copéret, Christophe</creator><creatorcontrib>Yakimov, Alexander V ; Kaul, Christoph J ; Kakiuchi, Yuya ; Sabisch, Sebastian ; Bolner, Felipe Morais ; Raynaud, Jean ; Monteil, Vincent ; Berruyer, Pierrick ; Copéret, Christophe</creatorcontrib><description>Treatment of Ziegler-Natta (ZN) catalysts with BCl
improves their activity by increasing the number of active sites. Here we show how
Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of
Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit
Ti NMR signatures (δ
= -170 ppm;
= 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl
support, formed upon post-treatment with BCl
and removal of the alkoxo ligands, paralleling the increased polymerization activity.</description><identifier>ISSN: 1948-7185</identifier><identifier>EISSN: 1948-7185</identifier><identifier>DOI: 10.1021/acs.jpclett.3c03119</identifier><identifier>PMID: 38478985</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Catalysis ; Chemical Sciences ; Material chemistry ; or physical chemistry ; Theoretical and</subject><ispartof>The journal of physical chemistry letters, 2024-03, Vol.15 (11), p.3178-3184</ispartof><rights>Distributed under a Creative Commons Attribution 4.0 International License</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23</citedby><cites>FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23</cites><orcidid>0000-0003-3530-1789 ; 0000-0003-0919-8538 ; 0000-0002-1963-595X ; 0000-0003-1783-6034 ; 0000-0001-9660-3890 ; 0000-0002-9538-5323 ; 0000-0002-8624-1002 ; 0000-0001-5882-2320</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,780,784,885,27924,27925</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/38478985$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://hal.science/hal-04782066$$DView record in HAL$$Hfree_for_read</backlink></links><search><creatorcontrib>Yakimov, Alexander V</creatorcontrib><creatorcontrib>Kaul, Christoph J</creatorcontrib><creatorcontrib>Kakiuchi, Yuya</creatorcontrib><creatorcontrib>Sabisch, Sebastian</creatorcontrib><creatorcontrib>Bolner, Felipe Morais</creatorcontrib><creatorcontrib>Raynaud, Jean</creatorcontrib><creatorcontrib>Monteil, Vincent</creatorcontrib><creatorcontrib>Berruyer, Pierrick</creatorcontrib><creatorcontrib>Copéret, Christophe</creatorcontrib><title>Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy</title><title>The journal of physical chemistry letters</title><addtitle>J Phys Chem Lett</addtitle><description>Treatment of Ziegler-Natta (ZN) catalysts with BCl
improves their activity by increasing the number of active sites. Here we show how
Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of
Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit
Ti NMR signatures (δ
= -170 ppm;
= 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl
support, formed upon post-treatment with BCl
and removal of the alkoxo ligands, paralleling the increased polymerization activity.</description><subject>Catalysis</subject><subject>Chemical Sciences</subject><subject>Material chemistry</subject><subject>or physical chemistry</subject><subject>Theoretical and</subject><issn>1948-7185</issn><issn>1948-7185</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpNkE1LAzEQhoMotn78AkFy9bBtstnsJsdSPyrUKrYieFnS7GxN2e4uSSr04m83tbV4mmF4n2HmQeiKkh4lMe0r7XrLVlfgfY9pwiiVR6hLZSKijAp-_K_voDPnloSkkojsFHWYSDIhBe-i73eoqugWSlNDgWcGT9e2VBrw1Hhw2NT4w8CiAhtNlPcKv1iIhsqrauO8w6VtVjjJ-on8RZvKFNHUKw94sg6HKYuf1KIGbzR-BdfUqt5ubkF72zjdtJsLdFKqysHlvp6jt_u72XAUjZ8fHoeDcaQppzyS4ZE5iUXBlMx0KiUUSRnHhebhbSnSkkudMCZixmmRZHpOOU-zWIUsTaSO2Tm62e39VFXeWrNSdpM3yuSjwTjfzkgQEpM0_aIhy3ZZHY50FsoDQEm-NZ8H8_nefL43H6jrHdWu5ysoDsyfavYDusiAwg</recordid><startdate>20240321</startdate><enddate>20240321</enddate><creator>Yakimov, Alexander V</creator><creator>Kaul, Christoph J</creator><creator>Kakiuchi, Yuya</creator><creator>Sabisch, Sebastian</creator><creator>Bolner, Felipe Morais</creator><creator>Raynaud, Jean</creator><creator>Monteil, Vincent</creator><creator>Berruyer, Pierrick</creator><creator>Copéret, Christophe</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>1XC</scope><scope>VOOES</scope><orcidid>https://orcid.org/0000-0003-3530-1789</orcidid><orcidid>https://orcid.org/0000-0003-0919-8538</orcidid><orcidid>https://orcid.org/0000-0002-1963-595X</orcidid><orcidid>https://orcid.org/0000-0003-1783-6034</orcidid><orcidid>https://orcid.org/0000-0001-9660-3890</orcidid><orcidid>https://orcid.org/0000-0002-9538-5323</orcidid><orcidid>https://orcid.org/0000-0002-8624-1002</orcidid><orcidid>https://orcid.org/0000-0001-5882-2320</orcidid></search><sort><creationdate>20240321</creationdate><title>Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy</title><author>Yakimov, Alexander V ; Kaul, Christoph J ; Kakiuchi, Yuya ; Sabisch, Sebastian ; Bolner, Felipe Morais ; Raynaud, Jean ; Monteil, Vincent ; Berruyer, Pierrick ; Copéret, Christophe</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Catalysis</topic><topic>Chemical Sciences</topic><topic>Material chemistry</topic><topic>or physical chemistry</topic><topic>Theoretical and</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Yakimov, Alexander V</creatorcontrib><creatorcontrib>Kaul, Christoph J</creatorcontrib><creatorcontrib>Kakiuchi, Yuya</creatorcontrib><creatorcontrib>Sabisch, Sebastian</creatorcontrib><creatorcontrib>Bolner, Felipe Morais</creatorcontrib><creatorcontrib>Raynaud, Jean</creatorcontrib><creatorcontrib>Monteil, Vincent</creatorcontrib><creatorcontrib>Berruyer, Pierrick</creatorcontrib><creatorcontrib>Copéret, Christophe</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Hyper Article en Ligne (HAL)</collection><collection>Hyper Article en Ligne (HAL) (Open Access)</collection><jtitle>The journal of physical chemistry letters</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Yakimov, Alexander V</au><au>Kaul, Christoph J</au><au>Kakiuchi, Yuya</au><au>Sabisch, Sebastian</au><au>Bolner, Felipe Morais</au><au>Raynaud, Jean</au><au>Monteil, Vincent</au><au>Berruyer, Pierrick</au><au>Copéret, Christophe</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy</atitle><jtitle>The journal of physical chemistry letters</jtitle><addtitle>J Phys Chem Lett</addtitle><date>2024-03-21</date><risdate>2024</risdate><volume>15</volume><issue>11</issue><spage>3178</spage><epage>3184</epage><pages>3178-3184</pages><issn>1948-7185</issn><eissn>1948-7185</eissn><abstract>Treatment of Ziegler-Natta (ZN) catalysts with BCl
improves their activity by increasing the number of active sites. Here we show how
Ti solid-state nuclear magnetic resonance (NMR) spectroscopy enables us to understand the electronic structure of the Ti surface sites present in such treated ZN pre-catalysts, prior to activation with alkyl aluminum. High-field (21.1 T) and low-temperature (∼100 K) NMR augmented by DFT modeling on the pre-catalyst and corresponding molecular analogues enables the detection of
Ti NMR signatures and a molecular level understanding of the electronic structure of Ti surface sites. The associated Ti surface sites exhibit
Ti NMR signatures (δ
= -170 ppm;
= 9.3 MHz; κ = 0.05) corresponding to well-defined fully chlorinated hexacoordinated Ti sites adsorbed on a distorted surface of the MgCl
support, formed upon post-treatment with BCl
and removal of the alkoxo ligands, paralleling the increased polymerization activity.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>38478985</pmid><doi>10.1021/acs.jpclett.3c03119</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0003-3530-1789</orcidid><orcidid>https://orcid.org/0000-0003-0919-8538</orcidid><orcidid>https://orcid.org/0000-0002-1963-595X</orcidid><orcidid>https://orcid.org/0000-0003-1783-6034</orcidid><orcidid>https://orcid.org/0000-0001-9660-3890</orcidid><orcidid>https://orcid.org/0000-0002-9538-5323</orcidid><orcidid>https://orcid.org/0000-0002-8624-1002</orcidid><orcidid>https://orcid.org/0000-0001-5882-2320</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1948-7185 |
| ispartof | The journal of physical chemistry letters, 2024-03, Vol.15 (11), p.3178-3184 |
| issn | 1948-7185 1948-7185 |
| language | eng |
| recordid | cdi_hal_primary_oai_HAL_hal_04782066v1 |
| source | American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list) |
| subjects | Catalysis Chemical Sciences Material chemistry or physical chemistry Theoretical and |
| title | Well-Defined Ti Surface Sites in Ziegler-Natta Pre-Catalysts from 47/49 Ti Solid-State Nuclear Magnetic Resonance Spectroscopy |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-06T23%3A38%3A37IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-pubmed_hal_p&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Well-Defined%20Ti%20Surface%20Sites%20in%20Ziegler-Natta%20Pre-Catalysts%20from%2047/49%20Ti%20Solid-State%20Nuclear%20Magnetic%20Resonance%20Spectroscopy&rft.jtitle=The%20journal%20of%20physical%20chemistry%20letters&rft.au=Yakimov,%20Alexander%20V&rft.date=2024-03-21&rft.volume=15&rft.issue=11&rft.spage=3178&rft.epage=3184&rft.pages=3178-3184&rft.issn=1948-7185&rft.eissn=1948-7185&rft_id=info:doi/10.1021/acs.jpclett.3c03119&rft_dat=%3Cpubmed_hal_p%3E38478985%3C/pubmed_hal_p%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-c1515-9948b028d3a97c699ed4f22dc5031986f59c43382351d47cb155672a7c6149c23%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_id=info:pmid/38478985&rfr_iscdi=true |