Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent

The choice of structure directing agents (SDAs) in zeolite synthesis significantly impacts the arrangement of active sites, thereby influencing the stabilization of reaction intermediates with profound implications for catalytic applications. Therefore, understanding the distribution of SDAs along w...

Descripción completa

Detalles Bibliográficos
Autores: Martinez-Ortigosa, Joaquin, Millan, Reisel, Simancas, Jorge, Hernández-Rodríguez, Manuel, Vidal-Moya, Alejandro, Jordá Moret, José Luis, Martineau-Corcos, Charlotte, Sarou-Kanian, Vincent, Boronat, Mercedes, Blasco, Teresa, Rey García, Fernando
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/364204
Acceso en línea:http://hdl.handle.net/10261/364204
Access Level:acceso abierto
id ES_a96a1739882f40cd71cbfcd6ee44b36b
oai_identifier_str oai:digital.csic.es:10261/364204
network_acronym_str ES
network_name_str España
repository_id_str
dc.title.none.fl_str_mv Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
title Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
spellingShingle Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
Martinez-Ortigosa, Joaquin
title_short Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
title_full Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
title_fullStr Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
title_full_unstemmed Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
title_sort Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agent
dc.creator.none.fl_str_mv Martinez-Ortigosa, Joaquin
Millan, Reisel
Simancas, Jorge
Hernández-Rodríguez, Manuel
Vidal-Moya, Alejandro
Jordá Moret, José Luis
Martineau-Corcos, Charlotte
Sarou-Kanian, Vincent
Boronat, Mercedes
Blasco, Teresa
Rey García, Fernando
author Martinez-Ortigosa, Joaquin
author_facet Martinez-Ortigosa, Joaquin
Millan, Reisel
Simancas, Jorge
Hernández-Rodríguez, Manuel
Vidal-Moya, Alejandro
Jordá Moret, José Luis
Martineau-Corcos, Charlotte
Sarou-Kanian, Vincent
Boronat, Mercedes
Blasco, Teresa
Rey García, Fernando
author_role author
author2 Millan, Reisel
Simancas, Jorge
Hernández-Rodríguez, Manuel
Vidal-Moya, Alejandro
Jordá Moret, José Luis
Martineau-Corcos, Charlotte
Sarou-Kanian, Vincent
Boronat, Mercedes
Blasco, Teresa
Rey García, Fernando
author2_role author
author
author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Agencia Estatal de Investigación (España)
Generalitat Valenciana
Universidad Politécnica de Valencia
Ministerio de Universidades (España)
ALBA Synchrotron
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
description The choice of structure directing agents (SDAs) in zeolite synthesis significantly impacts the arrangement of active sites, thereby influencing the stabilization of reaction intermediates with profound implications for catalytic applications. Therefore, understanding the distribution of SDAs along with the substitution of heteroatoms for silicon in zeolites is imperative for tailoring optimized materials for specific applications. This study is centered on the synthesis of all-silica RTH type zeolites in the presence of fluoride, utilizing triisopropyl(methyl)phosphonium as the organic SDA (OSDA). Zeolites produced under varying conditions of time and temperature exhibit differences in their X-ray diffractograms, indicating the presence of two distinct crystalline phases. The F NMR spectra confirm the presence of fluoride within the small rth cage and exhibit two distinct signals depending on the sample. The Si NMR spectra reveal the existence of penta-coordinated F-SiO species, resulting in sixteen non-equivalent Si sites. Through ab initio DFT methods, the stabilization energy and Si chemical shielding of several models featuring F-SiO situated at all crystallographic sites were computed. Comparison with experimental results enabled the identification of the framework position where the five-coordinate silicon is located, which differs between the two crystalline phases of the as-synthesized RTH zeolites. Consequently, the placement of fluoride in either of these two sites within the RTH zeolite can be controlled during the synthesis. It is expected that this methodology can be extended to manipulate the position of trivalent atoms (e.g., Al or B), which can affect the catalytic properties of the RTH zeolite.
publishDate 2023
dc.date.none.fl_str_mv 2023
2024
2024
2024
dc.type.none.fl_str_mv info:eu-repo/semantics/article
http://purl.org/coar/resource_type/c_6501
Publisher's version
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/364204
url http://hdl.handle.net/10261/364204
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv #PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
#PLACEHOLDER_PARENT_METADATA_VALUE#
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001230-S
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136934OB-I00
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C21
http://dx.doi.org/10.1039/d3ta06071c
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.publisher.none.fl_str_mv Royal Society of Chemistry (UK)
publisher.none.fl_str_mv Royal Society of Chemistry (UK)
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
collection DIGITAL.CSIC. Repositorio Institucional del CSIC
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869416019238322176
spelling Crystalline phase transition in as-synthesized pure silica zeolite RTH containing tetra-alkyl phosphonium as organic structure directing agentMartinez-Ortigosa, JoaquinMillan, ReiselSimancas, JorgeHernández-Rodríguez, ManuelVidal-Moya, AlejandroJordá Moret, José LuisMartineau-Corcos, CharlotteSarou-Kanian, VincentBoronat, MercedesBlasco, TeresaRey García, FernandoThe choice of structure directing agents (SDAs) in zeolite synthesis significantly impacts the arrangement of active sites, thereby influencing the stabilization of reaction intermediates with profound implications for catalytic applications. Therefore, understanding the distribution of SDAs along with the substitution of heteroatoms for silicon in zeolites is imperative for tailoring optimized materials for specific applications. This study is centered on the synthesis of all-silica RTH type zeolites in the presence of fluoride, utilizing triisopropyl(methyl)phosphonium as the organic SDA (OSDA). Zeolites produced under varying conditions of time and temperature exhibit differences in their X-ray diffractograms, indicating the presence of two distinct crystalline phases. The F NMR spectra confirm the presence of fluoride within the small rth cage and exhibit two distinct signals depending on the sample. The Si NMR spectra reveal the existence of penta-coordinated F-SiO species, resulting in sixteen non-equivalent Si sites. Through ab initio DFT methods, the stabilization energy and Si chemical shielding of several models featuring F-SiO situated at all crystallographic sites were computed. Comparison with experimental results enabled the identification of the framework position where the five-coordinate silicon is located, which differs between the two crystalline phases of the as-synthesized RTH zeolites. Consequently, the placement of fluoride in either of these two sites within the RTH zeolite can be controlled during the synthesis. It is expected that this methodology can be extended to manipulate the position of trivalent atoms (e.g., Al or B), which can affect the catalytic properties of the RTH zeolite.Financial support by the Spanish Ministry of Science and Innovation by MCIN/AEI/10.13039/501100011033 and “ERDF A way of making Europe” (Projects: CEX2021-001230-S, PID2022-136934OB-I00, PID2020-112590GB-C21) is deeply acknowledged. The authors also thank the Spanish Ministry of Science and Innovation by MCIN/AEI/10.13039/501100011033 and “European Union Next Generation EU/PRTR” (Projects: TED2021-130191B-C41 and TED2021-130739B-I00), Generalitat Valenciana (Project: Prometeo 2021/077) and “Advanced Materials Programme” of Generalitat Valenciana “European Union Next Generation EU/PRTR” (project: MFA/2022/047). Financial support from the IR INFRANALYTICS FR2054 for conducting the research is gratefully acknowledged. J.M-O acknowledges the financial support from the European Union – NextGeneration EU through the Universitat Politècnica de València, Ministerio de Universidades, Plan de Recuperación, Transformación y Resiliencia for the Margarita Salas grant. The authors thankfully acknowledge the Red Española de Supercomputación (RES) and Servei d’Informàtica de la Universitat de València (SIUV) for computational resources and technical support. The authors acknowledge the Microscopy Service of the Universitat Politècnica de València for its assistance in microscopy characterization and beamline MSPD at synchrotron ALBA for beamtime allocation.With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2021-001230-S).Peer reviewedRoyal Society of Chemistry (UK)Ministerio de Ciencia e Innovación (España)Ministerio de Ciencia, Innovación y Universidades (España)Agencia Estatal de Investigación (España)Generalitat ValencianaUniversidad Politécnica de ValenciaMinisterio de Universidades (España)ALBA SynchrotronConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]2024202420232024info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionhttp://hdl.handle.net/10261/364204reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/CEX2021-001230-Sinfo:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-136934OB-I00info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-112590GB-C21http://dx.doi.org/10.1039/d3ta06071cSíinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3642042026-05-22T06:33:51Z
score 15,811543

Similares en LA Referencia