Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions

Ammonia (NH3) is among the world's most widely produced bulk chemicals, given its extensive use in diverse sectors such as agriculture; however, it poses environmental and health risks at low concentrations. Therefore, there is a need for developing new technologies and materials to capture and...

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Detalhes bibliográficos
Autores: Carné-Sánchez, Arnau, Martínez Esaín, Jordi, Rookard, Tanner, Flood, Christopher J., Faraudo, Jordi, Stylianou, Kyriakos C., Maspoch, Daniel
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/336065
Acesso em linha:http://hdl.handle.net/10261/336065
https://api.elsevier.com/content/abstract/scopus_id/85147157740
Access Level:acceso abierto
Palavra-chave:Ammonia capture
Cages
Metal−organic polyhedra (MOPs)
Molecular dynamics
Regeneration
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network_name_str España
repository_id_str
dc.title.none.fl_str_mv Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
title Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
spellingShingle Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
Carné-Sánchez, Arnau
Ammonia capture
Cages
Metal−organic polyhedra (MOPs)
Molecular dynamics
Regeneration
title_short Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
title_full Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
title_fullStr Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
title_full_unstemmed Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
title_sort Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding Interactions
dc.creator.none.fl_str_mv Carné-Sánchez, Arnau
Martínez Esaín, Jordi
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi
Stylianou, Kyriakos C.
Maspoch, Daniel
author Carné-Sánchez, Arnau
author_facet Carné-Sánchez, Arnau
Martínez Esaín, Jordi
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi
Stylianou, Kyriakos C.
Maspoch, Daniel
author_role author
author2 Martínez Esaín, Jordi
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi
Stylianou, Kyriakos C.
Maspoch, Daniel
author2_role author
author
author
author
author
author
dc.contributor.none.fl_str_mv Ministerio de Ciencia e Innovación (España)
Agencia Estatal de Investigación (España)
Generalitat de Catalunya
European Commission
Ministerio de Ciencia, Innovación y Universidades (España)
Fundación la Caixa
Carné-Sánchez, Arnau [0000-0002-8569-6208]
Martínez Esaín, Jordi [0000-0002-8420-8559]
Faraudo, Jordi [0000-0002-6315-4993]
Stylianou, Kyriakos C. [0000-0003-1670-0020]
Maspoch, Daniel [0000-0003-1325-9161]
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Ammonia capture
Cages
Metal−organic polyhedra (MOPs)
Molecular dynamics
Regeneration
topic Ammonia capture
Cages
Metal−organic polyhedra (MOPs)
Molecular dynamics
Regeneration
description Ammonia (NH3) is among the world's most widely produced bulk chemicals, given its extensive use in diverse sectors such as agriculture; however, it poses environmental and health risks at low concentrations. Therefore, there is a need for developing new technologies and materials to capture and store ammonia safely. Herein, we report for the first time the use of metal-organic polyhedra (MOPs) as ammonia adsorbents. We evaluated three different rhodium-based MOPs: [Rh2(bdc)2]12 (where bdc is 1,3-benzene dicarboxylate); one functionalized with hydroxyl groups at its outer surface [Rh2(OH-bdc)2]12 (where OH-bdc is 5-hydroxy-1,3-benzene dicarboxylate); and one decorated with aliphatic alkoxide chains at its outer surface [Rh2(C12O-bdc)2]12 (where C12O-bdc is 5-dodecoxybenzene-1,3-benzene dicarboxylate). Ammonia-adsorption experiments revealed that all three Rh-MOPs strongly interact with ammonia, with uptake capacities exceeding 10 mmol/gMOP. Furthermore, computational and experimental data showed that the mechanism of the interaction between Rh-MOPs and ammonia proceeds through a first step of coordination of NH3 to the axial site of the Rh(II) paddlewheel cluster, which triggers the adsorption of additional NH3 molecules through H-bonding interaction. This unique mechanism creates H-bonded clusters of NH3 on each Rh(II) axial site, which accounts for the high NH3 uptake capacity of Rh-MOPs. Rh-MOPs can be regenerated through their immersion in acidic water, and upon activation, their ammonia uptake can be recovered for at least three cycles. Our findings demonstrate that MOPs can be used as porous hosts to capture corrosive molecules like ammonia, and that their surface functionalization can enhance the ammonia uptake performance.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
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/10261/336065
https://api.elsevier.com/content/abstract/scopus_id/85147157740
url http://hdl.handle.net/10261/336065
https://api.elsevier.com/content/abstract/scopus_id/85147157740
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#
info:eu-repo/grantAgreement/AEI//PID2021-124297NB-C33
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 20217-2020/CEX2019-000917-S
Carné-Sánchez, Arnau; Martínez Esaín, Jordi; Rookard, Tanner; Flood, Christopher J.; Faraudo, Jordi; Stylianou, Kyriakos C.; Maspoch, Daniel; 2023; Ammonia Capture in Rhodium(II)-Based Metal–Organic Polyhedra via Synergistic Coordinative and H‑Bonding Interactions [Dataset]; Figshare; https://doi.org/10.1021/acsami.2c19206.s001
https://doi.org/10.1021/acsami.2c19206
Sí
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
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spelling Ammonia Capture in Rhodium(II)-Based Metal-Organic Polyhedra via Synergistic Coordinative and H-Bonding InteractionsCarné-Sánchez, ArnauMartínez Esaín, JordiRookard, TannerFlood, Christopher J.Faraudo, JordiStylianou, Kyriakos C.Maspoch, DanielAmmonia captureCagesMetal−organic polyhedra (MOPs)Molecular dynamicsRegenerationAmmonia (NH3) is among the world's most widely produced bulk chemicals, given its extensive use in diverse sectors such as agriculture; however, it poses environmental and health risks at low concentrations. Therefore, there is a need for developing new technologies and materials to capture and store ammonia safely. Herein, we report for the first time the use of metal-organic polyhedra (MOPs) as ammonia adsorbents. We evaluated three different rhodium-based MOPs: [Rh2(bdc)2]12 (where bdc is 1,3-benzene dicarboxylate); one functionalized with hydroxyl groups at its outer surface [Rh2(OH-bdc)2]12 (where OH-bdc is 5-hydroxy-1,3-benzene dicarboxylate); and one decorated with aliphatic alkoxide chains at its outer surface [Rh2(C12O-bdc)2]12 (where C12O-bdc is 5-dodecoxybenzene-1,3-benzene dicarboxylate). Ammonia-adsorption experiments revealed that all three Rh-MOPs strongly interact with ammonia, with uptake capacities exceeding 10 mmol/gMOP. Furthermore, computational and experimental data showed that the mechanism of the interaction between Rh-MOPs and ammonia proceeds through a first step of coordination of NH3 to the axial site of the Rh(II) paddlewheel cluster, which triggers the adsorption of additional NH3 molecules through H-bonding interaction. This unique mechanism creates H-bonded clusters of NH3 on each Rh(II) axial site, which accounts for the high NH3 uptake capacity of Rh-MOPs. Rh-MOPs can be regenerated through their immersion in acidic water, and upon activation, their ammonia uptake can be recovered for at least three cycles. Our findings demonstrate that MOPs can be used as porous hosts to capture corrosive molecules like ammonia, and that their surface functionalization can enhance the ammonia uptake performance.This work was supported by the Spanish MINECO (project PID2021-124297NB-C33); the Catalan AGAUR (project 2017 SGR 238); the CERCA Program/Generalitat de Catalunya; the MCIN/AEI/10.13039/501100011033; and by the European Union “NextGenerationEU”/PRTR (EUR2020-112294). ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (grant SEV-2017-0706). We also thank the “Severo Ochoa” Program for Centers of Excellence in R&D Grant CEX2019-000917-S awarded to ICMAB. The project that generated these results received support from the “la Caixa” Foundation (ID 100010434), through a fellowship (LCF/BQ/PR20/11770011).With funding from the Spanish government through the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000917-S)Peer reviewedAmerican Chemical SocietyMinisterio de Ciencia e Innovación (España)Agencia Estatal de Investigación (España)Generalitat de CatalunyaEuropean CommissionMinisterio de Ciencia, Innovación y Universidades (España)Fundación la CaixaCarné-Sánchez, Arnau [0000-0002-8569-6208]Martínez Esaín, Jordi [0000-0002-8420-8559]Faraudo, Jordi [0000-0002-6315-4993]Stylianou, Kyriakos C. [0000-0003-1670-0020]Maspoch, Daniel [0000-0003-1325-9161]Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202320232023info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/336065https://api.elsevier.com/content/abstract/scopus_id/85147157740reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/AEI//PID2021-124297NB-C33info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 20217-2020/CEX2019-000917-SCarné-Sánchez, Arnau; Martínez Esaín, Jordi; Rookard, Tanner; Flood, Christopher J.; Faraudo, Jordi; Stylianou, Kyriakos C.; Maspoch, Daniel; 2023; Ammonia Capture in Rhodium(II)-Based Metal–Organic Polyhedra via Synergistic Coordinative and H‑Bonding Interactions [Dataset]; Figshare; https://doi.org/10.1021/acsami.2c19206.s001https://doi.org/10.1021/acsami.2c19206Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3360652026-05-22T06:33:51Z
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