Ammonia capture in rhodium(II)-based metal-organic polyhedra via synergistic coordinative and H-bonding interactions

Ammonia (NH) 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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Autores: Carné-Sánchez, Arnau|||0000-0002-8569-6208, Martínez-Esaín, Jordi|||0000-0002-8420-8559, Rookard, Tanner, Flood, Christopher J., Faraudo, Jordi|||0000-0002-6315-4993, Stylianou, Kyriakos C.|||0000-0003-1670-0020, Maspoch Comamala, Daniel|||0000-0003-1325-9161
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:271956
Acceso en línea:https://ddd.uab.cat/record/271956
https://dx.doi.org/urn:doi:10.1021/acsami.2c19206
Access Level:acceso abierto
Palabra clave:Metal-organic polyhedra (MOPs)
Cages
Ammonia capture
Molecular dynamics
Regeneration
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spelling Ammonia capture in rhodium(II)-based metal-organic polyhedra via synergistic coordinative and H-bonding interactionsCarné-Sánchez, Arnau|||0000-0002-8569-6208Martínez-Esaín, Jordi|||0000-0002-8420-8559Rookard, TannerFlood, Christopher J.Faraudo, Jordi|||0000-0002-6315-4993Stylianou, Kyriakos C.|||0000-0003-1670-0020Maspoch Comamala, Daniel|||0000-0003-1325-9161Metal-organic polyhedra (MOPs)CagesAmmonia captureMolecular dynamicsRegenerationAmmonia (NH) 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: [Rh(bdc)] (where bdc is 1,3-benzene dicarboxylate); one functionalized with hydroxyl groups at its outer surface [Rh(OH-bdc)] (where OH-bdc is 5-hydroxy-1,3-benzene dicarboxylate); and one decorated with aliphatic alkoxide chains at its outer surface [Rh(CO-bdc)] (where CO-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/g. 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 NH to the axial site of the Rh(II) paddlewheel cluster, which triggers the adsorption of additional NH molecules through H-bonding interaction. This unique mechanism creates H-bonded clusters of NH on each Rh(II) axial site, which accounts for the high NH 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. 22023-01-0120232023-01-01Articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://ddd.uab.cat/record/271956https://dx.doi.org/urn:doi:10.1021/acsami.2c19206reponame:Dipòsit Digital de Documents de la UABinstname:Universitat Autònoma de BarcelonaInglésengAgencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2021-124297NB-C33Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2017-0706Ministerio de Ciencia e Innovación https://doi.org/10.13039/501100004837 CEX2019-000917-SAgència de Gestió d'Ajuts Universitaris i de Recerca https://doi.org/10.13039/501100003030 2017/SGR-238open accesshttp://purl.org/coar/access_right/c_abf2Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccessoai:ddd.uab.cat:2719562026-06-06T12:50:31Z
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|||0000-0002-8569-6208
Metal-organic polyhedra (MOPs)
Cages
Ammonia capture
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|||0000-0002-8569-6208
Martínez-Esaín, Jordi|||0000-0002-8420-8559
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi|||0000-0002-6315-4993
Stylianou, Kyriakos C.|||0000-0003-1670-0020
Maspoch Comamala, Daniel|||0000-0003-1325-9161
author Carné-Sánchez, Arnau|||0000-0002-8569-6208
author_facet Carné-Sánchez, Arnau|||0000-0002-8569-6208
Martínez-Esaín, Jordi|||0000-0002-8420-8559
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi|||0000-0002-6315-4993
Stylianou, Kyriakos C.|||0000-0003-1670-0020
Maspoch Comamala, Daniel|||0000-0003-1325-9161
author_role author
author2 Martínez-Esaín, Jordi|||0000-0002-8420-8559
Rookard, Tanner
Flood, Christopher J.
Faraudo, Jordi|||0000-0002-6315-4993
Stylianou, Kyriakos C.|||0000-0003-1670-0020
Maspoch Comamala, Daniel|||0000-0003-1325-9161
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv Metal-organic polyhedra (MOPs)
Cages
Ammonia capture
Molecular dynamics
Regeneration
topic Metal-organic polyhedra (MOPs)
Cages
Ammonia capture
Molecular dynamics
Regeneration
description Ammonia (NH) 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: [Rh(bdc)] (where bdc is 1,3-benzene dicarboxylate); one functionalized with hydroxyl groups at its outer surface [Rh(OH-bdc)] (where OH-bdc is 5-hydroxy-1,3-benzene dicarboxylate); and one decorated with aliphatic alkoxide chains at its outer surface [Rh(CO-bdc)] (where CO-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/g. 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 NH to the axial site of the Rh(II) paddlewheel cluster, which triggers the adsorption of additional NH molecules through H-bonding interaction. This unique mechanism creates H-bonded clusters of NH on each Rh(II) axial site, which accounts for the high NH 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 2
2023-01-01
2023
2023-01-01
dc.type.none.fl_str_mv Article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://ddd.uab.cat/record/271956
https://dx.doi.org/urn:doi:10.1021/acsami.2c19206
url https://ddd.uab.cat/record/271956
https://dx.doi.org/urn:doi:10.1021/acsami.2c19206
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación https://doi.org/10.13039/501100011033 PID2021-124297NB-C33
Ministerio de Economía y Competitividad https://doi.org/10.13039/501100003329 SEV-2017-0706
Ministerio de Ciencia e Innovación https://doi.org/10.13039/501100004837 CEX2019-000917-S
Agència de Gestió d'Ajuts Universitaris i de Recerca https://doi.org/10.13039/501100003030 2017/SGR-238
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://creativecommons.org/licenses/by/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
https://creativecommons.org/licenses/by/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.source.none.fl_str_mv reponame:Dipòsit Digital de Documents de la UAB
instname:Universitat Autònoma de Barcelona
instname_str Universitat Autònoma de Barcelona
reponame_str Dipòsit Digital de Documents de la UAB
collection Dipòsit Digital de Documents de la UAB
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