Ammonia capture in rhodium(II)-based metal-organic polyhedra via synergistic coordinative and H-bonding interactions
Carné-Sánchez, Arnau (Institut Català de Nanociència i Nanotecnologia)
Martínez-Esaín, Jordi (Institut Català de Nanociència i Nanotecnologia)
Rookard, Tanner (Oregon State University. Department of Chemistry)
Flood, Christopher J. (Oregon State University. Department of Chemistry)
Faraudo, Jordi (Institut de Ciència de Materials de Barcelona)
Stylianou, Kyriakos C (Oregon State University. Department of Chemistry)
Maspoch Comamala, Daniel (Institut Català de Nanociència i Nanotecnologia)

Fecha:	2023
Resumen:	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.
Ayudas:	Ministerio de Economía y Competitividad PID2021-124297NB-C33 Ministerio de Economía y Competitividad SEV-2017-0706 Ministerio de Ciencia e Innovación CEX2019-000917-S Agència de Gestió d'Ajuts Universitaris i de Recerca 2017/SGR-238
Nota:	Altres ajuts: acords transformatius de la UAB
Nota:	Altres ajuts: this work was supported by the European Union "NextGenerationEU"/PRTR (EUR2020-112294).
Derechos:	Aquest 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.
Lengua:	Anglès
Documento:	Article ; recerca ; Versió publicada
Materia:	Metal−organic polyhedra (MOPs) ; Cages ; Ammonia capture ; Molecular dynamics ; Regeneration
Publicado en:	ACS applied materials & interfaces, Vol. 15, issue 5 (Feb. 2023) , p. 6747-6754, ISSN 1944-8252

DOI: 10.1021/acsami.2c19206
PMID: 36695491

8 p, 4.8 MB

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Documentos de investigación > Documentos de los grupos de investigación de la UAB > Centros y grupos de investigación (producción científica) > Ciencias > Institut Català de Nanociència i Nanotecnologia (ICN2)
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