Scalable synthesis and electrocatalytic performance of highly fluorinated covalent organic frameworks for oxygen reduction

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dc.contributor.authorMartínez‐Fernández, Marcos
dc.contributor.authorMartínez‐Periñán, Emiliano
dc.contributor.authorPeña Ruigómez, Alejandro de la
dc.contributor.authorCabrera Trujillo, Jorge Juan
dc.contributor.authorR. Navarro, Jorge A.
dc.contributor.authorAguilar Galindo, Fernando
dc.contributor.authorRodríguez‐San‐Miguel, David
dc.contributor.authorRamos, Mar
dc.contributor.authorVismara, Rebecca
dc.contributor.authorFélix Zamora
dc.contributor.authorLorenzo, Encarnación
dc.contributor.authorSegura Castedo, José Luis
dc.date.accessioned2024-02-08T11:15:58Z
dc.date.available2024-02-08T11:15:58Z
dc.date.issued2023-10-16
dc.descriptionhis work was financially supported by Ministerio de Ciencia e Innovación of Spain MICINN (TED2021-129886B-C41, TED2021-129886BC42; TED2021-129886BC43; PID2019-106268GB-C32; PID2019-106268GB-C33, PID2020-113608RB-I00; PID2022-138908NB-C33, PID2022-138470NB-100, RED2018-102412-T; PID2020-116728RB-I00). Comunidad de Madrid (P2018/NMT-4349 TRANSNANOAVANSENS Program; SI3/PJI/2021-0034). F. Z. acknowledge financial support from the Spanish Ministry of Science and Innovation, through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M). R. V. acknowledges “Programa Juan de la Cierva Formación” (FJC2020-045043-I). R. V. and J. A. R. N. acknowledge MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR.
dc.description.abstractAbstract In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of non‐scalable solvothermal procedures. Our method allows for the room‐temperature and scalable synthesis of a highly fluorinated DFTAPB‐TFTA‐COF, which exhibits intrinsic hydrophobicity. We used DFT‐based calculations to elucidate the role of the fluorine atoms in enhancing the crystallinity of the material through corrugation effects, resulting in maximized interlayer interactions, as disclosed both from PXRD structural resolution and theoretical simulations. We further investigated the electrocatalytic properties of this material towards the oxygen reduction reaction (ORR). Our results show that the fluorinated COF produces hydrogen peroxide selectively with low overpotential (0.062 V) and high turnover frequency (0.0757 s<jats:sup>−1</jats:sup>) without the addition of any conductive additives. These values are among the best reported for non‐pyrolyzed and metal‐free electrocatalysts. Finally, we employed DFT‐based calculations to analyse the reaction mechanism, highlighting the crucial role of the fluorine atom in the active site assembly. Our findings shed light on the potential of fluorinated COFs as promising electrocatalysts for the ORR, as well as their potential applications in other fields.
dc.description.departmentDepto. de Química Orgánica
dc.description.facultyFac. de Ciencias Químicas
dc.description.refereedTRUE
dc.description.sponsorshipMICINN
dc.description.sponsorshipComunidad de Madrid
dc.description.statuspub
dc.identifier.citationMartínez‐Fernández, M., Martínez‐Periñán, E., de la Peña Ruigómez, A., Cabrera‐Trujillo, J. J., Navarro, J. A., Aguilar‐Galindo, F., ... & Segura, J. L. (2023). Scalable synthesis and electrocatalytic performance of highly fluorinated covalent organic frameworks for oxygen reduction. Angewandte Chemie, 135(47), e202313940.
dc.identifier.doi10.1002/anie.202313940
dc.identifier.issn1433-7851
dc.identifier.issn1521-3773
dc.identifier.officialurlhttps://onlinelibrary.wiley.com/doi/10.1002/anie.202313940
dc.identifier.urihttps://hdl.handle.net/20.500.14352/100330
dc.issue.number47
dc.journal.titleAngewandte Chemie International Edition
dc.language.isoeng
dc.publisherWiley
dc.relation.projectIDTED2021-129886B-C41
dc.relation.projectIDTED2021-129886BC42
dc.relation.projectIDTED2021-129886BC43
dc.relation.projectIDPID2019-106268GB-C32
dc.relation.projectIDPID2019-106268GB-C33
dc.relation.projectIDPID2020-113608RB-I00
dc.relation.projectIDPID2022-138908NB-C33
dc.relation.projectIDPID2022-138470NB-100
dc.relation.projectIDRED2018-102412-T
dc.relation.projectIDPID2020-116728RB-I00
dc.relation.projectIDP2018/NMT-4349
dc.relation.projectIDSI3/PJI/2021-0034
dc.relation.projectIDCEX2018-000805-M
dc.relation.projectIDFJC2020-045043-I
dc.relation.projectIDMCIN/AEI/10.13039/501100011033
dc.rights.accessRightsopen access
dc.subject.cdu66.0
dc.subject.cdu620
dc.subject.ucmMateriales
dc.subject.unesco23 Química
dc.titleScalable synthesis and electrocatalytic performance of highly fluorinated covalent organic frameworks for oxygen reduction
dc.title.alternativeSíntesis escalable y rendimiento electrocatalítico de marcos orgánicos covalentes altamente fluorados para la reducción del oxígeno
dc.typejournal article
dc.type.hasVersionVoR
dc.volume.number62
dspace.entity.typePublication
relation.isAuthorOfPublication68fab0fd-9d51-411a-9cfe-317d279e7f3d
relation.isAuthorOfPublication78c95fd7-2774-4a6c-b42a-212d583cba93
relation.isAuthorOfPublication.latestForDiscovery78c95fd7-2774-4a6c-b42a-212d583cba93
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