RT Journal Article
T1 Scalable synthesis and electrocatalytic performance of highly fluorinated covalent organic frameworks for oxygen reduction
T2 Síntesis escalable y rendimiento electrocatalítico de marcos orgánicos covalentes altamente fluorados para la reducción del oxígeno
A1 Martínez‐Fernández, Marcos
A1 Martínez‐Periñán, Emiliano
A1 Peña Ruigómez, Alejandro de la
A1 Cabrera Trujillo, Jorge Juan
A1 R. Navarro, Jorge A.
A1 Aguilar Galindo, Fernando
A1 Rodríguez‐San‐Miguel, David
A1 Ramos, Mar
A1 Vismara, Rebecca
A1 Félix Zamora, 
A1 Lorenzo, Encarnación
A1 Segura Castedo, José Luis
AB Abstract 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.
PB Wiley
SN 1433-7851
SN 1521-3773
YR 2023
FD 2023-10-16
LK https://hdl.handle.net/20.500.14352/100330
UL https://hdl.handle.net/20.500.14352/100330
LA eng
NO Martínez‐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.
NO his 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.
NO MICINN
NO Comunidad de Madrid
DS Docta Complutense
RD 25 jul 2024