4 research outputs found
SĂntesis escalable y rendimiento electrocatalĂtico de marcos orgĂĄnicos covalentes altamente fluorados para la reducciĂłn del oxĂgeno
his work was financially supported by Ministerio de Ciencia e InnovaciĂłn 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.âZ. acknowledge financial support from the Spanish Ministry of Science and Innovation, through the âMarĂa de Maeztuâ Programme for Units of Excellence in R&D (CEX2018-000805-M). R.âV. acknowledges âPrograma Juan de la Cierva FormaciĂłnâ (FJC2020-045043-I). R.âV. and J.âA.âR.âN. acknowledge MCIN/AEI/10.13039/501100011033 and European Union NextGenerationEU/PRTR.Abstract In this study, we present a novel approach for the synthesis of covalent organic frameworks (COFs) that overcomes the common limitations of nonâscalable solvothermal procedures. Our method allows for the roomâtemperature and scalable synthesis of a highly fluorinated DFTAPBâTFTAâCOF, which exhibits intrinsic hydrophobicity. We used DFTâbased 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 (0.062â
V) and high turnover frequency (0.0757â
sâ1) without the addition of any conductive additives. These values are among the best reported for nonâpyrolyzed and metalâfree electrocatalysts. Finally, we employed DFTâbased 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.MICINNComunidad de MadridDepto. de QuĂmica OrgĂĄnicaFac. de Ciencias QuĂmicasTRUEpu