Scalable Synthesis and Electrocatalytic Performance of Highly Fluorinated Covalent Organic Frameworks for Oxygen Reduction.

Autor: Martínez-Fernández M; Facultad de CC. Químicas, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040, Madrid, Spain.; Departamento de Inorgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain., Martínez-Periñán E; Departamento de Química Analítica y Análisis Instrumental, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain., de la Peña Ruigómez A; Facultad de CC. Químicas, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040, Madrid, Spain.; Chemical and Environmental Technology Department, Univ. Rey Juan Carlos, Móstoles, 28933, Madrid, Spain., Cabrera-Trujillo JJ; CNRS/Université de Pau et des Pays de l'Adour E2S-UPPA, IPREM UMR 5254, 64053, Pau Cedex 09, France., Navarro JAR; Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain., Aguilar-Galindo F; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain.; Departamento de Química, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain., Rodríguez-San-Miguel D; Departamento de Inorgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain., Ramos M; Chemical and Environmental Technology Department, Univ. Rey Juan Carlos, Móstoles, 28933, Madrid, Spain., Vismara R; Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071, Granada, Spain., Zamora F; Departamento de Inorgánica, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain.; Condensed Matter Physics Center (IFIMAC), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain., Lorenzo E; Departamento de Química Analítica y Análisis Instrumental, Facultad de Ciencias, Universidad Autónoma de Madrid, Campus de Cantoblanco-Crta. Colmenar, 28049, Madrid, Spain.; Institute for Advanced Research in Chemical Sciences (IAdChem), Universidad Autónoma de Madrid Campus de Cantoblanco, 28049, Madrid, Spain.; Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA-Nanociencia), Cantoblanco, 28049, Madrid, Spain., Segura JL; Facultad de CC. Químicas, Universidad Complutense de Madrid, Avenida Complutense s/n, 28040, Madrid, Spain.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Nov 20; Vol. 62 (47), pp. e202313940. Date of Electronic Publication: 2023 Oct 25.
DOI: 10.1002/anie.202313940
Abstrakt: 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 -1 ) 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.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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