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oai:docta.ucm.es:20.500.14352/1005782026-06-17T00:08:41Zcom_20.500.14352_14col_20.500.14352_15

Covalent organic frameworks based on electroactive naphthalenediimide as active electrocatalysts toward oxygen reduction reaction Redes orgánicas covalentes basados en naftalendiimida electroactiva como electrocatalizadores activos para la reacción de reducción del oxígeno Martínez-Fernández, Marcos Martínez-Periñán, Emiliano Royuela Collado, Sergio Martínez, José Zamora, Felix Lorenzo, Encarnación Segura Castedo, José Luis 547 54 COF Covalent organic frameworks Napthalenediimide Electrocatalysis Oxygen reduction reaction Metal-free Pyrolysis-free Materiales 23 Química This work was financially supported by MICINN (PID2019- 106268GB-C33; RED2018-102412-T; PID2020-116728RB-I00), Comunidad de Madrid (P2018/NMT-4349 TRANSNANOAVANSENS Program; SI3/PJI/2021-00341) and the UCM (INV.GR.00.1819.10759) Developing organic electrocatalysts toward the oxygen reduction reaction (ORR) that avoid heteroatom doping processes and high-temperature carbonization is of great significance for the maturing of fuel cell applications. Herein, a series of two-dimensional imide-based covalent organic framework (COFs) electrocatalysts toward the ORR is reported. The hydrodynamic electrochemical study reveals that 3.5 electrons are exchanged during the ORR indicating that the process catalyzed by these COFs has a clear preference for the 4-electron reduction pathway. The COFs contain conjugated electroactive napthalenediimide (NDI) moieties that provides the active sites for the electrocatalysis and promotes the formation of COFs with face-to-face π-π stacked structures to provide intrinsic porosity and large surface areas. These COFs can be essentially considered as an organized pattern of active sites embedded in the pore walls of the COF. The choice of suitable comonomers with variable distortions from planarity offers the possibility of obtaining these electroactive COFs with similar redox ability but different degrees of porosity and interlaminar spacing. This work evidences a new insight into developing novel families of electrocatalysts from COFs. Structure and stacking fashion of the COF-systems are investigated on the basis of DFT calculations, as well as the photoabsorption spectra of the representative molecular entities and a proof-of-concept rationalization of the intermediate steps of the ORR mechanism. Depto. de Química Orgánica Fac. de Ciencias Químicas TRUE pub 2024-02-08T17:14:30Z 2024-02-08T17:14:30Z 2022 journal article AO https://hdl.handle.net/20.500.14352/100578 2352-9407 10.1016/j.apmt.2022.101384 eng info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-106268GB-C33/ES/DISEÑO DE MATERIALES 2D PARA APLICACIONES EN ENERGIA: REDES ORGANICAS COVALENTES/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2020-116728RB-I00/ES/DESARROLLO DE BIOSENSORES DE ULTIMA GENERACION PARA EL DIAGNOSTICO RAPIDO DE LA INFECCION CAUSADA POR SARS-COV-2/ Martínez-Fernández, M.; Martínez-Periñán, E.; Royuela, S.; Martínez, J. I.; Zamora, F.; Lorenzo, E.; Segura, J. L. Covalent organic frameworks based on electroactive naphthalenediimide as active electrocatalysts toward oxygen reduction reaction. Applied Materials Today 2022, 26, 101384 DOI:10.1016/j.apmt.2022.101384. open access application/pdf Elsevier