Two-dimensional Covalent Organic Frameworks for Energy Related Applications

Jose L. Segura^a, Marcos Martínez-Fernández^a, Alejandro de la Peña^a^,^b, Elena Gala^a^,^b, Marta Gordo Lozano^a, Matías J. Alonso-Navarro^a^,^b, Fátima Suárez Blas^a^,^b, M. Mar Ramos^b

^aDepartamento Química Orgánica I, Facultad Ciencias Químicas, Universidad Complutense de Madrid, E-28040, Madrid, Spain.

^bDepartamento de Tecnología Química y Ambiental, Univ. Rey Juan Carlos, Móstoles, 28933, Spain

Proceedings of Organic 2D Crystalline Materials: Chemistry, Physics and Devices (O2DMAT)

Madrid, Spain, 2022 September 15th - 16th

Organizers: Enrique Cánovas, Renhao Dong and Hai Wang

Contributed talk, Jose L. Segura, presentation 002
Publication date: 11th July 2022

Covalent organic frameworks (COFs) comprise an emerging class of materials based on the atomically precise organization of organic subunits into two- (2D) or three-dimensional (3D) porous crystalline structures connected by strong covalent bonds with predictable control over composition and topology.[1]

In our research group we are dealing with the synthesis of COFs based on imine[2] and/or imide linkages[3] by using both de novo synthesis and post-synthetic approaches.[4-9] We have addressed the issue of the processability of COFs to get suitable material dispersions. For this purpose, liquid phase exfoliation (LPE) assisted by sonication and chemical exfoliation (CE) have shown to be easy and scalable methods to disrupt the non-covalent interactions between COF layers and produce COF nanosheets (CONs) suitable to be processable for different applications.We are especially interested in the development of photo and electroactive COFs for applications related with energy. In this communication we will comment on our previous results on 2D-COFs for charge storage and catalysis and we will highlight our recent results on the development of COFs organic cathode materials with multiple redox sites (Figure) as efficient electrocatalysts for the oxygen reduction reaction (ORR).[10-14]

Important benefits of these new COFs are that they are not only metal free, but also no additional
pyrolysis process has to be applied before its use. Instead, the electrocatalytic activity is a consequence of the specific electroactive
moieties selected for the design of the new COF electrocatalysts.

References:

[1] Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; Matzger, A. J.; Yaghi, O. M., Science 2005, 310, 1166.

[2] Segura, J.L.; Mancheño, M.J.; Zamora, F. Chem. Soc. Rev. 2016, 45, 5635.

[3] S. Royuela, E. Martínez, M. Arrieta, J.I. Martínez, M.M. Ramos, F. Zamora, E. Lorenzo, J.L. Segura, Chem. Commun., 2020, 56,1267

[4] Segura, J.L.; Royuela, S.; Ramos, M.M. Chem. Soc. Rev. 2019, 48, 3903.

[5] Meri-Bofi, L.; Royuela, S.; Zamora, F.; Ruiz-Gonzalez, M. L., Segura, J. L.; Muñoz-Olivas, R.; Mancheño, M. J. J. Mater. Chem. A 2017, 5, 17973

[6] Royuela, S.; García-Garrido, E.; Martín Arroyo, M.; Mancheño, M.J.; Ramos, M.M.; González-Rodríguez, D.; Somoza, A.; Zamora, F.; Segura, J.L. Chem. Commun., 2018, 54, 8729

[7] Royuela, S.; Almarza, J.; Mancheño, M.J.; Pérez-Flores, J.C.; Michel, E.G.; Ramos, M. Mar; Zamora, F.; Ocón, P., Segura, J.L. Chem. Eur. J. 2019, 25, 12394.

[8] P. García-Arroyo, M.P. Arrieta, D. García-García, R. Cuervo-Rodríguez, V. Fombuena, M.J. Mancheño, J. L. Segura, Polymer, 2020, 196, 122466

[9] J. A. Martín-Illán, S. Royuela,M. M. Ramos, J. L. Segura, F. Zamora, Chem. Eur. J. 2020, 26, 6495

[10] M. Martínez-Fernández, R. Gavara, S. Royuela, L. Fernández-Ecija, J. I. Martínez, F. Zamora, J. L. Segura, J. Mat. Chem. A, 2022, 10, 4634

[11] Briega-Martos, V.; Ferre-Vilaplana, A.; de la Peña, A.; Segura, J. L.; Zamora, F.; Feliu, J. M.; Herrero, E. ACS Catal. 2017, 7, 1015.

[12] M.J. Alonso-Navarro, J. Barrio, S. Royuela, N. Karjule, M.M. Ramos, J.I. Martínez, M. Shalom, J.L. Segura , RSC Advances, 2021, 11, 2701

[13] M. Martínez-Fernández, E. Martínez-Periñán, S. Royuela, J.I. Martínez, F. Zamora, E. Lorenzo, José L. Segura, Appl. Mater. Today, 2202, 26, 101384

[14] P. García-Arroyo, E. Martínez-Periñán, J. J. Cabrera-Trujillo, E. Salagre, E G. Michel, J. I. Martínez, E. Lorenzo, José L. Segura, Nano Research 2022, 15, 3907

Acknowledgements:

Financial support by MICINN ( PID2019-106268GB-C33) and the UCM (INV.GR.00.1819.10759) is acknowledged

MMF and FSB acknowledge respectively Comunidad de Madrid and URJC for predoctoral contracts

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