Photocatalytic Water Splitting Promoted by 2D and 3D Porphyrin Covalent Organic Polymers Synthesized by Suzuki-Miyaura Carbon-Carbon Coupling
[EN] This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki-Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2022 |
| País: | España |
| Institución: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:riunet.upv.es:10251/194427 |
| Acceso en línea: | https://riunet.upv.es/handle/10251/194427 |
| Access Level: | acceso abierto |
| Palabra clave: | 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin Suzuki¿Miyaura coupling reaction Hydrogen generation Oxygen generation Solar fuels Photocatalytic water splitting Photocatalysis Covalent organic polymers Photoactive polymers Porphyrin 2D 3D QUIMICA ORGANICA |
| Sumario: | [EN] This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki-Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin, we have chosen different cross-linker monomers to induce 2-dimensional (2D) or 3-dimensional (3D) and different rigidity in their resulting polymeric molecular structure. The synthesised COPs were extensively characterised to reveal that the dimensionality and flexibility of the molecular structure play an intense role in the physical, photochemical, and electronic properties of the polymers. Photoinduced excited state of the COPs was evaluated by nanosecond time-resolved laser transient absorption spectroscopy (TAS) by analysing excited state kinetics and quenching experiments, photocurrent density measurements and photocatalytic deposition of Ru3+ to RuO2, and photocatalysis. In summary, TAS experiments demonstrated that the transient excited state of these polymers has two decay kinetics and exhibit strong interaction with water molecules. Moreover, photocurrent and photocatalytic deposition experiments proved that charges are photoinduced and are found across the COP molecular network, but more important charges can migrate from the surface of the COP to the medium. Among the various COPs tested, COP-3 that has a flexible and 3D molecular structure reached the best photocatalytic performances, achieving a photocatalytic yield of 0.4 mmol H-2 x g(COP-3)(-1) after 3 h irradiation. |
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