Processing and Design of Group (IV) Reticular Platforms: nanoparticles, thin films and crystals
- Autores: María Romero Ángel
- Directores de la Tesis: Sergio Tatay Aguilar (dir. tes.), Carlos Martí Gastaldo (codir. tes.)
- Lectura: En la Universitat de València ( España ) en 2024
- Idioma: inglés
- Número de páginas: 240
- Tribunal Calificador de la Tesis: Paolo Falcaro (presid.), Alicia Forment-Aliaga (secret.), José Puigmarti Luis (voc.)
- Programa de doctorado: Programa de Doctorado en Nanociencia y Nanotecnología por la Universidad de Alicante; la Universidad de Castilla-La Mancha; la Universidad de La Laguna; la Universidad Jaume I de Castellón y la Universitat de València (Estudi General)
- Materias:
- Enlaces
- Tesis en acceso abierto en: TESEO
- Resumen
La presente tesis doctoral titulada "Procesado y diseño de plataformas reticulares del grupo (IV): nanopartículas, películas delgadas y cristales" tiene como objetivo principal la preparación de catalizadores basados en estructuras metal-orgánicas (MOFs), que son estructuras porosas reticulares compuestas de una parte orgánica (la cual se denomina ligando) y otra inorgánica (normalmente compuesta de un metal o cluster metálico). Para la obtención de estos nuevos catalizadores se han seguido dos estrategias diferentes: el procesado de MOFs (publicados anteriormente) como películas delgadas para la fabricación de electrodos, y el diseño de nuevos ligandos para la creación de nuevos MOFs con mejores propiedades catalíticas. Para estos casos los MOFs están basados en plataformas reticulares homo- y heterometálicas de Ti(IV) o de Zr(IV), que se utilizarán para foto/fotoelectrocatálisis y electrocatálisis.
This thesis tackles the dual challenge of processing catalytic Metal-Organic Frameworks (MOFs) for photo/photoelectrocatalysis and the designing of new MOFs for electrocatalysis, all of them based on homo- and heterometallic Ti(IV) or mixed-metal Zr(IV) reticular platforms. In Chapter 1, a survey of MOF-based catalysts containing group (IV) metals used for electro-, photo- and photoelectrocatalysis and the approaches to enhance their catalytic properties are outlined. Following the literature review, we focus first on the processing of MOFs as catalysts in Chapters 2 and 3, and later on the design of new MOF-based catalysts in Chapter 4. Chapter 1 provides an overview of group (IV) MOF-based catalysts and their applications in photo-, electro-, and photoelectrocatalysis for energy related applications. This chapter describes how to tune M(IV)-MOFs catalysts for enhancing their catalytic properties, paying special attention to the chemical and physical properties that control their performance in the catalytic processes. Chapter 2 focuses on the design of MOF nanoparticles as a strategy to facilitate the processing of MOF films. This strategy has been widely used with these materials, and, in this chapter, it was tempted for the particular case of MIL-125-NH2 to improve its performance as a photoelectrode. Chapter 3 reports the use of Vapor-Assisted Conversion (VAC) methodology for heterometallic MOF thin films fabrication. This methodology strays from traditional deposition methods in which films are fabricated from preformed materials, regardless of particle size or orientation of the film. With VAC, the growth of the film can be better controlled for the fabrication of high-quality thin films. Chapter 4 explores the design of new porphyrinic MOF-based catalysts to be tested in the CO2 electroreduction reaction (CO2RR). These kinds of MOFs are excellent platforms for catalysis, since, by combining the properties of the MOFs (large surface areas, modulable functions, etc.) and the porphyrinic unit, they can exhibit a great number of active sites. Moreover, MOFs can be tuned to enhance their catalytic properties simply by solvothermal reaction.
