ABSTRACT
Aerogels composed of preformed titania nanocrystals exhibit a large surface area, open porosity, and high crystallinity, making these materials appealing for applications in gas-phase photocatalysis. Recent studies on nanoparticle-based titania aerogels have mainly focused on optimizing their composition to improve photocatalytic performance. Little attention has been paid to modification at the microstructural level to control fundamental properties such as gas permeability and light transmittance, although these features are of fundamental importance, especially for photocatalysts of macroscopic size. In this study, we systematically control the porosity and transparency of titania gels and aerogels by adjusting the particle loading and nonsolvent fraction during the gelation step. Mass transport and light transport were assessed by gas permeability and light attenuation measurements, and the results were related to the microstructure determined by gas sorption analysis and scanning electron microscopy. Mass transport through the aerogel network was found to proceed primarily via Knudsen diffusion leading to relatively low permeabilities in the range of 10-5-10-6 m2/s, despite very high porosities of 96-99%. While permeability was found to depend mainly on particle loading, the optical properties are predominantly affected by the amount of nonsolvent during gelation, allowing independent tuning of mass and light transport.
ABSTRACT
Photocatalysis has the potential to make a major technological contribution to solving pressing environmental and energy problems. There are many strategies for improving photocatalysts, such as tuning the composition to optimize visible light absorption, charge separation, and surface chemistry, ensuring high crystallinity, and controlling particle size and shape to increase overall surface area and exploit the reactivity of individual crystal facets. These processes mainly affect the nanoscale and are therefore summarized as nanostructuring. In comparison, microstructuring is performed on a larger size scale and is mainly concerned with particle assembly and thin film preparation. Interestingly, most structuring efforts stop at this point, and there are very few examples of geometry optimization on a millimeter or even centimeter scale. However, the recent work on nanoparticle-based aerogel monoliths has shown that this size range also offers great potential for improving the photocatalytic performance of materials, especially when the macroscopic geometry of the monolith is matched to the design of the photoreactor. This review article is dedicated to this aspect and addresses some issues and open questions that arise when working with macroscopically large photocatalysts. Guidelines are provided that could help develop novel and efficient photocatalysts with a truly 3D architecture.
ABSTRACT
Monolithic aerogels composed of crystalline nanoparticles enable photocatalysis in three dimensions, but they suffer from low mechanical stability and it is difficult to produce them with complex geometries. Here, an approach to control the geometry of the photocatalysts to optimize their photocatalytic performance by introducing carefully designed 3D printed polymeric scaffolds into the aerogel monoliths is reported. This allows to systematically study and improve fundamental parameters in gas phase photocatalysis, such as the gas flow through and the ultraviolet light penetration into the aerogel and to customize its geometric shape to a continuous gas flow reactor. Using photocatalytic methanol reforming as a model reaction, it is shown that the optimization of these parameters leads to an increase of the hydrogen production rate by a factor of three from 400 to 1200 µmol g-1 h-1 . The rigid scaffolds also enhance the mechanical stability of the aerogels, lowering the number of rejects during synthesis and facilitating handling during operation. The combination of nanoparticle-based aerogels with 3D printed polymeric scaffolds opens up new opportunities to tailor the geometry of the photocatalysts for the photocatalytic reaction and for the reactor to maximize overall performance without necessarily changing the material composition.
Subject(s)
Nanoparticles , Printing, Three-DimensionalABSTRACT
Colloidal nanocrystals are the ideal building blocks for the fabrication of functional materials. Using various assembly, patterning or processing techniques, the nanocrystals can be arranged with unprecedented flexibility in 1-, 2- or 3-dimensional architectures over several orders of length scales, providing access to ordered or disordered, porous or non-porous, and simple as well as hierarchical structures. Careful selection of colloidal nanocrystals allows the properties of the final materials to be predefined. Moreover, by combining different nanocrystals, these properties can be fine-tuned for a specific application, opening up fascinating opportunities to create new materials for energy storage and conversion, catalysis, photocatalysis, biomedicine or optics. Indeed, functional materials made of preformed nanoparticles have been realized for metals, polymers, semiconductors, and ceramics, as well as for composites and organic-inorganic hybrids. In this review article, we introduce some concepts for the fabrication of colloidal nanocrystals and their assembly into dense and porous 3-dimensional structures. Porosity is a particularly important material property that strongly influences its application potential. Therefore, we pay special attention to this aspect and compare porous materials synthesized from nanoparticles with those from molecular routes. An additional focus is set on the degree of structural order that can be achieved on different length scales.
