Search

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., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

In food-grade emulsions, particles with an appropriate surface modification can be used to replace surfactants and potentially enhance the stability of emulsions. During the life cycle of products based on such emulsions, they can be exposed to a broad range of pH conditions and hence it is crucial to understand how pH changes affect stability of emulsions stabilized by particles. Here, we report on a comprehensive study of the stability, microstructure, and macroscopic behavior of pH-controlled oil-in-water emulsions containing silica nanoparticles modified with chitosan, a food-grade polycation. We found that the modified colloidal particles used as stabilizers behave differently depending on the pH, resulting in unique emulsion structures at multiple length scales. Our findings are rationalized in terms of the different emulsion stabilization mechanisms involved, which are determined by the pH-dependent charges and interactions between the colloidal building blocks of the system. At pH 4, the silica particles are partially hydrophobized through chitosan modification, favoring their adsorption at the oil-water interface and the formation of Pickering emulsions. At pH 5.5, the particles become attractive and the emulsion is stabilized by a network of agglomerated particles formed between the droplets. Finally, chitosan aggregates form at pH 9 and these act as the emulsion stabilizers under alkaline conditions. These insights have important implications for the processing and use of particle-stabilized emulsions. On one hand, changes in pH can lead to undesired macroscopic phase separation or coalescence of oil droplets. On the other hand, the pH effect on emulsion behavior can be harnessed in industrial processing, either to tune their flow response by altering the pH between processing stages or to produce pH-responsive emulsions that enhance the functionality of the emulsified end products.

Edible solid particles constitute an attractive alternative to surfactants as stabilizers of food-grade emulsions for products requiring a long-term shelf life. Here, we report on a new approach to stabilize edible emulsions using silica nanoparticles modified by noncovalently bound chitosan oligomers. Electrostatic modification with chitosan increases the hydrophobicity of the silica nanoparticles and favors their adsorption at the oil-water interface. The interfacial adsorption of the chitosan-modified silica particles enables the preparation of oil-in-water emulsions with small droplet sizes of a few micrometers through high-pressure homogenization. This approach enables the stabilization of food-grade emulsions for more than 3 months. The emulsion structure and stability can be effectively tuned by controlling the extent of chitosan adsorption on the silica particles. Bulk and interfacial rheology are used to highlight the two stabilization mechanisms involved. Low chitosan concentration (1 wt % with respect to silica) leads to the formation of a viscoelastic film of particles adsorbed at the oil-water interface, enabling Pickering stabilization of the emulsion. By contrast, a network of agglomerated particles formed around the droplets is the predominant stabilization mechanism of the emulsions at higher chitosan content (5 wt % with respect to silica). These two pathways against droplet coalescence and coarsening open up different possibilities to engineer the long-term stabilization of emulsions for food applications.

We report the assembly of monodisperse colloidosomes containing a wide range of functional nanoparticles in the outer shell using a double emulsion templating method in a microfluidic device. By selecting nanoparticles of specific functionalities, hollow capsules with inert, magnetic, photocatalytic, and potentially biocompatible and piezoelectric shells are easily obtained. Proper control over the surface chemistry of the nanoparticles forming the shell and of the liquid interfaces involved is key to enable the assembly of colloidosomes using this double emulsification route.

The stabilization of nanoparticles in concentrated aqueous suspensions is required in many manufacturing technologies and industrial products. Nanoparticles are commonly stabilized through the adsorption of a dispersant layer around the particle surface. The formation of a dispersant layer (adlayer) of appropriate thickness is crucial for the stabilization of suspensions containing high nanoparticle concentrations. Thick adlayers result in an excessive excluded volume around the particles, whereas thin adlayers lead to particle agglomeration. Both effects reduce the maximum concentration of nanoparticles in the suspension. However, conventional dispersants do not allow for a systematic control of the adlayer thickness on the particle surface. In this study, we synthesized dispersants with a molecular architecture that enables better control over the particle adlayer thickness. By tailoring the chemistry and length of these novel dispersants, we were able to prepare fluid suspensions (viscosity < 1 Pa.s at 100 s-1) with more than 40 vol % of 65-nm alumina particles in water, as opposed to the 30 vol % achieved with a state-of-the-art dispersing agent. This remarkably high concentration facilitates the fabrication of a wide range of products and intermediates in materials technology, cosmetics, pharmacy, and in all other areas where concentrated nanoparticle suspensions are required. On the basis of the proposed molecular architecture, one can also envisage other similar molecules that could be successfully applied for the functionalization of surfaces for biosensing, chromatography, medical imaging, drug delivery, and aqueous lubrication, among others.