Tailoring Composition and Material Distribution in Multicomponent Cryoaerogels for Application in Photocatalysis.

In this article, we demonstrate the fabrication of tailored multicomponent cryoaerogels from colloidal nanoparticles via the cryogelation method. With this method, it is possible to control the amount of components very precisely. Furthermore, the microscopic distribution of the different nanoparticle components in the resulting monolithic structure is shown to be adjustable by simply mixing calculated amounts of colloidal nanoparticle solutions with a suitable surface charge. We focus on titania cryoaerogels due to their potential for optical applications and investigate the properties of synthesized titania-gold cryoaerogels in dependency of the composition. In addition, titania-platinum cryoaerogels were tested for photocatalytic applications such as hydrogen evolution and showed a significant increase in performance and stability compared to their respective colloidal solutions. While showing comparable results for hydrogen evolution with aerogels as reported in literature, the fabrication is much faster and less complex and therefore might enable future industrial application.

Versatile Aerogel Fabrication by Freezing and Subsequent Freeze-Drying of Colloidal Nanoparticle Solutions.

A versatile method to fabricate self-supported aerogels of nanoparticle (NP) building blocks is presented. This approach is based on freezing colloidal NPs and subsequent freeze drying. This means that the colloidal NPs are directly transferred into dry aerogel-like monolithic superstructures without previous lyogelation as would be the case for conventional aerogel and cryogel fabrication methods. The assembly process, based on a physical concept, is highly versatile: cryogelation is applicable for noble metal, metal oxide, and semiconductor NPs, and no impact of the surface chemistry or NP shape on the resulting morphology is observed. Under optimized conditions the shape and volume of the liquid equal those of the resulting aerogels. Also, we show that thin and homogeneous films of the material can be obtained. Furthermore, the physical properties of the aerogels are discussed.

Aerogels: Aerogels from CdSe/CdS Nanorods with Ultra-long Exciton Lifetimes and High Fluorescence Quantum Yields (Adv. Mater. 40/2015).

The fabrication of gels from semiconductor nanoparticles by means of a controlled and optimized destabilization process is investigated by N. C. Bigall and co-workers on page 6152. Aerogels with high photoluminescence quantum yield and ultra-long radiative lifetimes are fabricated from CdSe/CdS seeded nanorods. It is shown that excited electrons can be delocalized within the aerogel monolith while, at the same time, holes stay confined in the CdSe cores. This type of assembly of nanoparticles shows novel properties in comparison to those of the nanoparticle building blocks and of the bulk material.

Aerogels from CdSe/CdS Nanorods with Ultra-long Exciton Lifetimes and High Fluorescence Quantum Yields.

Hydrogels are fabricated from CdSe/CdS seeded nanorod building blocks by the addition of hydrogen peroxide and converted to aerogels by supercritical drying. The aerogels show higher photoluminescence quantum yields and longer lifetimes than the hydrogels and the nanoparticle solutions. A model for this observation is derived.