Ru/CdS Quantum Dots Templated on Clay Nanotubes as Visible-Light-Active Photocatalysts: Optimization of S/Cd Ratio and Ru Content.

A nanoarchitectural approach based on in situ formation of quantum dots (QDs) within/outside clay nanotubes was developed. Efficient and stable photocatalysts active under visible light were achieved with ruthenium-doped cadmium sulfide QDs templated on the surface of azine-modified halloysite nanotubes. The catalytic activity was tested in the hydrogen evolution reaction in aqueous electrolyte solutions under visible light. Ru doping enhanced the photocatalytic activity of CdS QDs thanks to better light absorption and electron-hole pair separation due to formation of a metal/semiconductor heterojunction. The S/Cd ratio was the major factor for the formation of stable nanoparticles on the surface of the azine-modified clay. A quantum yield of 9.3 % was reached by using Ru/CdS/halloysite containing 5.2 wt % of Cd doped with 0.1 wt % of Ru and an S/Cd ratio of unity. In vivo and in vitro studies on the CdS/halloysite hybrid demonstrated the absence of toxic effects in eukaryotic cells and nematodes in short-term tests, and thus they are promising photosensitive materials for multiple applications.

Nanoparticles Formed onto/into Halloysite Clay Tubules: Architectural Synthesis and Applications.

Nanoparticles, being objects with high surface area are prone to agglomeration. Immobilization onto solid supports is a promising method to increase their stability and it allows for scalable industrial applications, such as metal nanoparticles adsorbed to mesoporous ceramic carriers. Tubular nanoclay - halloysite - can be an efficient solid support, enabling the fast and practical architectural (inside / outside) synthesis of stable metal nanoparticles. The obtained halloysite-nanoparticle composites can be employed as advanced catalysts, ion-conducting membrane modifiers, inorganic pigments, and optical markers for biomedical studies. Here, we discuss the possibilities to synthesize halloysite decorated with metal, metal chalcogenide, and carbon nanoparticles, and to use these materials in various fields, especially in catalysis and petroleum refinery.

Rapid and Controlled In Situ Growth of Noble Metal Nanostructures within Halloysite Clay Nanotubes.

A rapid (≤2 min) and high-yield low-temperature synthesis has been developed for the in situ growth of gold nanoparticles (NPs) with controlled sizes in the interior of halloysite nanotubes (HNTs). A combination of HAuCl4 in ethanol/toluene, oleic acid, and oleylamine surfactants and ascorbic acid reducing agent with mild heating (55 °C) readily lead to the growth of targeted nanostructures. The sizes of Au NPs are tuned mainly by adjusting nucleation and growth rates. Further modification of the process, through an increase in ascorbic acid, allows for the formation of nanorods (NRs)/nanowires within the HNTs. This approach is not limited to gold-a modified version of this synthetic strategy can also be applied to the formation of Ag NPs and NRs within the clay nanotubes. The ability to readily grow such core-shell nanosystems is important to their further development as nanoreactors and active catalysts. NPs within the tube interior can further be manipulated by the electron beam. Growth of Au and Ag could be achieved under a converged electron beam suggesting that both Au@HNT and Ag@HNT systems can be used for the fundamental studies of NP growth/attachment.

Formation of metal clusters in halloysite clay nanotubes.

We developed ceramic core-shell materials based on abundant halloysite clay nanotubes with enhanced heavy metal ions loading through Schiff base binding. These clay tubes are formed by rolling alumosilicate sheets and have diameter of c.50 nm, a lumen of 15 nm and length ~1 µm. This allowed for synthesis of metal nanoparticles at the selected position: (1) on the outer surface seeding 3-5 nm metal particles on the tubes; (2) inside the tube's central lumen resulting in 10-12 nm diameter metal cores shelled with ceramic wall; and (3) smaller metal nanoparticles intercalated in the tube's wall allowing up to 9 wt% of Ru, and Ag loading. These composite materials have high surface area providing a good support for catalytic nanoparticles, and can also be used for sorption of metal ions from aqueous solutions.

Fluorescence and Cytotoxicity of Cadmium Sulfide Quantum Dots Stabilized on Clay Nanotubes.

Quantum dots (QD) are widely used for cellular labeling due to enhanced brightness, resistance to photobleaching, and multicolor light emissions. CdS and CdxZn1-xS nanoparticles with sizes of 6⁻8 nm were synthesized via a ligand assisted technique inside and outside of 50 nm diameter halloysite clay nanotubes (QD were immobilized on the tube's surface). The halloysite⁻QD composites were tested by labeling human skin fibroblasts and prostate cancer cells. In human cell cultures, halloysite⁻QD systems were internalized by living cells, and demonstrated intense and stable fluorescence combined with pronounced nanotube light scattering. The best signal stability was observed for QD that were synthesized externally on the amino-grafted halloysite. The best cell viability was observed for CdxZn1-xS QD immobilized onto the azine-grafted halloysite. The possibility to use QD clay nanotube core-shell nanoarchitectures for the intracellular labeling was demonstrated. A pronounced scattering and fluorescence by halloysite⁻QD systems allows for their promising usage as markers for biomedical applications.