Abstract
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.
Highlights
Architectural metal nanostructures allowing for fine-tuning particle size, shape and location were based on a one-step reduction of metal salts bound to an interface of block co-polymer dendrites and amphiphile ensembles
We found that furfuraldehyde shows good intercalation abilities allowing for further formation of organic ligands for metal ions inside the nanotubes
For the internal tube lumen synthesis, halloysite was loaded with silver acetate, clay outermost was washed, and reaction was performed with loaded reagents
Summary
Architectural metal nanostructures allowing for fine-tuning particle size, shape and location were based on a one-step reduction of metal salts bound to an interface of block co-polymer dendrites and amphiphile ensembles. This study used 3–5 nm diameter Pt, Au, Pd, and their bi-metallic composites to form highly porous dendritic mesostructures [1,2] Extending this strategy, we synthesized Ru nanoparticles inside clay nanotubes. We found that furfuraldehyde shows good intercalation abilities allowing for further formation of organic ligands for metal ions inside the nanotubes. This procedure of halloysite modification with furfuraldehyde based Schiff bases significantly enhances an intercalative loading of metal ions (Ru, Ag as well as Rh, Pt, Co, Fe) both into the lumen and into interlayer space of the nanotubes. Elongated heavy metal particles of 3–4 nm diameter were formed both on the inner lumen surface and in the interlayer slit-like pockets of the halloysite walls
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