Halloysite nanotubes as nanoreactors for heterogeneous micellar catalysis

Halloysite clay tubes have 50 nm diameter and chemically different inner and outer walls (inner surface of aluminum oxide and outer surface of silica). Due to this different chemistry, the selective etching of alumina from inside the tube was realized, while preserving their external diameter (lumen diameter changed from 15 to 25 nm). This increases 2-3 times the tube lumen capacity for loading and further sustained release of active chemical agents such as metals, corrosion inhibitors, and drugs. In particular, halloysite loading efficiency for the benzotriazole increased 4 times by selective etching of 60% alumina within the tubes' lumens. Specific surface area of the tubes increased over 6 times, from 40 to 250 m(2)/g, upon acid treatment.

Micellar catalysis is nowadays a well established approach to convert traditional catalytic reactions commonly run in organic solvents into more efficient, selective, recyclable green catalytic reactions. The present review paper deals with the development of catalytic systems in water in the presence of micelles obtained by addition of surfactants, focusing on the effects of these simple, economic, and green reaction media on important aspects like recyclability, activity, product and substrate selectivity. Contributions from 2005 to 2014 are surveyed with particular emphasis on emerging findings and directions in the field of catalysis. Surfactants enable formation of nanosized apolar aggregates in bulk water where the catalysts and reagents can be dissolved thanks to weak intermolecular interactions like the hydrophobic effect and ion pairing operating in a more concentrated system compared to the bulk solvent. While in the past the use of surfactants was a straightforward approach to enable solubilization of reaction mixtures in water, nowadays specific interactions between substrates, catalysts and micelles are investigated by means of NMR and other techniques to better understand the molecular basis of this kind of supramolecular catalysis. Specifically designed surfactants to engineer micelles in order to compete efficiently with traditional catalysis in organic solvents are nowadays available.