Chemical functionalization of nanostructured materials using supercritical reaction media

There exists a need for durable and thin functional coatings to utilize the afforded surface area of highly porous ceramic materials. Deposition of silane-based Self Assembled Monolayers (SAMs) has thus far been limited to maximum coverages of 4-5 molecules/nm² and long processing times (up to 2 weeks), due to the restricted internal geometry of the substrates. Results are presented for SAMs deposited on high surface area silica from supercritical fluids (SCFs). The SAMs so produced display unprecedented coverages, high monolayer integrity, and extremely low surface defect density. Moreover, the depositions and subsequent removal of reaction byproducts are complete in a matter of minutes rather than days. Nuclear Magnetic Resonance (NMR) spectra of the surface modified silica are presented, demonstrating the SAM integrity and evolution over time. Sorption of aqueous metal ions is demonstrated, and results are given demonstrating the broad pH stability of the deposited SAMs. A chemical explanation for the enhanced deposition is posited, and the kinetics of mass transport into and out of the nanostructured spaces are discussed. Related experiments using zeolite substrates show deposition of thiol-terminated silanes to internal surfaces of 6 Å microporous material. After oxidation of the thiol functional group size selective chemistry was demonstrated using the produced catalyst, proving the efficacy of the supercritical reaction medium for installing functional coatings inside pores of similar diameters to the chain length of the deposited molecule. Comparisons are made between the response of the different substrates to the supercritical fluid-based processing, and remarks on the utility of SCF based processing of nanostructured materials are presented