Title

Incorporation of precious metal nanoparticles into various aerogels by different supercritical deposition methods

Date of Completion

January 2005

Keywords

Engineering, Chemical|Engineering, Materials Science

Degree

Ph.D.

Abstract

One major hurdle in nanoparticle fabrication is the difficulty in controlling size, distribution and concentration. Conventional methods in nanoparticle formation require high temperatures which lead to particle agglomeration and size broadening, or involve substantial amount of organic solvents. A clean route to supported-nanoparticles fabrication was investigated using various supercritical (SC) based deposition methods. The SC deposition involves the organometallic precursor (OP) (dimethyl(1,5-cyclooctadiene)platinum(II)[CODPtMe 2] or bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene) ruthenium(II)) dissolution in SC fluid and contacting this solution with a substrate. The OP is adsorbed and subsequent reduction of the OP-impregnated substrate produces metal/substrate composites. The various methods were: (1) thermal reduction at atmospheric pressure in an inert atmosphere; (2) thermal reduction in SC carbon dioxide (scCO2); (3) chemical reduction in scCO2 with H2; and (4) chemical reduction at atmospheric pressure with H2. The synthesis of resorcinol-formaldehyde aerogels (RFAs) and carbon aerogels (CAs) was also studied and used as substrates (along with commercial silica aerogels (SAs)) in the SC deposition. The surface area, pore properties, and density of these aerogels were evaluated and the effects of reactant concentration, pyrolysis and SC deposition on these properties were determined. ^ Using a static method, the adsorption isotherms of CODPtMe2 in scCO2 on two CAs with different pore sizes were measured at 28 MPa and 80°C to determine the maximum metal loading and the effect of pore properties on adsorption and to examine the interactions between the three components. The isotherms could be represented by the Langmuir model and the adsorption data indicated a strong CODPtMe2-CA interaction and that almost all the preexistent micropore area was covered with CODPtMe 2 molecules even at adsorption lower than the maximum capacity. The observed strong precursor-substrate interaction was corroborated by thermo-gravimetric analyses and N2 physisorption. Transmission electron microscopy, x-ray diffraction, H2 and CO chemisorption and N2 physisorption were employed to demonstrate the homogeneity of particle dispersion, to determine the morphology, range and variation in particle size within the solid matrices and to fully identify the resultant particles as Pt and Ru metals. (Abstract shortened by UMI.)^