Author:

Keywords:

Gold nanoparticles, Carbon materials, Cyclohexane oxidation, Catalysis, Science & Technology, Physical Sciences, Life Sciences & Biomedicine, Chemistry, Physical, Environmental Sciences, Chemistry, Environmental Sciences & Ecology, SELECTIVE OXIDATION, AEROBIC OXIDATION, ALKANE OXIDATION, HYDROCARBON OXYGENATIONS, SURFACE-CHEMISTRY, ACTIVATED CARBON, IRON COMPLEXES, CATALYSTS, ACID, ADSORPTION, 0306 Physical Chemistry (incl. Structural), 0904 Chemical Engineering, Physical Chemistry, 3402 Inorganic chemistry, 4004 Chemical engineering

Abstract:

Gold (1 wt.%) was loaded on several types of carbon materials (activated carbon, polymer based carbon xerogels, multi-walled carbon nanotubes, nanodiamonds, microdiamonds, graphite and silicon carbide) using two different methods (sol immobilisation and double impregnation). Samples were characterised by N-2 adsorption at -196 degrees C, temperature programmed desorption, high-resolution transmission electron microscopy, selected area electron diffraction, energy dispersive X-ray spectrometry, high-angle annular dark-field imaging (Z-contrast), X-ray photoelectron spectroscopy and atomic absorption spectroscopy. The obtained Au/carbon materials were used as catalysts for the oxidation of cyclohexane to cyclohexanol and cyclohexanone, with aqueous H2O2, under mild conditions. The most active catalyst was prepared by supporting gold nanoparticles on carbon nanotubes by the sol method, achieving an overall turnover number of ca. 171 and an overall yield of 3.6% after 6 h reaction time. These values are comparable to the industrial process (that uses Co catalysts and high temperature), but were obtained at ambient temperature with considerable low loads of catalyst (Au catalyst to substrate molar ratio always lower than 1 x 10(-3)), which is of relevance for establishing a greener catalytic process for cyclohexane oxidation. Moreover, a very high selectivity towards the formation of cyclohexanol and cyclohexanone was achieved, since no traces of by-products were detected. The promoting effect of pyrazine carboxylic acid was observed and an optimum peroxide-to-catalyst molar ratio was found to be 2 X 10(4). Further increase of the oxidant amount results in decreased yield due to overoxidation reactions at higher H2O2 amounts. Catalyst recycling was tested up to six consecutive cycles for the most active catalytic system (gold deposited on carbon nanotubes by sol immobilisation), and it was found that the catalyst maintains almost the original level of activity after several reaction cycles (there was only a 6% drop in activity after the sixth cycle) with a rather high selectivity to cyclohexanol and cyclohexanone and with no catalyst leaching. The differences in activity for the other samples can be explained in terms of gold nanoparticle size and the textural properties of the carbon support.