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- Gold nanoparticles deposited on surface modified carbon xerogels as reusable catalysts for cyclohexane C-H activation in the presence of CO and waterPublication . Ribeiro, Ana Paula da Costa; Martins, Luisa; Carabineiro, Sonia Alexandra Correia; Figueiredo, José; Pombeiro, ArmandoThe use of gold as a promotor of alkane hydrocarboxylation is reported for the first time. Cyclohexane hydrocarboxylation to cyclohexanecarboxylic acid (up to 55% yield) with CO, water, and peroxodisulfate in a water/acetonitrile medium at circa 50 °C has been achieved in the presence of gold nanoparticles deposited by a colloidal method on a carbon xerogel in its original form (CX), after oxidation with HNO3 (-ox), or after oxidation with HNO3 and subsequent treatment with NaOH (-ox-Na). Au/CX-ox-Na behaves as re-usable catalyst maintaining its initial activity and selectivity for at least seven consecutive cycles. Green metric values of atom economy or carbon efficiency also attest to the improvement brought by this novel catalytic system to the hydrocarboxylation of cyclohexane. View Full-Text
- Supported C-Scorpionate Vanadium(IV) Complexes as Reusable Catalysts for Xylene OxidationPublication . Wang, Jiawei; Martins, Luisa; Da Costa Ribeiro, Ana Paula; Carabineiro, Sonia Alexandra Correia; Figueiredo, José L.; Pombeiro, ArmandoC-Scorpionate vanadium(IV) [VOxCl3-x{k(3)-RC(pz)(3)}] [pz = pyrazol-1-yl; x=0, R = SO3 (1); x = 1, R= CH2OH (2) or CH2OSO2Me (3)] complexes supported on functionalized carbon nanotubes (CNTs) are the first V-scorpionate catalysts used so far for the neat oxidation of o-, m- or p-xylene, with TBHP (70% aqueous solution), to the corresponding toluic acids (main products), tolualdehydes and methylbenzyl alcohols. Remarkably, a p-toluic acid yield of 43% (73% selectivity, TON = 1.34 V 10(3)) was obtained with 2@CNT in a simple microwave-assisted mild oxidation procedure, using a very low catalyst charge (3.2 x 10(-2) mol% vs. substrate). Further, this occurred in the absence of any bromine source, what is significant towards the development of a greener and more sustainable process for oxidation of xylenes. Moreover, reuse of catalysts with preservation of their activity was found for up to six consecutive cycles. The effects of reaction parameters, such as reaction time, temperature, amount of catalyst or type of heating source, on the performance of the above catalytic systems are reported and discussed.
- Supported gold nanoparticles as reusable catalysts for oxidation reactions of industrial significancePublication . Martins, Luisa; Carabineiro, Sonia Alexandra Correia; Wang, Jiawei; Rocha, Bruno G. M.; Maldonado Hódar, Francisco Jose; Pombeiro, ArmandoThe efficient single-pot oxidative functionalisation of alkanes and alcohols under mild conditions was catalysed by Au nanoparticles supported on Al2O3, Fe2O3, ZnO and TiO2. The obtained materials were tested for cyclohexane oxidation under mild conditions (60 °C, atmospheric pressure) using an environmentally friendly oxidant (H2O2). The materials were also tested in the oxidation of benzyl alcohol and methylbenzyl alcohol in the presence of tert-butylhydroperoxide as the oxidant under microwave irradiation. With regard to cyclohexane oxidation, all materials were highly selective towards the formation of cyclohexanol and cyclohexanone. No traces of byproducts were detected under the optimised conditions. Au on Fe2O3 led to the best results (13.5 % yield). This system showed an interesting almost exclusive formation of cyclohexanol at 4 h reaction time. Catalyst recycling was tested in up to five cycles, and the catalyst maintained almost the original level of activity after three cycles with no significant leaching. With regard to oxidation of benzyl alcohol and methylbenzyl alcohol, all materials were highly selective towards the formation of benzaldehyde or acetophenone, respectively. No traces of byproducts were detected. Addition of Au increased alcohol conversion from 5 (TiO2) to 91 % (Au/TiO2). The recycling of Au/TiO2 was tested in up to 10 cycles, and the catalytic activity remained high in the first four cycles.