RESUMO
The quest for efficient catalysts based on abundant elements that can promote the selective CO2 hydrogenation to green methanol still continues. Most of the reported catalysts are based on Cu/ZnO supported in inorganic oxides, with not much progress with respect to the benchmark Cu/ZnO/Al2O3 catalyst. The use of carbon supports for Cu/ZnO particles is much less explored in spite of the favorable strong metal support interaction that these doped carbons can establish. This manuscript reports the preparation of a series of Cu-ZnO@(N)C samples consisting of Cu/ZnO particles embedded within a N-doped graphitic carbon with a wide range of Cu/Zn atomic ratio. The preparation procedure relies on the transformation of chitosan, a biomass waste, into N-doped graphitic carbon by pyrolysis, which establishes a strong interaction with Cu nanoparticles (NPs) formed simultaneously by Cu2+ salt reduction during the graphitization. Zn2+ ions are subsequently added to the Cu-graphene material by impregnation. All the Cu/ZnO@(N)C samples promote methanol formation in the CO2 hydrogenation at temperatures from 200 to 300 °C, with the temperature increasing CO2 conversion and decreasing methanol selectivity. The best performing Cu-ZnO@(N)C sample achieves at 300 °C a CO2 conversion of 23% and a methanol selectivity of 21% that is among the highest reported, particularly for a carbon-based support. DFT calculations indicate the role of pyridinic N doping atoms stabilizing the Cu/ZnO NPs and supporting the formate pathway as the most likely reaction mechanism.
RESUMO
Photodecarboxylation of biomass-derived fatty acids to alkanes offers significant potential to obtain hydrocarbons and economic benefits due to the mild conditions and high activity. Herein, the photodecarboxylation of hexanoic acid into alkanes using TiO2-supported monometallic Au or Pd and bimetallic Au-Pd catalysts is reported. It was found that bimetallic Au-Pd catalysts, featuring a core-shell structure evidenced by EDX-mapping and element line profile, show better photocatalytic performance, achieving 94.7% conversion of hexanoic acid and nearly 100% selectivity to pentane under UV-vis irradiation in the absence of H2 than the monometallic Au analogue. This remarkable enhancement in activity compared to its TiO2 supported monometallic Au or Pd analogues can be attributed to the synergistic effect between Au and Pd within the nanostructured Au(core)-Pd(shell) alloy for achieving more efficient charge-separation efficiency upon visible light excitation. This photocatalyst exhibits a wide scope converting multiple fatty acids into hydrocarbons. Moreover, it can even photocatalyze the conversion of raw bio-oils into alkanes directly. No obvious activity loss was observed during the reusability tests, demonstrating the good stability of the present catalyst. Density functional theory (DFT) calculations indicate that oxidation of carboxylates on TiO2 leads to alkyl radicals that become bound to metal nanoparticles. The superior catalytic performance of Au(core)-Pd(shell)/TiO2 is derived from the weaker adsorption for H on the alloy and the lower hydrogen evolution reaction overpotential. Our research can result in an efficient bio-oil upgrading, resulting in the synthesis of biofuels from biomass under mild conditions.
