RESUMO
Major research efforts are being carried out for the technological advancement to an energetically sustainable society. However, for the full commercial integration of electrochemical energy storage devices, not only materials with higher performance should be designed and manufactured but also more competitive production techniques need to be developed. The laser processing technology is well extended at the industrial sector for the versatile and high throughput modification of a wide range of materials. In this work, a method based on laser processing is presented for the fabrication of hybrid electrodes composed of graphene nanowalls (GNWs) coated with different transition-metal oxide nanostructures for electrochemical capacitor (EC) applications. GNW/stainless steel electrodes grown by plasma enhanced chemical vapor deposition were decorated with metal oxide nanostructures by means of their laser surface processing while immersed in aqueous organometallic solutions. The pseudocapacitive nature of the laser-induced crystallized oxide materials prompted an increase of the GNW electrodes' capacitance by 3 orders of magnitude, up to ca. 28 F/cm3 at 10 mV/s, at both the positive and negative voltages. Finally, asymmetric aqueous and solid-state ECs revealed excellent stability upon tens of thousands of charge-discharge cycles.
RESUMO
The aim of this work is focused on the study of a series of non-traditional catalytic nanomaterials to transform greenhouse CO2 gas into added-value products. We found encouraging results of CO2 hydrogenation activity over sodium titanates with different morphologies. The yield to methanol increases with the increase in the Na incorporated in the nanostructures confirming the proposed mechanism. Samples were prepared at different times of hydrothermal treatment (HTT) with NaOH solutions, and these materials were labeled as Ti-nR-x with x as the hours on the HTT. HRTEM initially showed sphere-shaped nanoparticles in the TiO2 commercial nanopowder, increasing the HTT resulted in morphological changes in which the structures passed from nanosheets and finally to nanorods after 30 h. The X-ray diffraction and Raman spectroscopy results indicated the formation of sodium titanates such as Na2Ti3O7 with short Ti-O bonds and that Na begins to be incorporated into the distorted TiO6 crystalline structure after 5 h of HTT (until 12 wt%). The crystalline and shape transformation resulted in a significant modification on the textural properties passing from 51 m2.g-1 to 150 m2.g-1 and from a pore volume of 0.12 cm3.g-1 to 1.03 cm3.g-1 for Ti-ref and Ti-nR-30 respectively. We also observed differences in the electronic properties as the bandgap presented a blue shift from 3.16 eV on the TiO2 reference nano-powder to 3.44 eV for the Ti-nR-30 calcined sample. This fact coincides with the presence of a more electron-rich state of the Ti4+ and the formation of negative charge layer induced by the presence of Na+ interlayer cations detected by XPS analysis, at the same this helped us to explain the catalytic activity results.
