CO2 Hydrogenation Catalyzed by Graphene-Based Materials.

In the context of an increased interest in the abatement of CO2 emissions generated by industrial activities, CO2 hydrogenation processes show an important potential to be used for the production of valuable compounds (methane, methanol, formic acid, light olefins, aromatics, syngas and/or synthetic fuels), with important benefits for the decarbonization of the energy sector. However, in order to increase the efficiency of the CO2 hydrogenation processes, the selection of active and selective catalysts is of utmost importance. In this context, the interest in graphene-based materials as catalysts for CO2 hydrogenation has significantly increased in the last years. The aim of the present paper is to review and discuss the results published until now on graphene-based materials (graphene oxide, reduced graphene oxide, or N-dopped graphenes) used as metal-free catalysts or as catalytic support for the thermocatalytic hydrogenation of CO2. The reactions discussed in this paper are CO2 methanation, CO2 hydrogenation to methanol, CO2 transformation into formic acid, CO2 hydrogenation to high hydrocarbons, and syngas production from CO2. The discussions will focus on the effect of the support on the catalytic process, the involvement of the graphene-based support in the reaction mechanism, or the explanation of the graphene intervention in the hydrogenation process. Most of the papers emphasized the graphene's role in dispersing and stabilizing the metal and/or oxide nanoparticles or in preventing the metal oxidation, but further investigations are needed to elucidate the actual role of graphenes and to propose reaction mechanisms.

Reversible Martensitic Phase Transition in Yttrium-Stabilized ZrO2 Nanopowders by Adsorption of Water.

The present study was aimed at revealing the influence of the mechanical stress induced by water molecule adsorption on the composition of crystalline phases in the ZrO2 + 3 mol% Y2O3-nanoparticles. Three basic methods were used to determine the phase transition: neutron diffraction, Raman microspectroscopic scanning, and X-ray diffraction. The fact of reversible phase-structural ß â†’ α transformation and the simultaneous presence of two polymorphic structural modifications (ß is the phase of the tetragonal syngony and α of monoclinic syngony in nanosized particles (9 nm)) under normal physical conditions was established by these methods. An assumption was made regarding the connection of the physical mechanism of transformation of the extremely nonequilibrium surface of nanoparticles with electronic exchange of the material of the near-surface layer of nanoparticles with the adsorption layer through donor-acceptor interaction. The principal possibility of creating direct-acting hydroelectric converters based on nanoscale YSZ (Yttria-Stabilized Zirconia) systems due to the reversible character of the considered effect was shown.

Photodynamic effect of light emitting diodes on E. coli and human skin cells induced by a graphene-based ternary composite.

In this paper, the photodynamic effect of a ternary nanocomposite (TiO2-Ag/graphene) on Escherichia coli bacteria and two human cell lines: A375 (melanoma) and HaCaT (keratinocyte) after exposure to different wavelength domains (blue, green or red-Light Emitting Diode, LED) was analyzed. The results obtained through bioassays were correlated with the morphological, structural and spectral data obtained through FT-IR, XPS and UV-Vis spectroscopy, powder X-Ray diffractometry (XRD) and STEM/EDX techniques, leading to conclusions that showed different photodynamic activation mechanisms and effects on bacteria and human cells, depending on the wavelength. The nanocomposite proved a therapeutic potential for blue light-activated antibacterial treatment and revealed a keratinocyte cytotoxic effect under blue and green LEDs. The red light-nanocomposite duo gave a metabolic boost to normal keratinocytes and induced stasis to melanoma cells. The light and nanocomposite combination could be a potential therapy for bacterial keratosis or for skin tumors.

Pt/UiO-66 Nanocomposites as Catalysts for CO2 Methanation Process.

Pt/UiO-66 nanocomposites with platinum target concentration of 3 wt.% were prepared by 3 preparation methods, characterized and tested in the CO2 methanation process. Choice of the microporous UiO-66 metal-organic framework (Zr6O4(OH)4 with 1,4-benzene-dicarboxylate ligand) as catalytic support was motivated by the CO2 chemisorption capacity (proven by CO2-TPD profiles), large specific surface area (1477 m²/g) which favors a high dispersion of metal nanoparticles and good thermal stability. The preparation methods for the Pt/UiO-66 nanocomposites are: (1) wetimpregnation followed by reduction in H2 at 200 °C for 2 h; (2) wet-impregnation followed by reduction with an aqueous solution of NaBH4; and (3) "double-solvent" method, followed by reduction with NaBH4. The UiO-66 based nanocomposites were characterized by N2 adsorption-desorption (BET method), XRD, and SEM/TEM. The Pt/UiO-66 catalyst prepared by method 3 was chosen for catalytic testing due to its highest surface area, smallest platinum nanoparticles (PtNPs) size, the localization of PtNPs both on the grain's internal and external surface and best thermal stability in the desired temperature range. Its capacity to adsorb and activate CO2 and H2 was evaluated in thermo-programmed desorption experiments (H2-TPD and CO2-TPD). Hydrogen is molecularly adsorbed, while CO2 is adsorbed both molecularly and dissociatively. The catalytic performance in the CO2 methanation process was evaluated by Temperature Programmed Reactions (TPRea, 2 °C/min, 30-350 °C), at atmospheric pressure. The best results were obtained at 350 °C, CO2:H2 molar ratio of 1:5.2 and GHSV ═ 1650 h-1. In these conditions CO2 conversion is almost 50% and CH4 selectivity is 36%, the rest of the converted CO2 being transformed in CO.

Graphene-bimetallic nanoparticle composites with enhanced electro-catalytic detection of bisphenol A.

This study brings for the first time novel knowledge about the synthesis by catalytic chemical vapor deposition with induction heating of graphene-bimetallic nanoparticle composites (Gr-AuCu and Gr-AgCu) and their morphological and structural characterization by transmission electron microscopy, Raman spectroscopy, and x-ray powder diffraction. Gold electrodes modified with the obtained materials exhibit an enhanced electro-catalytic effect towards one of the most encountered estrogenic disruptive chemicals, bisphenol A (BPA). The BPA behavior in varying pH solutions was investigated using the electrochemical quartz crystal microbalance, which allowed the accurate determination of the number of molecules involved in the oxidation process. The modified electrodes promote the oxidation of BPA at significantly lower potentials (0.66 V) compared to bare gold (0.78 V). In addition, the peak current density recorded with such electrodes greatly exceeded that obtained with bare gold (e.g. one order of magnitude larger, for a Au/Gr-AgCu electrode). The two modified electrodes have low detection limits, of 1.31 × 10-6 M and 1.91 × 10-6 M for Au/Gr-AgCu and Au/Gr-AuCu, respectively. The bare gold electrode has a higher detection limit of 5.1 × 10-6 M. The effect of interfering species (e.g. catechol and 3-nitrophenol) was also investigated. Their presence influenced not only the BPA peak potential, but also the peak current. With both modified electrodes, no peak currents were recorded below 3 × 10-5 M BPA.

Few-layer graphene sheets with embedded gold nanoparticles for electrochemical analysis of adenine.

This work describes the synthesis of few-layer graphene sheets embedded with various amounts of gold nanoparticles (Gr-Au-x) over an Aux/MgO catalytic system (where × = 1, 2, or 3 wt%). The sheet-like morphology of the Gr-Au-x nanostructures was confirmed by transmission electron microscopy and high resolution transmission electron microscopy, which also demonstrated that the number of layers within the sheets varied from two to seven. The sample with the highest percentage of gold nanoparticles embedded within the graphitic layers (Gr-Au-3) showed the highest degree of crystallinity. This distinct feature, along with the large number of edge-planes seen in high resolution transmission electron microscopic images, has a crucial effect on the electrocatalytic properties of this material. The reaction yields (40%-50%) and the final purity (96%-98%) of the Gr-Au-x composites were obtained by thermogravimetric analysis. The Gr-Au-x composites were used to modify platinum substrates and subsequently to detect adenine, one of the DNA bases. For the bare electrode, no oxidation signal was recorded. In contrast, all of the modified electrodes showed a strong electrocatalytic effect, and a clear peak for adenine oxidation was recorded at approximately +1.05 V. The highest increase in the electrochemical signal was obtained using a platinum/Gr-Au-3-modified electrode. In addition, this modified electrode had an exchange current density (I(0), obtained from the Tafel plot) one order of magnitude higher than that of the bare platinum electrode, which also confirmed that the transfer of electrons took place more readily at the Gr-Au-3-modified electrode.