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.

Evaluation of the Photocatalytic Properties of Copper Oxides/Graphene/TiO2 Nanoparticles Composites.

Easy and cost-efficient modifications of titanium dioxide nanoparticles that improve their efficiency in the visible light domain represent a continuous and challenging research topic. In addition, the effect of graphene on the overall photocatalytic process is still debated. Consequently, herein, we prepared a series of TiO2 nanoparticle-based composites with different copper oxide mass content (1-3%) and co-doped with graphene of different oxidation degrees. Different characterization techniques were used to analyze the structural and physico-chemical properties of the obtained composites: Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy (TEM)/Energy-dispersive X-ray spectroscopy (EDX) analysis, X-ray powder diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic performance was evaluated by the degradation of methylene blue under both UVA and visible light irradiation. The nanocomposites show very good photocatalytic activity independent of the presence of reduced graphene oxide, due to the Cu2O/CuO-TiO2 heterojunctions. This finding has been confirmed by the very efficient visible-light-driven degradation of amoxicillin and ciprofloxacin.

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.