Promotion of Ru or Ni on Alumina Catalysts with a Basic Metal for CO2 Hydrogenation: Effect of the Type of Metal (Na, K, Ba).

Ru and Ni on alumina catalysts have been promoted with a 10 wt% of alkali metal (K or Na) or alkaline earth metal (Ba) and tested in CO2 methanation. For the catalyst consisting of Ni and Ba, the variation of Ba loading while keeping Ni loading constant was studied. The promotion in terms of enhanced CH4 yield was found only for the addition of barium to 15 wt% Ni/Al2O3. In contrast, K and Na addition increased the selectivity to CO while decreasing conversion. For the Ru-based catalyst series, no enhancement in conversion or CH4 yield was attained by any of the alkaline metals. CO2 temperature-programed desorption (CO2-TPD) revealed that the amount of chemisorbed CO2 increased significantly after the addition of the base metal. The reactivity of COx ad-species for each catalyst was assessed by temperature-programed surface reaction (TPSR). The characterization revealed that the performance in the Sabatier reaction was a result of the interplay between the amount of chemisorbed CO2 and the reactivity of the COx ad-species, which was maximized for the (10%Ba)15%Ni/Al2O3 catalyst.

Waterborne Graphene- and Nanocellulose-Based Inks for Functional Conductive Films and 3D Structures.

In the vast field of conductive inks, graphene-based nanomaterials, including chemical derivatives such as graphene oxide as well as carbon nanotubes, offer important advantages as per their excellent physical properties. However, inks filled with carbon nanostructures are usually based on toxic and contaminating organic solvents or surfactants, posing serious health and environmental risks. Water is the most desirable medium for any envisioned application, thus, in this context, nanocellulose, an emerging nanomaterial, enables the dispersion of carbon nanomaterials in aqueous media within a sustainable and environmentally friendly scenario. In this work, we present the development of water-based inks made of a ternary system (graphene oxide, carbon nanotubes and nanocellulose) employing an autoclave method. Upon controlling the experimental variables, low-viscosity inks, high-viscosity pastes or self-standing hydrogels can be obtained in a tailored way. The resulting inks and pastes are further processed by spray- or rod-coating technologies into conductive films, and the hydrogels can be turned into aerogels by freeze-drying. The film properties, with respect to electrical surface resistance, surface morphology and robustness, present favorable opportunities as metal-free conductive layers in liquid-phase processed electronic device structures.

Graphene aerogels via hydrothermal gelation of graphene oxide colloids: Fine-tuning of its porous and chemical properties and catalytic applications.

Recently, 3D graphene aerogel has garnered a high interest aiming at benefiting of the excellent properties of graphene in devices for energy storage or environmental remediation. Hydrothermal gelation of GO dispersion is a straightforward method that offers many opportunities for tuning its properties and for processing it to devices. By adjusting hydrothermal gelation and drying conditions, it is possible to tune the density (from ~3 mg cm-3 to ~2 g cm-3), pore volume, pores size (micro to macropores), pore distribution, surface chemical polarity (hydrophobic or hydrophilic), and electrical conductivity (from ~0.5 S m-1 to S cm-1). Besides other well explored applications in energy storage or environmental remediation, graphene aerogels have excellent prospects as support for catalysis since they combine the advantages of graphene sheets (high surface area, high electrical conductivity, surface chemistry tunability, high adsorption capacity…) while circumventing their drawbacks such as difficult separation from reaction media or tendency to stacking. Compared to other 3D porous carbon materials used as catalyst support, graphene aerogels have unique porous structure. The pore walls are the thinnest to be expected for a carbon material (the thickness of monolayer graphene is 0.335 nm), hence leading to the highest exposed surface area per weight and even per volume for compacted aerogels. This has the potential to maximize the catalytic site density per reactor mass and volume while minimizing the pressure drop for continuous reactions in flow. Herein, different strategies to control the porous texture, chemical and physical properties are revised along with their processability and scalability for the implementation into different morphologies and devices. Finally, the application of graphene aerogels in the catalysis field are overviewed, giving a perspective about future directions needing further research.

Origin of the Excellent Performance of Ru on Nitrogen-Doped Carbon Nanofibers for CO2 Hydrogenation to CH4.

Carbon materials have rarely been used as support for CO2 methanation, which is usually carried out using catalysts supported on metal oxides. Here, it is shown that Ru nanoparticles supported on nitrogen-doped carbon nanofibers (NCNF) provide competitive CH4 production rate and stability compared to Al2 O3 -supported catalysts. Contrary to the general belief about the inert nature of carbon supports, it is demonstrated that NCNF is a non-innocent spectator in CO2 methanation due to its ability to store a high amount of COad reaction intermediates. This explains the excellent catalytic behaviour afforded by this unconventional catalyst support.

Carbon nanofibers modified with heteroatoms as metal-free catalysts for the oxidative dehydrogenation of propane.

Carbon nanofibres (CNFs) were modified with B and P by an ex situ approach. In addition, CNFs doped with N were prepared in situ using ethylenediamine as the N and C source. After calcination, the doped CNFs were used as catalysts for the oxidative dehydrogenation of propane. For B-CNFs, the effects of boron loading and calcination temperature on B speciation and catalytic conversion were studied. For the same reaction temperatures and conversions, B- and P-doped CNFs exhibited higher selectivities to propene than pristine CNFs. The N-CNFs were the most active but the least selective of the catalysts tested here. Our results also show that the type of P precursor affects the selectivity to propene and that CNFs modified using triphenylphosphine as the precursor provided the highest selectivity at isoconversion.

Control of nitrogen insertion during the growth of nitrogen-containing carbon nanofibers on cordierite monolith walls.

A well attached coating of nitrogen-functionalised carbon nanofibers (N-CNFs) has been prepared on the walls of cordierite monolith channels. It is formed via concurrent decomposition of ethane and ammonia catalysed by nickel nanoparticles dispersed on alumina coated cordierite monolith. N-CNF/monoliths synthesis employing several growth temperatures and NH(3) compositions was exhaustively characterised by Raman, XPS, elemental analysis and TEM. Synthesis conditions affected profoundly content and type of nitrogen functionality, enabling its fine tuning. N-CNFs surface chemistry and microstructure differed remarkably from its N-free counterparts.