Formic acid is a promising liquid organic hydrogen carrier (LOHC) since it has relatively high hydrogen content (4.4 wt%), low inflammability, low toxicity and can be obtained from biomass or from CO₂. The aim of the present research was the creation of efficient 1 wt% Pd catalysts supported on mesoporous graphitic carbon (Sibunit) for the hydrogen production from gas-phase formic acid. For this purpose, the carbon support was modified by pyrolysis of deposited precursors containing pyridinic nitrogen such as melamine (Mel), 2,2′-bipyridine (Bpy) or 1,10-phenanthroline (Phen) at 673 K. The following activity trend of the catalysts Pd/Mel/C > Pd/C ~ Pd/Bpy/C > Pd/Phen/C was obtained. The activity of the Pd/Mel/C catalyst was by a factor of 4 higher than the activity of the Pd/C catalyst at about 373 K and the apparent activation energy was significantly lower than those for the other catalysts (32 vs. 42–46 kJ/mol). The high activity of the melamine-based samples was explained by a high dispersion of Pd nanoparticles (~2 nm, HRTEM) and their strong electron-deficient character (XPS) provided by interaction of Pd with pyridinic nitrogen species of the support. The presented results can be used for the development of supported Pd catalysts for hydrogen production from different liquid organic hydrogen carriers.

The development of solvent-free methods for the synthesis of catalysts is one of the main tasks of green chemistry. A nickel–alumina catalyst for CO₂ methanation was synthesized by solid-state combustion method using hexakis-(imidazole) nickel (II) nitrate complex. Using X-ray Powder Diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Hydrogen temperature-programmed reduction (H₂-TPR), it was shown that the synthesized catalyst is characterized by the localization of easily reduced nickel oxide on alumina surface. This provided low-temperature activation of the catalyst in the reaction mixture containing 4 vol% CO₂. In addition, the synthesized catalyst had higher activity in low-temperature CO₂ methanation compared to industrial NIAP-07-01 catalyst, which contained almost three times more hard-to-reduce nickel–aluminum spinel. Thus, the proposed approaches to the synthesis and activation of the catalyst make it possible to simplify the catalyst preparation procedure and to abandon the use of solvents, which must be disposed of later on.

Porous ceramometal Al₂O₃/CoAlO/CoAl was studied by set of physicochemical techniques such as XRD, SEM, internal field ⁵⁹Co and ²⁷Al MAS NMR, and porosity measurements. They revealed the cermet containing three parts. First, cobalt-free large porous alumina particles which surrounded by the second oxide part representing spinel Co_xAl_3-xO₄ (x=1,2,3) oxides. And third, oxygen-free metallic part consists of cobalt metal particles covered by Co-Al oxide protecting the metallic part from oxidation. Porosity measurements ascertained high porosity (60%) and good SSA (122 m²/g). Also the enhanced adsorption of microwaves due to metallic particles randomly distributed in oxides was found.