Zsolt Fejes

Palladium nanocatalyst has been prepared via sonication-induced reductive deposition for the hydrogenation of nitro groups, tested in the two industrially most significant nitro compound hydrogenation processes: nitrobenzene hydrogenation to aniline and 2,4-dinitrotoluene to 2,4-toluene diamine. The main feature of the catalyst beside the fact that it is well usable for both reactions with high efficiency (~ 99% at 60 °C and 20 bar with 192 substrate-to-palladium ratio), the paramagnetic properties owing to the presence of magnetite (20.9 wt%), which enables separation via magnetic field (5.7 A m ² k g ⁻¹ ). This feature provides further alternative possibility for both laboratory and industrial applications. Furthermore, the use of AEROSIL 200 (fumed amorphous silica) with a straightforward magnetite preparation method provides a cost-efficient support with advantageous properties for a promising catalyst.

A separable bamboo-like carbon nanotube-based catalyst was prepared by the spherfication method using sodium alginate and nickel. The spheres were carbonized and then decorated with palladium nanoparticles before they were tested in nitrobenzene hydrogenation. The test was repeated with five different commonly used solvents (methanol, ethanol, isopropanol, tetrahydrofuran, and acetonitrile). According to the results, polar solvents showed a significantly higher aniline yield than the more apolar solvents and exceptional results were reported for ethanol (~100%). The catalyst was reused two more times (four hours each) to check the Pd leaching where the spheres kept their shape (despite the high mechanical friction caused by the mixer) and only a relatively low Pd amount was lost (5.48 rel.%). The catalyst was easily retrievable.

A naturally derived silicate, diatomaceous earth has been endowed with magnetic properties by depositing magnetite nanoparticles on its surface. Palladium crystallites were created on the resulting magnetizable catalyst support. The support provided high specific surface area with high porosity which were ideal for the binding of both the magnetic particles and the palladium. The catalyst was successfully tested in the hydrogenation of benzophenone in three different solvents (methanol, ethanol, and isopropanol). Significant differences in catalytic activity were observed, allowing selective production of benzhydrol (BH) or diphenylmethane (DPM) by a simple solvent change. Beside the excellent selectivity, the featured catalyst also provided an easy and fast method for catalyst recoverability using a simple magnet.

Catalytic activity of a palladium catalyst with a porous carbon support was prepared and tested for benzophenone hydrogenation. The selectivity and yields toward the two possible reaction products (benzhydrol and diphenylmethane) can be directed by the applied solvent. It was found that in isopropanol, the prepared support was selective towards diphenylmethane with high conversion (99% selectivity and 99% benzophenone conversion on 323 K after 240 min). This selectivity might be explained by the presence of the incorporated structural nitrogens in the support.

A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile in the presence of different tertiary amine catalysts was performed. The reaction mechanisms in the absence and presence of experimentally applied catalysts were described by using the G3MP2BHandHLYP composite method. The apparent activation energies obtained from the calculations were in good agreement with the experimental data (ΔΔE = −1). Both experimental and theoretical results proved the important effect of tertiary amine catalysts on urethane formation. These results can aid in polyurethane catalyst design and development.

The alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile in the presence of different cyclic amine catalysts was examined using a combined kinetic and mechanistic approach. The molecular mechanism of urethane formation without and in the presence of cyclic amine catalysts was studied using the G3MP2BHandHLYP composite method in combination with the SMD implicit solvent model. It was found that the energetics of the model reaction significantly decreased in the presence of catalysts. The computed and measured thermodynamic properties were in good agreement with each other. The results prove that amine catalysts are important in urethane synthesis. Based on the previous and current results, the design of new catalysts will be possible in the near future.

Polyurethanes (PUs) are widely used in different applications, and thus various synthetic procedures including one or more catalysts are applied to prepare them. For PU foams, the most important catalysts are nitrogen-containing compounds. Therefore, in this work, the catalytic effect of eight different nitrogen-containing catalysts on urethane formation will be examined. The reactions of phenyl isocyanate (PhNCO) and methanol without and in the presence of catalysts have been studied and discussed using the G3MP2BHandHLYP composite method. The solvent effects have also been considered by applying the SMD implicit solvent model. A general urethane formation mechanism has been proposed without and in the presence of the studied catalysts. The proton affinities (PA) were also examined. The barrier height of the reaction significantly decreased (∆E₀ > 100 kJ/mol) in the presence of the studied catalysts, which proves the important effect they have on urethane formation. The achieved results can be applied in catalyst design and development in the near future.

A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate using 1-propanol as the alcohol was undertaken. A molecular mechanism of urethane formation in both alcohol and isocyanate excess is explored using a combination of an accurate fourth generation Gaussian thermochemistry (G4MP2) with the Solvent Model Density (SMD) implicit solvent model. These mechanisms were analyzed from an energetic point of view. According to the newly proposed two-step mechanism for isocyanate excess, allophanate is an intermediate towards urethane formation via six-centered transition state (TS) with a reaction barrier of 62.6 kJ/mol in the THF model. In the next step, synchronous 1,3-H shift between the nitrogens of allophanate and the cleavage of the C–N bond resulted in the release of the isocyanate and the formation of a urethane bond via a low-lying TS with 49.0 kJ/mol energy relative to the reactants. Arrhenius activation energies of the stoichiometric, alcohol excess and the isocyanate excess reactions were experimentally determined by means of HPLC technique. The activation energies for both the alcohol (measured in our recent work) and the isocyanate excess reactions were lower compared to that of the stoichiometric ratio, in agreement with the theoretical calculations.