This study is focused on the development of liquid organic hydrogen carriers (LOHC) based on N-heterocyclic compounds. These LOHC-substrates are attractive for their lower hydrogen extraction temperature compared to cycloalkanes, which is caused by the low enthalpy of the dehydrogenation reaction of the N-heterocyclic compounds. The low hydrogen extraction temperature, as well as the low volatility of the heterocycles, provide high purity hydrogen from the reaction. Under similar reaction conditions, the comparison of the efficacy of three promising heterocycles (1-methyl-octahydroindole (8HMI), tetradecahydrophenazine and decahydroquinoline) was carried out in the presence of palladium-containing catalysts. As a result, the advantages of using catalysts supported by alumina, and the high perspectivity of the 8MHI application as a LOHC-substrate, were shown. The dehydrogenation of 8HMI in the presence of 1 wt.% Pd/Al₂O₃ allowed for reaching a 100% yield in hydrogen under the conditions of the standard catalytic test (1 h, 240 °C). In order to study the high reactivity of 8HMI, thermodynamic dehydrogenation reaction profiles were computationally evaluated, which showed that 8HMI was the most energetically preferred in the field of hydrogen storage from the studied heterocyclic compounds.

Tetradecahydrophenazine (14HP) is a nitrogen-containing heterocycle compound with a high content of hydrogen that can be released during its dehydrogenation to phenazine (P). The high stability of the 14HP/P pair and relatively low dehydrogenation temperature make 14HP a promising organic hydrogen carrier. This manuscript is devoted to the investigation of hydrogen production by 14HP dehydrogenation over Pd supported on a series of magnesium-aluminum oxides prepared by the aerogel method. This technique made it possible to synthesize catalyst supports characterized by a high surface area and high concentration of surface active sites where active transition metals could be stabilized in a finely dispersed state. The synthesized aerogels had high specific surface areas and pore volumes. A surface area as high as 600 m²/g after calcination at 500 °C was observed for the mixed aerogel with an Mg:Al ratio of 1:4. An increase in the concentration of acidic electron-acceptor sites determined by EPR on the surface of the mixed magnesium-aluminum oxide supports with a high surface area prepared by the aerogel method was found to result in higher hydrogen production due to the faster dehydrogenation of sterically hindered nitrogen-containing tetradecahydrophenazine heterocycles.