In this work, bimetallic Cu-Ni catalysts supported on binary oxides containing ZnO, ZrO₂, CeO₂ and Al₂O₃ were investigated in hydrogen production via the oxidative steam reforming of methanol (OSRM). Their physicochemical properties were extensively studied using various methods such as BET, TPR-H₂, TPD-NH₃, XRD, SEM-EDS, ToF-SIMS and XPS. The reactivity measurements showed that the active phase and support composition played an important role in the activity of the catalyst in the OSRM. The most active system at higher temperatures was 30% Cu–10% Ni/CeO₂·Al₂O₃, with high catalytic activity attributed to the Cu_0.8Ni_0.2 alloy formation. In addition, the reactivity results showed that the most active catalyst exhibited high acidity and was easily reduced. At low temperatures, the best catalytic properties were exhibited by 30% Cu–10% Ni/ZrO₂·Al₂O₃. The reactivity and physicochemical properties of the studied catalysts confirmed the crucial role of alloy composition on their catalytic properties in the oxy-steam reforming of methanol. The obtained results validate the possibility of using Cu-Ni catalysts for hydrogen production.

Ni catalysts supported on ZrO₂, 5%CeO₂-ZrO₂, and 5%La₂O₃-ZrO₂ were prepared via the impregnation method and tested in the oxy-steam reforming of methane and liquified natural gas (LNG). All tested catalysts exhibited high catalytic activity in the studied process at 700 and 900 °C. The improvement of the stability of Ni catalysts after the addition of CeO₂ oxide in the studied oxy-steam reforming of LNG process was confirmed. In addition, high activity and selectivity towards hydrogen was proven in the oxy-steam reforming process at 900 °C over a 20%Ni/5%CeO₂-ZrO₂ catalyst. It was also proved that the addition of CeO₂ onto a ZrO₂ carrier leads to a decrease in the NiO and metallic Ni crystallite sizes that were detected by the X-Ray diffraction (XRD) technique. The solid solution formation between NiO and ZrO₂ and/or NiO and CeO₂ was proved. Superior reactivity in the oxy-steam reforming of CH₄ and the LNG process exhibited a 20%Ni/ZrO₂ catalyst, which showed the highest methane conversions at 500 and 600 °C, equal to 63% and 89%, respectively. In addition, also in the case of the LNG reforming reaction, the most active catalyst was the 20%Ni/ZrO₂ system, which demonstrated 46.3% and 76.9% of the methane conversion value at 500 and 600 °C and the total conversion of others hydrocarbons (ethane, propane and butane). In addition, this catalytic system exhibited the highest selectivity towards hydrogen formation in the oxy-steam reforming of the LNG reaction equal to 71.2% and 71.3% at 500 and 600 °C, respectively. The highest activity of this system can be explained by the uniform distributions of Ni species and their highest concentration compared to the rest of the monometallic Ni catalysts. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results also confirmed a strong interaction of NiO with ZrO₂ in the case of the 20%Ni/ZrO₂ catalysts. The presence of selected NiZrO⁺ ions emitted from the investigated surface of the 20%Ni/ZrO₂ system was detected.

This work presents, for the first time, the catalytic studies of bimetallic Ag-Ni catalysts in the oxy-steam reforming (OSR) of liquefied natural gas (LNG) to hydrogen generation. The physicochemical properties of monometallic Ni and bimetallic catalysts were investigated using various techniques, such as: BET, TPR-H₂, TPD-NH₃, XRD, TG and SEM-EDS. The catalytic studies showed that the promotion of 20% Ni/ZrO₂ catalyst by silver (by 1 or 2 wt.%) improves the efficiency of the produced hydrogen in the oxy-steam reforming of LNG at high temperature. The promotional effect of silver on the reducibility of a Ni/ZrO₂ catalyst has been proven. The interactions between Ag and Ni have been proven, and explain the catalytic activity of the catalysts in the investigated processes. TG-DTA-MS results obtained for the spent catalysts proved that the small addition of silver to monometallic nickel catalyst reduces the amount of the carbon deposit formed on the catalyst surface during the oxy-steam reforming of LNG process. Obtained results in this work confirmed that liquid natural gas processing may become an alternative to fossil fuels and confirmed the validity of the hydrogen production via oxy-steam reforming of LNG.