CO_x-Free Hydrogen Production via CH₄ Decomposition on Alkali-Incorporated (Mg, La, Ca, Li) Ni-Al Catalysts

The catalytic decomposition of CH₄ is a promising method for producing high-purity CO_x-free hydrogen. A Ni-Al-LDH catalyst synthesized via coprecipitation was modified with alkali metals (Mg, La, Ca, or Li) through reconstruction to enhance catalytic activity and resistance to deactivation during catalytic methane decomposition (CMD). The catalysts were evaluated by two activation methods: H₂ reduction and direct heating with CH₄. The MgNA-R catalyst achieved the highest CH₄ conversion (65%) at 600 °C when reduced with H₂, attributed to a stronger Ni-Al interaction. Under CH₄ activation, LaNA-C achieved a 55% conversion at the same temperature, associated with a smaller crystallite size and higher reducibility due to La incorporation. Although all catalysts deactivated due to carbon deposition and/or sintering, LaNA-C was the only sample that could resist deactivation for a longer period, as La appears to have a protective effect on the active phase. Post-reaction characterizations revealed the formation of graphitic and filamentous carbon. Raman spectroscopy exhibited a higher degree of graphitization and structural order in LaNA-C, whereas SEM showed a more uniform distribution of carbon filaments. TEM confirmed the presence of multi-walled carbon nanotubes with encapsulated Ni particles in La-promoted samples. These results demonstrate that La addition improves the catalytic performance under CH₄ activation and carbon structure. This finding offers a practical advantage for CMD processes, as it reduces or eliminates the need to use hydrogen during catalyst activation.