Thermo-Catalytic Decomposition of Natural Gas: Connections Between Deposited Carbon Nanostructure, Active Sites and Kinetic Rates

Thermo-catalytic decomposition (TCD) presents a promising pathway for producing hydrogen from natural gas without emitting CO2. This process represents a form of fossil fuel decarbonization where the byproduct, rather than being a greenhouse gas, is a solid carbon material with potential for commercial value. This study examines the dynamic behavior of TCD, showing that carbon formed during the reaction first enhances and later dominates methane decomposition. Three types of carbon materials were employed as starting catalysts. Methane decomposition was continuously monitored using on-line Fourier transform infrared (FT-IR) spectroscopy. The concentration and nature of surface-active sites were determined using a two-step approach: oxygen chemisorption followed by elemental analysis through X-ray photoelectron spectroscopy (XPS). Changes in the morphology and nanostructure of the carbon catalysts, both before and after TCD, were examined using high-resolution transmission electron microscopy (HRTEM). Thermogravimetric analysis (TGA) was used to study the reactivity of the TCD deposits in relation to the initial catalysts. Partial oxidation altered the structural and surface chemistry of the initial carbon catalysts, resulting in activation energies of 69.7–136.7 kJ/mol for methane. The presence of C2 and C3 species doubled methane decomposition (12% → 24%). TCD carbon displayed higher reactivity than the nascent catalysts and sustained long-term activity.