Abstract
Thermal catalytic decomposition of methane is an innovative pathway to produce CO2-free hydrogen from natural gas. We investigated the role of Cu content in carbon-supported bimetallic NiCu catalysts. A graphitic carbon material was used as a model support, and we combined operando methane decomposition experiments in a thermogravimetric analyzer with in situ electron microscopy measurements. The carbon yield was maximum with around 30% Cu in the nanoparticles. Adding more Cu drastically lowered the carbon solubility in the metal nanoparticles, which lowered the initial reaction rate and overall carbon yield. In situ TEM measurements showed that the addition of Cu to the catalysts strongly influenced the metal nanoparticle shape and size during carbon growth, and the growth mode. NiCu particles were larger, remained spherical and facilitated steady CNF growth. In contrast, pure Ni nanoparticles fluctuated in shape, sometimes fragmented, and showed stuttering CNF growth. This was ascribed to fluctuating coverage of part of the Ni nanoparticle surface with amorphous carbon, which increased the chance of total encapsulation and hence deactivation of the individual Ni nanoparticles. This supports a picture where balancing the carbon supply, transport, and nucleation of amorphous and crystalline carbon is crucial. Our results also highlight the importance of combining statistically relevant measurements with microscopic information on individual nanoparticles to understand overall catalytic trends from the combined behavior of individual catalyst nanoparticles.