Porous nanographene formation on γ-alumina nanoparticles via transition-metal-free methane activation

γ-Al(2)O(3) nanoparticles promote pyrolytic carbon deposition of CH(4) at temperatures higher than 800 °C to give single-walled nanoporous graphene (NPG) materials without the need for transition metals as reaction centers. To accelerate the development of efficient reactions for NPG synthesis, we have investigated early-stage CH(4) activation for NPG formation on γ-Al(2)O(3) nanoparticles via reaction kinetics and surface analysis. The formation of NPG was promoted at oxygen vacancies on (100) surfaces of γ-Al(2)O(3) nanoparticles following surface activation by CH(4). The kinetic analysis was well corroborated by a computational study using density functional theory. Surface defects generated as a result of surface activation by CH(4) make it kinetically feasible to obtain single-layered NPG, demonstrating the importance of precise control of oxygen vacancies for carbon growth.