Diverse technologies from catalyst coking to graphene synthesis entail hydrocarbon dehydrogenation and condensation reactions on metals and assembly into carbon overlayers. Imperative to gaining control over these processes, through thermal steering of the formation of polyaryl intermediates and the controlled prevention of coking, is the exploration and elucidation of the detailed reaction scheme that starts with adsorbed hydrocarbons and culminates with the formation of extended graphene. Here we use scanning tunneling microscopy, high-resolution electron energy loss and thermal desorption spectroscopies, in combination with theoretical simulations to uncover the hierarchy of pathways and intermediates underlying the catalyzed evolution of ethene adsorbed on Rh(111) to form graphene. These investigations allow formulation of a reaction scheme whereby, upon heating, adsorbed ethene evolves via coupling reactions to form segmented one-dimensional polyaromatic hydrocarbons (1D-PAH). Further heating leads to dimensionality crossover (1D → 2D) and dynamical restructuring processes at the PAH chain ends with subsequent activated detachment of size-selective carbon clusters. Rate-limiting diffusional coalescence of these dynamically self-evolved precursors culminates (≤1000 K) in condensation into graphene of high structural perfection.     «

Diverse technologies from catalyst coking to graphene synthesis entail hydrocarbon dehydrogenation and condensation reactions on metals and assembly into carbon overlayers. Imperative to gaining control over these processes, through thermal steering of the formation of polyaryl intermediates and the controlled prevention of coking, is the exploration and elucidation of the detailed reaction scheme that starts with adsorbed hydrocarbons and culminates with the formation of extended graphene....     »