Vitreous silica supported metal catalysts for direct non-oxidative methane coupling

[Display omitted] •Vitreous silica-supported 3d metal (M/SiO2-v) catalysts were studied for NMC.•Catalyst stability followed the order of Mn > Fe ≈ Co > Ni > Cu in NMC reaction.•Mn- and Ni/SiO2-v had high methane reaction and coke formation rates.•Fe- and Co/SiO2-v had the best hydrocarbon product selectivity.•Co/SiO2-v catalyst was optimal in terms of hydrocarbon and minimal coke formation. Direct non-oxidative methane coupling (NMC) transforms methane into valuable chemicals and hydrogen, which is a promising pathway to boost industrial decarbonization. The reaction, however, is challenged by high C-H bond activation temperature, catalyst coking, and low selectivity towards hydrocarbon products. Here we studied the efficacy of five vitreous silica supported 3d transition metal (Mn, Fe, Co, Ni, and Cu) catalysts (denoted as M/SiO2-v) for NMC. These catalysts were prepared by flame fusion of mixtures of quartz and metal silicate precursors. The metal species in the as-synthesized catalysts were fully or partially oxidized, with their stability following the order of Mn > Fe ≈ Co > Ni > Cu in the NMC reaction. The Cu species has low methane reaction rate, due to the high adsorption and dissociation energies of methane. The Mn and Ni species have high methane reaction and coke formation rates, which is supported by easy kinetics of methane deep dehydrogenation to carbon. In contrast, Fe and Co species showed the best hydrocarbon product selectivity. Particularly, the Co species emerged as the optimal catalyst for NMC, showcasing a balanced methane activation, hydrocarbon formation, and low coke yield. The relationship between the evolved metal species under reaction conditions and their NMC performance was discussed. The present study screens and provides effective catalyst formulations for NMC reactions.