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One of the challenges for the non-oxidative coupling of methane (NOCM) is to effectively remove the deposited coke over catalysts owing to the over-dehydrogenation of methane. Herein, we show that an insitu growth of carbon nanotubes (CNTs) instead of coke were observed during NOCM over a CuSO4/γ-Al2O3 catalyst. The as-grown CNTs depict an unexpected promoting effect for NOCM with a highest activity of 0.48 mol kg cat·h, and maintained 85% activity after 200 h running time. The equilibrium methane conversion is 9.8% with a selectivity of 78.2% for C2 (C2H4 + C2H6) products. Highly dispersed Cu nanoparticles distributed on the top of CNTs measured by transmission electron microscopy is proposed to result in high catalyst stability during NOCM for 200 h instead of deactivation in several hours. Here, we firstly prove that the as-grown CNTs can promote the catalytic activity of NOCM instead of deactivation by coking over catalysts.

Unexpectedly Promoting Effect of Carbon Nanotubes Grown During the Non-oxidative Coupling of Methane over Copper Catalysts