Simultaneous production of hydrogen and carbon nanostructures by decomposition of propane and cyclohexane over alumina supported binary catalysts

Nano-scale, binary, 4.5 wt.% Fe–0.5 wt.% M (M = Pd, Mo or Ni) catalysts supported on alumina have been shown to be very effective for the decomposition of lower alkanes to produce hydrogen and carbon nanofibers or nanotubes. After pre-reduction at 700 °C, all three binary catalysts exhibited significantly lower propane decomposition temperatures and longer time-on-stream performances than either the non-metallic alumina support or 5 wt.% Fe/Al2O3. Catalytic decomposition of propane using all three catalysts yielded only hydrogen, methane, unreacted propane, and carbon nanotubes. Above 475 °C, hydrogen and methane were the only gaseous products. Catalytic decomposition of cyclohexane using the (4.5 wt.% Fe–0.5 wt.% Pd)/Al2O3 catalyst produced primarily hydrogen, benzene, and unreacted cyclohexane below 450 °C, but only hydrogen, methane, and carbon nanotubes above 500 °C. The carbon nanotubes exhibited two distinct forms depending on the reaction temperature. Above 600 °C, they were predominantly in form of multi-walled nanotubes with parallel walls in the form of concentric graphene sheets. At or below 500 °C, carbon nanofibers with capped and truncated stacked-cone structure were produced. At 625 °C, decomposition of cyclohexane produced a mixture of the two types of carbon nanostructures.