Activation of Alkanes by Transition Metal Nitrides and Carbides

Abstract

AbstractGroup V and VI nitrides and carbides were synthesized by the temperature programmed reaction of metal oxides with ammonia or an equimolar mixture of methane/hydrogen. The synthesis protocols were developed using thermogravimetric techniques. The resulting nitrides and carbides were primarily mesoporous and possessed surface areas in the range of 11 – 81 m2/g. Their alkane activation rates were comparable to a Pt-Sn/AL20 3 dehydrogenation catalyst and the surface area normalized reaction rates decreased in the following order: Mo2N > W2C > WC > W2N > WC1−x > VCoa0.05N > MO2C > VN = VC > NbMo0.01 N > NbMo0.05 > NbN = NbC. The activities measured at 450°C ranged between 1011 – 1013 molecules/cm2/s for n-butane and 1012 – 1013 molecules/cm2/s for n-hexane. The Group VI nitrides and carbides were far more active than the Group V materials. The Group VI materials catalyzed the hydrogenolysis and dehydrogenation reactions with similar activities whereas the Group V materials were more than 98% selective to dehydrogenation. While the metal atom type had the most significant effect on the catalytic properties, the lattice structure of the material also played a role. In particular, we observed that WC (hex) was almost twice as active as WC1-x (fcc). Nitrides and carbides of the same metal and lattice structure possessed similar catalytic properties, implying that the effect of the non-metal atom type was minimal. The W2N catalyst was found to be highly selective towards n-butane isomerization. The multimetallic nitrides each demonstrated some form of synergy.