The co-ammonolysis of V(NMe₂)₄ and Si(NHMe)₄ with ammonia in THF and in the presence of ammonium triflate ([NH₄][CF₃SO₃]) leads to the formation of monolithic gels. Pyrolysing these gels produces mesoporous composite materials containing nanocrystalline VN and amorphous silicon imidonitride. Elemental mapping indicated a thorough distribution of VN with no evidence of large cluster segregation. Whilst not active for ammonia synthesis, the silicon nitride based materials were found to possess activity for the CO_x-free production of H₂ from methane, which makes them candidates for applications in which the presence of low levels of CO in H₂ feedstreams is detrimental.