Formic
acid (FA) can be considered a bridge between biomass and
green fuels, as biomass can be oxidized to FA, followed by FA dehydration
to CO for Fischer–Tropsch synthesis. In this work, a series
of γ-Mo2N-based catalysts used for FA dehydration
was prepared by the facile pyrolysis of a Mo-containing precursor
at different temperatures. It was found that the γ-Mo2N-based catalysts exhibited high performance for FA dehydration to
CO with a maximum selectivity of ∼99.8%, and the onset reaction
temperature over the γ-Mo2N-based catalysts was also
much lower (100–200 °C) than those over conventional solid
acid catalysts. In particular, the γ-Mo2N obtained
at a pyrolysis temperature of 625 °C exhibited the highest activity,
which was followed by those of the catalysts obtained at 600, 650,
and 700 °C, which was consistent with the acidities of these
catalysts. However, the CO selectivity monotonically increased with
the increase in the catalyst preparation temperature but decreased
with the increase in the FA decomposition temperature. FA conversion
decreased when the contact time between the catalyst and the FA was
reduced, but conversely, the CO selectivity increased. The enhanced
CO selectivity might be ascribed to dehydrogenation having comparatively
lower kinetics than that of dehydration, and thus, compared to dehydration,
dehydrogenation could be more apparently suppressed by the reduced
contact time, resulting in a higher CO selectivity. Moreover, it was
found that the γ-Mo2N catalyst had no obvious deactivation
for FA dehydration over the 20 h continuous operation period.