Abstract

A temperature programmed treatment of MoO3 in flowing N-2 + H-2 has been employed to prepare beta-phase molybdenum nitride (beta-Mo2N) which has been used to promote, for the first time, the catalytic hydrogenation of p-chloronitrobenzene. The reduction/nitridation synthesis steps have been monitored in situ and the starting oxide, reaction intermediates and nitride product have been identified and characterized by powder X-ray diffraction (XRD), diffuse reflectance UV-Vis (DRS UV-Vis), elemental analysis, scanning electron microscopy (SEM) and BET/pore volume measurements. Our results demonstrate that MoO3 -> beta-Mo2N is a kinetically controlled process where an initial reduction stage generates (sequentially) MoO2 and Mo as reaction intermediates with a subsequent incorporation of N to produce beta-Mo2N. SEM analysis has established that the transformation is non-topotactic with a disruption to the platelet morphology that characterizes MoO3 and an increase in BET area (from 1 m(2) g(-1) to 17 m(2) g(-1)). Moreover, temperature programmed desorption measurements have revealed a significant hydrogen uptake (0.71 mu mol m(-2)) on beta-Mo2N. This has been exploited in the hydrogenation of p-chloronitrobenzene where p-chloroaniline was generated as the sole product with an associated rate constant (k = 2.0 min(-1)) that is higher than values recorded for supported transition metals. Our study establishes the reaction mechanism involved in the synthesis of beta-Mo2N and demonstrates its viability to promote selective -NO2 group reduction as an alternative sustainable, high throughput route to commercially important haloamines.

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