Ultrafine NiMoO(x) nanoparticles confined in mesoporous carbon for the reduction of nitroarenes: effect of the composition and accessibility of the active sites

The design of ultrafine NiMoO(x) nanoparticles (NPs) confined in hierarchically porous carbon remains a great challenge due to its high calcination temperature. In addition, the composition of active sites of NiMoO(x) NPs for the hydrogenation reaction is still ambiguous. Herein, we report a general approach for the synthesis of ultrafine NiMoO(x) NPs confined in mesoporous carbon with different morphologies and compositions using the replication method with SBA-15 as a hard template. The pore structure of mesoporous carbon and the Ni/Mo composition valence-state were discovered to be the main factors in the reduction of nitroarenes. The NiMoO(x)/mesoporous carbon-platelet (NiMoO(x)/MC-PL) with short mesochannels (∼350 nm) and high surface area (∼995 m(2) g(−1)) possessed excellent catalytic activity towards the reduction of 4-nitrophenol, whereas NiMoO(x)/mesoporous carbon-hexagonal-prism (NiMoO(x)/MC-HP), NiMoO(x)/mesoporous carbon-long-rod (NiMoO(x)/MC-LR), and NiMoO(x)/mesoporous carbon-spherical (NiMoO(x)/MC-SP) with long mesochannels and relatively less surface area exhibited poor catalytic performance. The bifunctional mechanism or electronic synergistic effects of Ni and Mo species enhanced their catalytic performance. A good balance between MoO(x) and metallic Ni (NiMoO(x)/MC-PL-450) was found to be suitable for the reduction of 4-NP.