Metal–Organic‐Framework‐Derived Co₃S₄ Hollow Nanoboxes for the Selective Reduction of Nitroarenes

Abstract

MOF-derived Co S /CN hollow nanoboxes (CN=nitrogen-doped carbon) was used to catalyze the chemoselective reduction of nitroarenes to anilines under mild reaction conditions with H as the reducing agent. The catalyst provides high conversion efficiencies and selectivities for a variety of nitroarene substrates that contain electron-donating or electron-withdrawing substituents under mild reaction conditions (in methanol at 60 °C). Further, the nanobox inhibits both dehalogenation and vinyl hydrogenation reactions, which are common limitations of state-of-the-art Pd-based catalysts. Because the reactions result in pure aniline products, the need for separation by column chromatography is eliminated. The resulting anilines are easily separated from the methanolic reaction solution in just three simple steps (centrifugation, decantation, and drying). If employed in industrial processes, catalysts of this kind would significantly reduce the amount of waste organic solvent generated and thus satisfy the need for sustainable chemical processes.

Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives

“…nitro-compounds hydrogenations,244,263,276,280,281,285,[304][305][306][307] alcohols oxidations,247,293,297 CO oxidation250,259,[264][265][266][267][268][277][278][279]289,[294][295][296]301,246,254,285,[290][291][292]309,310 Ox, achieved by the direct calcination of a bimetallic Ce(Cu)-MOF at 600 °C for 3 h. The catalytic activity was tested using a continuous flow fixed-bed micro-reactor at atmospheric pressure with a CO/O2/N2 mixture in a volume ratio of 1:10:89. The authors found the CeO2-CuO exhibited a high catalytic activity in comparison to that of Ce-Cu-Ox; an almost 80% CO conversion for CeO2-CuO at 250 °C and only 22% for Ce-Cu-Ox derived from the Ce(Cu)-MOF.…”

Multi-purpose heterogeneous catalyst material from an amorphous cobalt metal–organic framework

“…While TBHP-driven oxidations of arylmethanes have been reported to be catalyzed by Fe-N-C materials effectively, 23,[27][28][29] the cobalt corresponding Co-N-C catalysts were not. 30 Typically, Co-N-C catalysts are used for reduction reactions (nitroarenes, 31,32 N-heterocycles, 33 and hydrocarbons 34 ), reductive aminations 35 and alkylations, 36,37 while the oxidative esterification of benzyl alcohols were done under dioxygen. [38][39][40] Overall, the cobalt materials outperformed the three previously reported related Fe-N-C systems (TAL-1-900, TAL-6-900, TAL-7-900), 22,23 and importantly, they sustained their activity over a larger number of cycles (Fig.…”

Incorporating Sulfur Atoms into Palladium Catalysts by Reactive Metal–Support Interaction for Selective Hydrogenation

“…8,12,13,[15][16][17][18][19][20] Developing new hydrogenation catalysts with high intrinsic chemoselectivity is a straightforward and effective strategy to tackle this tough problem. 8,[21][22][23][24][25][26][27] Some important progresses have been achieved recently by employing Au-, Ag-based, and pyrolyzed Fe(or Co)/nitrogen/carbon catalysts for selective reduction of the nitro group of substituted nitroarenes. 8,21,25,[28][29][30] Nevertheless, these catalysts always suffer from low activity and thus often require harsh reaction conditions, such as high temperature (≥120 °C), high H 2 pressure (≥5.0 MPa), and long reaction time (≥12 h).…”