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Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste
The utilization and valorization of agricultural waste is a key strategy for the implementation of a sustainable economy to lessen the environmental footprint of human activities on Earth. This work describes the use of rice husk (RH) from agricultural waste to prepare a highly active catalyst for the reduction of nitro compounds. RH was impregnated with various cobalt complexes bearing N-donor ligands, then pyrolyzed and the resulting composite was etched with a base to remove the silica domains. The composition and morphology of the prepared materials were investigated by IR, AAS, ICP-OES, XRD, BET, XPS and SEM technics. The material showed excellent activity and selectivity in the hydrogenation of nitro groups in aromatic and aliphatic substrates. A remarkable selectivity towards nitro groups was found in the presence of various reactive functionalities, including halogens, carbonyls, borates, and nitriles. Apart from their excellent activity and selectivity, these catalysts showed remarkable stability, allowing their easy recovery and multiple reuse without requiring re-activation.
Cobalt-based nanoparticles prepared from MOF-carbon templates as efficient hydrogenation catalysts
The development of efficient and selective nanostructured catalysts for industrially relevant hydrogenation reactions continues to be an actual goal of chemical research. In particular, the hydrogenation of nitriles and nitroarenes is of importance for the production of primary amines, which constitute essential feedstocks and key intermediates for advanced chemicals, life science molecules and materials. Herein, we report the preparation of graphene shell encapsulated Co3O4- and Co-nanoparticles supported on carbon by the template synthesis of cobalt-terephthalic acid MOF on carbon and subsequent pyrolysis. The resulting nanoparticles create stable and reusable catalysts for selective hydrogenation of functionalized and structurally diverse aromatic, heterocyclic and aliphatic nitriles, and as well as nitro compounds to primary amines (>65 examples). The synthetic and practical utility of this novel non-noble metal-based hydrogenation protocol is demonstrated by upscaling several reactions to multigram-scale and recycling of the catalyst.
Efficient and selective hydrogenation of amides to alcohols and amines using a well-defined manganese-PNN pincer complex
Novel well-defined NNP and PNP manganese pincer complexes have been synthetized and fully characterized. The catalyst Mn-2 containing an imidazolyaminolphosphino ligand shows high activity and selectivity in the hydrogenation of a wide range of secondary and tertiary amides to the corresponding alcohols and amines, under relatively mild conditions. For the first time, more challenging substrates like primary aromatic amides including an actual herbicide can also be hydrogenated using this earth-abundant metal-based pincer catalyst.
Selective cobalt nanoparticles for catalytic transfer hydrogenation of N-heteroarenes
Nitrogen modified cobalt catalysts supported on carbon were prepared by pyrolysis of the mixture generated from cobalt(ii) acetate in aqueous solution of melamine or waste melamine resins, which are widely used as industrial polymers. The obtained nanostructured materials catalyze the transfer hydrogenation of N-heteroarenes with formic acid in the absence of base. The optimal Co/Melamine-2@C-700 catalyst exhibits high activity and selectivity for the dehydrogenation of formic acid into molecular hydrogen and carbon dioxide and allows for the reduction of diverse N-heteroarenes including substrates featuring sensitive functional groups.
A robust iron catalyst for the selective hydrogenation of substituted (iso)quinolones
By applying N-doped carbon modified iron-based catalysts, the controlled hydrogenation of N-heteroarenes, especially (iso)quinolones, is achieved. Crucial for activity is the catalyst preparation by pyrolysis of a carbon-impregnated composite, obtained from iron(ii) acetate and N-aryliminopyridines. As demonstrated by TEM, XRD, XPS and Raman spectroscopy, the synthesized material is composed of Fe(0), Fe3C and FeNx in a N-doped carbon matrix. The decent catalytic activity of this robust and easily recyclable Fe-material allowed for the selective hydrogenation of various (iso)quinoline derivatives, even in the presence of reducible functional groups, such as nitriles, halogens, esters and amides. For a proof-of-concept, this nanostructured catalyst was implemented in the multistep synthesis of natural products and pharmaceutical lead compounds as well as modification of photoluminescent materials. As such this methodology constitutes the first heterogeneous iron-catalyzed hydrogenation of substituted (iso)quinolones with synthetic importance.
Kinetic investigation of para-nitrophenol reduction with photodeposited platinum nanoparticles onto tunicate cellulose
Photodeposition is a specific method for depositing metallic co-catalysts onto photocatalysts and was applied for immobilizing platinum nanoparticles onto cellulose, a photocatalytically inactive biopolymer. The obtained Pt@cellulose catalysts show narrow and well-dispersed nanoparticles with average sizes between 2 and 5 nm, whereby loading, size and distribution depend on the preparation conditions. The catalysts were investigated for the hydrogenation of para-nitrophenol via transfer hydrogenation using sodium borohydride as the hydrogen source, and the reaction rate constant was determined using the pseudo-first-order reaction rate law. The Pt@cellulose catalysts are catalytically active with rate constant values k from 0.09 × 10−3 to 0.43 × 10−3 min−1, which were higher than the rate constant of a commercial Pt@Al2O3 catalyst (k = 0.09 × 10−3 min−1). Additionally, the Pt@cellulose catalyst can be used for electrochemical hydrogenation of para-nitrophenol where the hydrogen is electrocatalytically formed. The electrochemical hydrogenation is faster compared to the transfer hydrogenation (k = 0.11 min−1).