Ni@Pd core-shell nanoparticles supported on a metal-organic framework as highly efficient catalysts for nitroarenes reduction

Ni@Pd core-shell nanoparticles with a mean particle size of 8–9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine.Subsequently,the first-ever deposition of Ni@Pd core-shell nanoparticles having different compositions on a metal-organic framework（MIL-101）was accomplished by wet impregnation in n-hexane.The Ni@Pd/MIL-101 materials were characterized by powder X-ray diffraction,Fourier transform infrared spectroscopy,transmission electron microscopy,and energy-dispersive X-ray spectroscopy and also investigated as catalysts for the hydrogenation of nitrobenzene under mild reaction conditions.At 30 °C and 0.1 MPa of H2 pressure,the Ni@Pd/MIL-101 gives a TOF as high as 375 h–1 for the hydrogenation of nitrobenzene and is applicable to a wide range of substituted nitroarenes.The exceptional performance of this catalyst is believed to result from the significant Ni-Pd interaction in the core-shell structure,together with promotion of the conversions of aromatics by uncoordinated Lewis acidic Cr sites on the MIL-101 support.

Synergism of Pt nanoparticles and iron oxide support for chemoselective hydrogenation of nitroarenes under mild conditions

An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors andα-Fe2O3 as a support.The catalyst with Pt content as low as 0.2 wt%exhibits high activities,chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes.The conversion of nitrobenzene can reach 3170 molconv h^–1 molPt^–1 under mild conditions(30°C,5 bar),which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions.The spatial separation of the active sites for H2 dissociation and hydrogenation should be responsible for the high chemoselectivity,which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles.The unique surface properties ofα-Fe2O3 play an important role in the reaction process.It provides active sites for hydrogen spillover and reactant adsorption,and ultimately completes the hydrogenation of the nitro group on the catalyst surface.

Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide(CO)as both reductant and carbonyl source,which enables facile access to amides with excellent regioselectivity and broad substrate scope.It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity.Branched amides were mainly obtained with K2PdCl4 as the metal catalyst,and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity.However,phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH3CN)4(OTf)2 was used;monodentate phosphines tended to form branched amides,and bidentate phosphines mainly formed linear amides.Trapping experiments,primary kinetic studies,and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene(further converted to enamide)and aniline,respectively,different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines.Furthermore,the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.

Carbon film encapsulated Fe_2O_3: An efficient catalyst for hydrogenation of nitroarenes

Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were embedded into carbon films,was prepared via the pyrolysis of iron‐polyaniline complexes on carbon particles.The obtained catalyst shows a large surface area,uniform pore channel distribution,with the Fe2O3NPs homogeneously dispersed across the hybrid material.Scanning electron microscopy,Raman spectroscopy and X‐ray diffraction analyses of the catalyst prepared at900°C(Fe2O3@G‐C‐900)and an acid‐pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles.Observation of high‐resolution transmission electron microscopy images also revealed that the Fe2O3NPs in the hybrid were encapsulated by a thin carbon film.The Fe2O3@G‐C‐900composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions,where previously noble metals were required.The synthetic strategy and the structure of the iron oxide‐based composite may lead to the advancement of cost‐effective and sustainable industrial processes.

Chemoselective transfer hydrogenation to nitroarenes mediated by oxygen-implanted MoS_2

We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst（O-MoS2）.O-MoS2 was prepared by incomplete sul idation and reduction of an ammonium molybdate precursor.A number of Mo-O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets.As a consequence of the different coordination geometries of O（Mo O2） and S（MoS2）,and lengths of the Mo-O and Mo-S bonds,the implanted Mo-O bonds induced obvious defects and more coordinatively unsaturated（CUS） Mo sites in O-MoS2,as confirmed by X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,high resolution transmission electron microscopy,and extended X-ray absorption fine structure characterization of various MoS2-based materials.O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.

Biosynthesis of copper nanoparticles supported on manganese dioxide nanoparticles using Centella asiatica L. leaf extract for the efficient catalytic reduction of organic dyes and nitroarenes

In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐sourced reducing agent,without stabilizers or surfactants.This synthetic process is environmentally‐friendly and avoids the use of toxic reducing agents.Phenolic hydroxyl groups in the leaf extract are believed to reduce Cu2+in solution to generate Cu NPs that are subsequently stabilized on the MnO2NP surfaces.The resulting Cu/MnO2nanocomposite was fully characterized using X‐ray diffraction,transmission electron microscopy,field emission scanning electron microscopy,energy‐dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy.This material was found to function as a highly active,efficient and recyclable heterogeneous catalyst for the reduction of Congo red,rhodamine B and methylene blue as well as nitro compounds such as2,4‐dinitrophenylhydrazine and4‐nitrophenol in the presence of NaBH4in aqueous media at ambient temperature.The high stability of the Cu/MnO2nanocomposite also allows the catalyst to be separated and reused several times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Chemoselective Catalytic Hydrogenation of Nitroarenes Using MOF-Derived Graphitic Carbon Layers Encapsulated Ni Catalysts

Replacement of precious noble metal catalysts with cost-effective,non-noble heterogeneous catalysts for chemoselective hydrogenation of nitroarenes holds tremendous promise for the clean synthesis of nitrogen-containing chemicals.Graphitic carbon layers encapsulated Ni catalysts(Ni@CN)are generated by a facile,scalable and straightforward strategy via the pyrolysis of 2,5-pyridinedicarboxylic acid coordinated Ni-MOF acting as the precursor.Physicochemical properties of the Ni@CN catalysts have been investigated by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,elemental analysis and N2 adsorption-desorption analysis.The Ni@CN catalysts were found to be highly efficient in the chemoselective hydrogenation of various nitroarenes with other functional groups towards corresponding anilines under mild reaction conditions(85℃,1.0 MPa of H2 pressure).Based on the results of controlled tests,the catalytic activity can be attributed to the Ni NPs,while the presence of graphitic carbon layers favors the preferential adsorption of the nitro groups.The recyclability and anti-sulfur poisoning capability of Ni@CN were also investigated.

A solvent-free,selective liquid phase hydrogenation of nitroarenes to aniline in slurry bubble mode on porous NiMo bimetallic catalyst

NiMo bimetallic catalysts were prepared by a solid reaction method.On the NiMo catalyst,the selective liquid phase hydrogenation of nitrobenzene to aniline was achieved in slurry bubble mode.And the high yields(98.9%)were obtained under the conditions of 80℃,solvent-free and atmospheric pressure.The effect of Mo on the catalytic behavior of Ni based catalyst was investigated.The characterization displayed that the inclusion of Mo could improve the specific surface area and pore volume,and the solid reaction method made metal Mo enrichment on the surface of catalyst.These two aspects should be responsible for excellent catalytic performance of NiMo catalyst.In sum,we described a simple and efficient NiMo catalyst and provided a facile and green procedure for liquid phase hydrogenation of nitrobenzene to aniline.

Ultrasound-assisted Highly Efficient Reduction of Nitroarenes to Corresponding N-Arylhydroxylamines

A convenient, environmentally benign, and highly efficient protocol for the preparation of N-arylhydroxylamines from the corresponding nitroarenes in a Zn/HCOONH4/CH3CN system under ultrasound is described The advantages of the present method include high chemoselectivity, simple and practical work-up procedure and high yield.

Cobalt nanoparticles encapsulated in nitrogen-doped carbon for room-temperature selective hydrogenation of nitroarenes

Here,we report cobalt nanoparticles encapsulated in nitrogen‐doped carbon(Co@NC)that exhibit excellent catalytic activity and chemoselectivity for room‐temperature hydrogenation of nitroarenes.Co@NC was synthesized by pyrolyzing a mixture of a cobalt salt,an inexpensive organic molecule,and carbon nitride.Using the Co@NC catalyst,a turnover frequency of^12.3 h?1 and selectivity for 4‐aminophenol of>99.9%were achieved for hydrogenation of 4‐nitrophenol at room temperature and 10 bar H2 pressure.The excellent catalytic performance can be attributed to the cooperative effect of hydrogen activation by electron‐deficient Co nanoparticles and energetically preferred adsorption of the nitro group of nitroarenes to electron‐rich N‐doped carbon.In addition,there is electron transfer from the Co nanoparticles to N‐doped carbon,which further enhances the functionality of the metal center and carbon support.The catalyst also exhibits stable recycling performance and high activity for nitroaromatics with various substituents.

Decarboxylative Amination with Nitroarenes via Synergistic Catalysis

In this paper,we have developed a decarboxylative amination of carboxylic acids with nitroarenes for the synthesis of secondary amines.The protocol is performed at mild conditions without the use of noble metals as catalysts.A wide range of structurally diverse secondary amines could be obtained in good yields(up to 94%)with good functional group tolerance.This transformation shows good to excellent selectivity,avoiding the generation of over alkylated byproducts.

Chemoselective Transfer Hydrogenation of Nitroarenes with Ammonia Borane Catalyzed by Copper N-Heterocyclic Carbene Complexes

Herein,we present a method for the homogeneous hydrogenation of nitroarenes to produce anilines using low catalyst loading(1 mo%)of copper N-heterocyclic carbene complexes as the catalyst and ammonia borane as the source of hydrogen.A wide range of nitroarenes,featuring diverse functional groups,were selectively transformed into their corresponding primary aromatic amines with high yields.This process can be readily scaled up and exhibits compatibility with various sensitive functional groups,including halogen,trifluoromethyl,aminomethyl,alkenyl,cyano,ester,amide,and hydroxyl.Notably,this catalytic methodology finds application in the synthesis of essential drug compounds.Mechanistic investigations suggest that the in-situ-generated Cu-H species may serve as active intermediates,with reduction pathways involving species such as azobenzene,1,2-diphenylhydrazine,nitrosobenzene,and N-phenylhydroxylamine.

One-pot synthesis of Fe_(x)O_(y)nanoparticles embedded within N-doped carbon layers as highly efficient and selective catalysts for the hydrogenation of nitroarenes

Inhibiting the side reactions while promoting hydrogenation are the main target for the production of functional anilines from nitroarenes;consequently,the preparation of an ideal catalyst to improve chemical selectivity is one of the hot issues.In this work,we provided an easy-to-prepare catalyst with Ndoped carbon layers,where the Fe_(x)O_(y)nanoparticles were encapsulated and distributed uniformly.The structural features of catalyst were characterized by several techniques,and the selected catalyst was next applied to the hydrogenation of nitrobenzene under varied conditions,involving temperature,holding period and H2 pressure.Subsequently,we conducted the synthesis of more than 16 substrates for the corresponding anilines with varied functional groups.The hydrogenation protocol to gram-scale synthesis as well as lifecycle performance were also demonstrated in the batch reactor,together with the explanation of its catalytic mechanisms.Overall,the present work provides an available preparation of simple but highly efficient catalysts for the production or aromatic amines,which will be benefit for the sustainable development of this field in near future.

Electrochemical borylation of nitroarenes

A simple electrochemically mediated method for the conversion of nitroarenes to aryl boronic esters is presented.Electrochemical borylation of a diverse range of nitroarenes,including the late-stage borylation of bioactive molecules,is furnished at room temperature under simple conditions,thereby demonstrating the broad utility and functional-group tolerance of this protocol.This transformation provides a convenient and practical access to aryl boronic esters from widely available nitroarenes,which would significantly streamline the synthetic process of diverse functionalized arenes.

Iron-catalyzed reductive cyclization of nitroarenes: Synthesis of aza-heterocycles and DFT calculations

Research into environmentally friendly strategies for hydrogen transfer reduction is increasing, along with the need for more elaborate heterocyclic platforms. Within this context, we develop a new approach for substituted dihydrobenzo[c]carbazoles and indoles. These compounds were synthesized through an iron-catalyzed hydrogen transfer reduction of nitroarenes, followed by intramolecular cyclization. This transformation involves using a Kn?lker-type catalyst, Cs_(2)CO_(3) as the base, and benzyl alcohol as the nonexpensive and low volatile hydrogen donor. We synthesize 30 examples of aza-heterocycles with moderate to excellent yields by applying this strategy. Additionally, DFT calculations demonstrated that the pathway reaction could follow an anionic mechanism.

Tuning electron delocalization and surface area in COFs derived N,B co-doped carbon materials for efficient selective hydrogenation of nitroarenes

Metal-free carbon catalysts with excellent conduction performance have drawn much research attention in reduction reactions.Herein,a N,B co-doped carbon catalyst with high pyrrolic N proportion(35.75%)and excellent surface area(1409 m^(2)/g)was successfully prepared via carbonizing covalent organic framework materials(COFs)containing N and B atoms assisted by ZnCl_(2)molten salt.The presence of ZnCl_(2)maintains the micropore structure of COFs to provide high specific surface areas and abundant lattice defects for carbon materials.In addition,electron-withdrawing B heteroatom further facilitates the formation of pyrrolic N at defect sites by modifying the electronic structure of carbon network.The tuning of surface areas and active N species in carbon catalysts successfully improve the selective hydrogenation of nitrobenzene to aniline.The optimized carbon material exhibits excellent nitrobenzene conversion(99.9%)and aniline selectivity(>99%)within 15 min,as well as excellent substrate suitability.This work provides a certain guiding for the design and application of metal-free catalysis.

Cobalt single atoms anchored on N-doped ultrathin carbon nanosheets for selective transfer hydrogenation of nitroarenes

Selective transfer hydrogenation of nitroarenes to amines with transition metal nanocatalysts is appealing due to its low-cost, moderate reaction conditions, good activity and excellent selectivity. Single-atom catalysts (SACs) possessing advantages of maximum atom efficiency and particular electronic structure are expected to be more effective for this reaction, yet no report about it. Herein, cobalt single atoms anchored on N-doped ultrathin carbon nanosheets (denoted as CoSAs/NCNS) were produced and demonstrated as an outstanding SAC for selective transfer hydrogenation of nitroarenes to amines with formic acid as hydrogen donor. The turnover frequency (TOF) reached 110.6 h^-1, which was 20 times higher than the best results of cobalt nanopartides reported in literatures under similar reaction conditions. Moreover, CoSAs/NCNS exhibited excellent selectivity for a variety of nitroarenes bearing other reducible functionalities, such as iodo, cyano, keto, vinyl, alkynyl and ester groups. The findings further highlight the ability and advantages of SACs in heterogeneous catalysis.

Photocatalytic hydrogenation of nitroarenes using Cu1.94S-Zn0.23Cd0.77S heteronanorods

Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/ proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu1.94S-Zn0.23Cd0.775 semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.

Metallo-aerogels derived from chitosan with encapsulated metal nanoparticles as robust,efficient and selective nanocatalysts towards reduction of nitroarenes

A series of robust metallo-aerogels are readily fabricated by pyrolysis of xerogels derived from chitosan-metal(M=Fe,Co,Ni)hydrogels.Owing to the strong coordination between metal ions and the functional groups(NH2 and OH)of chitosan,metallo-aerogels consisting of encapsulated metal-nanoparticles(MNPs)by graphite shells were obtained,as supported by various characterizations including high-resolution transmission electron microscope(HR-TEM),X-ray diffraction(XRD),and Raman.The resulting metalloaerogels could be functioned as highly stable,efficient and selective nanocatalysts towards the hydrogenation of nitroarenes to amines at low catalyst loading(1.2 mol.%-2.4 mol.%).Remarkably,the metallo-aerogels could be reused for more than 30 runs without obvious loss of activity and selectivity.These distinguished performances were attributed to the graphitic shells formed during the pyrolysis,which hampered the possible aggregation of MNPs,prevented metal leaching and increased their stability.

Magnetic graphene nanocomposite as an efficient catalyst for hydrogenation of nitroarenes

Graphene-Fe3O4 nanocomposite（G-Fe3O4） was synthesized by a chemical co-precipitation method which was used as an efficient catalyst for the reduction of nitroarenes with hydrazine hydrate.The method has been applied to a broad range of compounds with different properties and the yields were in the range of 75%-92%.The G-Fe3O4 catalyst can be readily recovered and reused 5 times without significant loss of the catalytic activity.