15411-43-5Relevant articles and documents
Highly chemoselective reduction of aromatic nitro compounds by copper nanoparticles/ammonium formate
Saha, Amit,Ranu, Brindaban
, p. 6867 - 6870 (2008)
(Chemical Equation Presented) A highly chemoselective reduction of aromatic nitro compounds to the corresponding amino derivatives has been achieved by a combination of copper nanoparticles and ammonium formate in ethylene glycol at 120°C. The reductions are successfully carried out in presence of a wide variety of other reducible functional groups in the molecule, such as Cl, I, OCH2Ph, NHCH2Ph, COR, COOR, CN, etc. The reactions are very clean and high yielding.
'From the mole to the molecule': Ruthenium catalyzed nitroarene reduction studied with 'bench', high-throughput and single molecule fluorescence techniques
Carrillo, Adela I.,Stamplecoskie, Kevin G.,Marin, M. Luisa,Scaiano, Juan C.
, p. 1989 - 1996 (2014)
Single molecule fluorescence microscopy techniques are used to complement conventional catalysis and high-throughput experiments in order to gain a complete picture of a model reaction. In these experiments a model nitroarene is reduced to an amine where, upon reduction, a red shift in absorption/emission, as well as an increase in emission, is observed. The reaction is studied under bulk reaction conditions by NMR spectroscopy and the fluorescence activation makes it possible to also study this reaction at the single molecule level. Fluorescence correlation spectroscopy is a valuable technique in supporting the proposed reaction mechanism and understanding the nature and duration of molecular 'visits' to catalytic sites, where both the starting material, nitroarene, and the amine product have an affinity for the catalyst. The Royal Society of Chemistry 2014.
Transforming nonselective into chemoselective metal catalysts for the hydrogenation of substituted nitroaromatics
Corma, Avelino,Serna, Pedro,Concepcion, Patricia,Calvino, Jose Juan
, p. 8748 - 8753 (2008)
It is generally accepted that good hydrogenation noble and nonnoble metal catalysts such as Pt, Ru, or Ni are not chemoselective for hydrogenation of nitro groups in substituted aromatic molecules. We have found that it is possible to transform nonchemoselective into highly chemoselective metal catalysts by controlling the coordination of metal surface atoms while introducing a cooperative effect between the metal and a properly selected support. Thus, highly chemoselective and general hydrogenation Pt, Ru, and Ni catalysts can be prepared by generating nanosized crystals of the metals on the surface of a TiO2 support and decorating the exposed (111) and (100) crystal faces by means of a simple catalyst activation procedure. By doing this, it has been possible to change the relative rate for hydrogenating competitive groups present in the molecule by almost 2 orders of magnitude, increasing the chemoselectivity from less than 1% to more than 95%.
Effects of divalent metal ions of hydrotalcites on catalytic behavior of supported gold nanocatalysts for chemoselective hydrogenation of 3-nitrostyrene
Tan, Yuan,Liu, Xiao Yan,Li, Lin,Kang, Leilei,Wang, Aiqin,Zhang, Tao
, p. 174 - 182 (2018)
The effect of the divalent metal ions on the hydrotalcite (HT) (MAl-HT; M = Mg, Zn, Ni)-supported thiolated Au25 nanoclusters (NCs) as the precatalysts for the chemoselective hydrogenation of 3-nitrostyrene to 3-vinylaniline was investigated. The highest chemoselectivity was obtained over the Au25/ZnAl-HT-300 (calcined at 300 °C) catalyst, with a maintained selectivity of desired product above 98%. The Au25/NiAl-HT-300 catalyst exhibited the highest activity, although the particle size of gold (3.2 nm) was greater than those of the Au25/MgAl-HT-300 (2.2 nm) and Au25/ZnAl-HT-300 (1.7 nm) catalysts. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) results of CO adsorption revealed that Ni interacting intimately with gold could be reduced easily, which affected the catalytic behavior of the Au25/NiAl-HT-300 catalyst. Furthermore, the results of the in situ DRIFTS of the adsorption of nitrostyrene at 10 bar of hydrogen suggested that, besides the condensation route, it also followed the direct route to produce aniline on Au25/NiAl-HT-300, which was different from the other two catalysts. This work provides new insight into the support effect over the gold catalysts for selective hydrogenation reactions.
Chemoselective Hydrogenation of Nitroaromatics at the Nanoscale Iron(III)–OH–Platinum Interface
Fu, Gang,Li, Laiyang,Ming, Jiang,Qin, Ruixuan,Ren, Juan,Wang, Yongke,Wang, Yu,Zhang, Wuyong,Zheng, Nanfeng,Zhou, Wenting
, p. 12736 - 12740 (2020)
Catalytic hydrogenation of nitroaromatics is an environment-benign strategy to produce industrially important aniline intermediates. Herein, we report that Fe(OH)x deposition on Pt nanocrystals to give Fe(OH)x/Pt, enables the selective hydrogenation of nitro groups into amino groups without hydrogenating other functional groups on the aromatic ring. The unique catalytic behavior is identified to be associated with the FeIII-OH-Pt interfaces. While H2 activation occurs on exposed Pt atoms to ensure the high activity, the high selectivity towards the production of substituted aniline originates from the FeIII-OH-Pt interfaces. In situ IR, X-ray photoelectron spectroscopy (XPS), and isotope effect studies reveal that the Fe3+/Fe2+ redox couple facilitates the hydrodeoxygenation of the -NO2 group during hydrogenation catalysis. Benefitting from FeIII-OH-Pt interfaces, the Fe(OH)x/Pt catalysts exhibit high catalytic performance towards a broad range of substituted nitroarenes.
Supported Au-Ni nano-alloy catalysts for the chemoselective hydrogenation of nitroarenes
Wei, Haisheng,Wei, Xing,Yang, Xiaofeng,Yin, Guangzhao,Wang, Aiqin,Liu, Xiaoyan,Huang, Yanqiang,Zhang, Tao
, p. 160 - 167 (2015)
A modified two-step approach was developed for the synthesis of uniform and highly dispersed Au-Ni alloy nanoparticles on a silica support. The supported Au-Ni alloy nanoparticles were investigated for the chemoselective hydrogenation of substituted nitro
Finely Controlled Platinum Nanoparticles over ZnO Nanorods for Selective Hydrogenation of 3-Nitrostyrene to 3-Vinylaniline
Gao, Tongtong,Liu, Zhong-Wen,Shi, Wen,Zhang, Bingsen,Zhang, Liyun,Zhang, Ying
, (2020)
Metallic platinum nanocatalysts play a key role in the liquid-phase selective hydrogenation of substrates with more than one unsaturated bond. However, the commonly applied explanation for the effects of different electronic and geometric properties of catalysts on reactions remains of a heuristic nature due to the difficulties involved in preparing catalysts with precise structure. In this work, we have directly loaded pre-synthesized metallic platinum nanoparticles onto well-structured ZnO nanorods and then subjected them to thermal treatment in a reductive atmosphere for different temperatures. The effects of the different electronic and geometric properties of the catalysts on the selective reduction of 3-nitrostyrene to 3-vinylaniline as a model reaction have been rigorously explored through an analysis of the catalyst structures and the activity and selectivity profiles. Both the electron transfer from zinc to platinum and the decreased platinum surface density as a result of the formation of PtZn intermetallic compounds are key factors for improving the selectivity for the desired 3-vinylaniline. Azobenzene was detected in the reaction with all the Pt/ZnO catalysts after 10–90 min, which indicates that the reaction follows a condensation mechanism.
Study of Catalyst Deactivation in Liquid-Phase Hydrogenation of 3-Nitrostyrene Over Au/Al2O3 Catalyst in Flow Reactor
Nuzhdin,Reshetnikov,Bukhtiyarova,Moroz,Gerasimov, E. Yu.,Pyrjaev,Bukhtiyarov
, p. 572 - 580 (2017)
Abstract: For the first time, we report the results of the study of dynamics of the Au/Al2O3catalyst deactivation during the selective liquid-phase 3-nitrostyrene (3-NS) hydrogenation in a fixed bed flow reactor. It is shown that the
Chemoselective hydrogenation of 3-nitrostyrene over Ag/TiO2-SiO2 catalyst in a flow reactor
Nuzhdin, Alexey L.,Bukhtiyarova, Galina A.,Lin, Tingting,Gerasimov, Evgeny Yu.,Bukhtiyarov, Valerii I.
, p. 553 - 555 (2019)
Hydrogenation of 3-nitrostyrene in a flow reactor over silver nanoparticles on TiO2-modified silica affords 3-vinylaniline with selectivity of 97% at the full conversion of the substrate.
Structure Evolution and Hydrogenation Performance of IrFe Bimetallic Nanomaterials
Lu, Ting,Lin, Jian,Liu, Xin,Wang, Xiaodong,Zhang, Tao
, p. 2771 - 2779 (2016)
By a reverse microemulsion method, a series of IrFe bimetallic nanomaterials of variable morphologies and compositions is synthesized and characterized by 57Fe M?ssbauer spectroscopy, XRD, XPS, and TEM. The structure evolution, such as IrFe alloy nanoparticles to Ir nanoparticles on Fe2O3 flakes, can be simply tuned by changing the molar ratio of Ir to Fe precursors. In terms of Fe, the relative content of IrFe alloy decreased with the increase of Fe species doped, while that of Fe2O3 flakes increased until reached 100%. The as-prepared IrFe bimetallic nanomaterials were served as catalysts for the selective hydrogenation of 3-nitrostyrene to 3-aminostyrene, and it is found that the catalytic performance was related to the morphology and composition of these nanomaterials. Ir1Fe4 was subsequently identified to be a highly active and exceedingly selective catalyst with good stability and recyclability for the hydrogenation of 3-nitrostyrene, underscoring a remarkable "synergistic effect" of the two metals appearing as the form of Ir nanoparticles loaded on Fe2O3 flakes. For Ir nanoparticles, they act as an active species for the hydrogenation; for Fe2O3 flakes, they favor the preferential adsorption of nitro groups, which account for the better chemoselectivity to objective product.
