The solvent-free selective hydrogenation of nitrobenzene to aniline: an unexpected catalytic activity of ultrafine Pt nanoparticles deposited on carbon nanotubes

Sun, Zhenyu; Zhao, Yanfei; Xie, Yun; Tao, Ranting; Zhang, Hongye; Huang, Changliang; Liu, Zhimin

doi:10.1039/c002391d

Cited by 120 publications

(69 citation statements)

References 22 publications

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“…Gas phase nitrobenzene hydrogenation over Cu/SiO 2 generated aniline as sole product. Industrial aniline production via high pressure (2-50 atm) batch liquid-phase hydrogenation over supported Pd [27] or Pt [52] catalysts generates toxic by-products (phenylhydroxylamine (VI), azobenzene (VII), and azoxybenzene (VIII), see Fig. 1).…”

Section: Catalytic Responsementioning

confidence: 99%

‘‘Hydrogen-Free’’ Hydrogenation of Nitrobenzene Over Cu/SiO2 Via Coupling with 2-Butanol Dehydrogenation

Hao

Cárdenas‐Lizana

et al. 2014

Top Catal

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The feasibility of a coupled reaction system for the simultaneous production of 2-butanone (from 2-butanol dehydrogenation) and aniline (from nitrobenzene hydrogenation) over Cu/SiO 2 in continuous gas phase operation without an external H 2 supply has been established. Two (15.9 and 1.8 % w/w) Cu/SiO 2 catalysts were prepared by deposition-precipitation and characterised in terms of N 2 physisorption, temperature programmed reduction (TPR), H 2 chemisorption, powder XRD, STEM and XPS analysis. Following TPR, the higher Cu loading showed a wider particle size distribution (1-15 nm, mean 7.8 nm) than 1.8 % w/w Cu/SiO 2 (1-6 nm, mean 3.1 nm), where the latter exhibited a modified electronic character based on XPS measurements and a (fourfold) higher H 2 uptake capacity. The reactions showed antipathetic (dehydrogenation) and sympathetic (hydrogenation) structure sensitivity in terms of turnover frequency (TOF) dependence on Cu size. We have achieved, for the first time, 100 % yield to both target products (2-butanone and aniline) with appreciably (by a factor of 50) enhanced hydrogen utilisation in the coupled system relative to conventional nitrobenzene reduction using pressurised H 2 . Our results establish in situ hydrogen generation via catalytic dehydrogenation as a viable hydrogenation route to commercially important products.

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Section: Catalytic Responsementioning

confidence: 99%

‘‘Hydrogen-Free’’ Hydrogenation of Nitrobenzene Over Cu/SiO2 Via Coupling with 2-Butanol Dehydrogenation

Hao

Cárdenas‐Lizana

et al. 2014

Top Catal

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“…The common industrial method for aniline production is through catalytic hydrogenation of nitrobenzene [1,2]. In the process, carbon supported noble metal catalysts are widely used [2][3][4][5][6][7][8][9][10]. However, improvement of the catalyst is limited by some obstacles.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of mesoporous γ-Fe2O3 supported palladium nanoparticles and investigation of their roles as magnetically recyclable catalysts for nitrobenzene hydrogenation

Jiang

Jafari

et al. 2015

Applied Catalysis A: General

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a b s t r a c tThe mesoporous ␥-Fe 2 O 3 (maghemite) supported palladium catalysts (written as Pd/meso-␥-Fe 2 O 3 ) are synthesized using impregnation and one-step sol-gel methods and characterized by PXRD, BET, TEM, EDX, and XPS. The synthesized Pd/meso-␥-Fe 2 O 3 catalysts are applied in nitrobenzene hydrogenation reactions under 50 • C and 1 atm and their catalytic activities are compared with Pd/comm-Fe 2 O 3 , Pd/meso-SiO 2 , and Pd/meso-C catalysts, in order to study the effect of the catalyst support. The TOF number of a 1% Pd/meso-␥-Fe 2 O 3 -im catalyst is highest among all the synthesized catalysts, attributed to the well dispersed Pd nanoparticles on the iron oxide support of large surface area, large pore size, and an interconnected network. All the mesoporous ␥-Fe 2 O 3 nanoparticle catalysts show characteristics of superparamagnetic behavior and thus can be easily retrieved by an external magnetic field. Significant catalyst activity decay is observed with 1% Pd/meso-␥-Fe 2 O 3 -im catalyst due to Pd leaching. However, improvement in activity of the recycled catalyst is observed when the one-step sol-gel synthesis method is used.

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“…Liu and co-workers [19] prepared Pt NPs supported on multiwall carbon nanotubes (MWCNTs), which exhibited excellent activity for the solvent-free hydrogenation of NB to AN at a pressure of 2.0 MPa. Nie et al [20] used Pt/reduced graphene oxide (rGO) nanocomposites as the catalysts for the hydrogenation of nitroarenes, which showed higher catalytic activity than Pt/CNTs at 1.0 MPa.…”

Section: Introductionmentioning

confidence: 99%

In situ thermolysis of Pt-carbonyl complex to form supported clean Pt nanoclusters with enhanced catalytic performance

Wei

Zhao

et al. 2017

Sci. China Mater.

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at 25°C and 1 atm. This number is higher than the previously reported value for the heterogeneously catalyzed hydrogenation of nitrobenzene. The proposed process follows a direct hydrogenation mechanism, as is revealed by the analyses of the intermediate products. This work presents a facile and effective synthetic approach for achieving highly efficient nanocatalysts, and can be extended to obtain other metal catalysts with ultra-small sizes and excellent performance.

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The solvent-free selective hydrogenation of nitrobenzene to aniline: an unexpected catalytic activity of ultrafine Pt nanoparticles deposited on carbon nanotubes

Cited by 120 publications

References 22 publications

‘‘Hydrogen-Free’’ Hydrogenation of Nitrobenzene Over Cu/SiO2 Via Coupling with 2-Butanol Dehydrogenation

‘‘Hydrogen-Free’’ Hydrogenation of Nitrobenzene Over Cu/SiO2 Via Coupling with 2-Butanol Dehydrogenation

Synthesis of mesoporous γ-Fe2O3 supported palladium nanoparticles and investigation of their roles as magnetically recyclable catalysts for nitrobenzene hydrogenation

In situ thermolysis of Pt-carbonyl complex to form supported clean Pt nanoclusters with enhanced catalytic performance

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