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      Microwave-activated Ni/carbon catalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine

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          Abstract

          Biocarbon supported Ni catalysts have been prepared by facile impregnation of Ni species by microwave-heating and used for selective hydrogenation of nitrobenzene to cyclohexylamine. These catalysts were characterized by X-ray diffraction, Raman spectra, N2 sorption measurement, X-ray photoelectron spectroscopy, temperature programmed reduction of H2 and H2 temperature-programmed desorption. The morphology and particle size of catalysts were imaged by scanning electron microscope and transmission electron microscope. For the hydrogenation of nitrobenzene to cyclohexylamine, 10%Ni/CSC-II(b) exhibits the best catalytic activity to achieve 100 mol% conversion of nitrobenzene and 96.7% selectivity of cyclohexylamine under reaction conditions of 2.0 MPa H2 and 200 °C, ascribed to high dispersion of Ni species and formation of nanosized Ni particles on the support aided by microwave-heating. Thus-prepared Ni/CSC catalyst is greatly activated, in which the addition of precious metal like Rh is totally avoided.

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          XPS study of silver, nickel and bimetallic silver–nickel nanoparticles prepared by seed-mediated growth

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            A Molecular mechanism for the chemoselective hydrogenation of substituted nitroaromatics with nanoparticles of gold on TiO2 catalysts: a cooperative effect between gold and the support.

            Nanoparticles of gold on TiO2 are highly chemoselective for the reduction of substituted nitroaromatics, such as nitrostyrene. By combining kinetics and in situ IR spectroscopy, it has been found that there is a preferential adsorption of the reactant on the catalyst through the nitro group. IR studies of nitrobenzene, styrene, and nitrostyrene adsorption, together with quantum chemical calculations, show that the nitro and the olefinic groups adsorb weakly on the Au(111) and Au(001) surfaces, and that although a stronger adsorption occurs on low-coordinated atoms in gold nanoparticles, this adsorption is not selective. On the other hand, an energetically and geometrically favored adsorption through the nitro group occurs on the TiO2 support and in the interface between the gold nanoparticle and the TiO2 support. Such preferential adsorption is not observed with nanoparticles of gold on silica which, contrary to the Au/TiO2 catalyst, is not chemoselective for the reduction of substituted nitroaromatic compounds. Therefore, the high chemoselectiviy of the Au/TiO2 catalyst can be attributed to a cooperation between the gold nanoparticle and the support that preferentially activates the nitro group.
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              High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes.

              Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.9%. The superior catalytic performance can be attributed to a cooperative effect between the highly dispersed sub-nanometric Pd clusters for hydrogen activation and unique surface sites of PN-CeO2 with a high concentration of oxygen vacancy for an energetically and geometrically preferential adsorption of nitroarenes via nitro group. The high concentration of surface defects of PN-CeO2 and large Pd dispersion contribute to the enhanced catalytic activity for the hydrogenation reactions. The high chemoselectivity is mainly governed by the high Pd dispersion on the support. The catalysts also deliver high catalytic activity and selectivity for nitroaromatics with various reducible substituents into the corresponding aminoarenes.
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                Author and article information

                Contributors
                d.zhou@hubu.edu.cn
                xiaqh518@aliyun.com
                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group UK (London )
                2045-2322
                1 June 2017
                1 June 2017
                2017
                : 7
                : 2676
                Affiliations
                [1 ]ISNI 0000 0001 0727 9022, GRID grid.34418.3a, Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, , Hubei University, ; Wuhan, 430062 P. R. China
                [2 ]ISNI 0000 0001 0727 9022, GRID grid.34418.3a, Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, , School of Chemistry and Chemical Engineering, Hubei University, ; Wuhan, 430062 P. R. China
                Article
                2519
                10.1038/s41598-017-02519-0
                5453968
                e5ab2d4f-3e6b-4751-b727-2633cd428f71
                © The Author(s) 2017

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 14 February 2017
                : 11 April 2017
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