caa a22 4500 606174001 CHVBK 20210128100736.0 cr unu---uuuuu 210128e20150301xx s 000 0 eng 10.1007/s11244-014-0354-9 doi (NATIONALLICENCE)springer-10.1007/s11244-014-0354-9 ‘‘Hydrogen-Free'' Hydrogenation of Nitrobenzene Over Cu/SiO2 Via Coupling with 2-Butanol Dehydrogenation [Elektronische Daten] [Maoshuai Li, Yufen Hao, Fernando Cárdenas-Lizana, Humphrey Yiu, Mark Keane] 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/SiO2 in continuous gas phase operation without an external H2 supply has been established. Two (15.9 and 1.8% w/w) Cu/SiO2 catalysts were prepared by deposition-precipitation and characterised in terms of N2 physisorption, temperature programmed reduction (TPR), H2 chemisorption, powder XRD, STEM and XPS analysis. Following TPR, the higher Cu loading showed a wider particle size distribution (1-15nm, mean 7.8nm) than 1.8% w/w Cu/SiO2 (1-6nm, mean 3.1nm), where the latter exhibited a modified electronic character based on XPS measurements and a (fourfold) higher H2 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 H2. Our results establish in situ hydrogen generation via catalytic dehydrogenation as a viable hydrogenation route to commercially important products. Springer Science+Business Media New York, 2014 2-Butanol nationallicence 2-Butanone nationallicence Nitrobenzene nationallicence Aniline nationallicence Dehydrogenation-hydrogenation coupling nationallicence Cu/SiO2 nationallicence Li Maoshuai Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut Hao Yufen Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut Cárdenas-Lizana Fernando Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut Yiu Humphrey Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut Keane Mark Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut Topics in Catalysis Springer US; http://www.springer-ny.com 58/2-3(2015-03-01), 149-158 1022-5528 58:2-3<149 2015 58 11244 https://doi.org/10.1007/s11244-014-0354-9 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s11244-014-0354-9 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Li Maoshuai Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut NATIONALLICENCE 700 1- Hao Yufen Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut NATIONALLICENCE 700 1- Cárdenas-Lizana Fernando Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut NATIONALLICENCE 700 1- Yiu Humphrey Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut NATIONALLICENCE 700 1- Keane Mark Chemical Engineering, School of Engineering and Physical Sciences, Heriot-Watt University, EH14 4AS, Edinburgh, Scotland, UK aut NATIONALLICENCE 773 0- Topics in Catalysis Springer US; http://www.springer-ny.com 58/2-3(2015-03-01), 149-158 1022-5528 58:2-3<149 2015 58 11244