Abstract
The catalytic continuous gas phase hydrogenation of p-chloronitrobenzene (P=1 atm;T=423 K) has been investigated over a series of oxide (Al2O3, TiO2, Fe2O3 and CeO2) supported Au (1 mol %) catalysts. The application of two catalyst synthesis routes,i.e. impregnation (IMP) and deposition-precipitation (DP), has been considered where the DP route generated smaller mean Au particle sizes (1.5-2.8 nm) compared with the IMP preparation (3.5-9.0 nm). The catalysts have been characterised in terms H2 chemisorption and BET area measurements where the formation of metallic Au post-activation has been verified by diffuse reflectance UV-Vis, XRD and HRTEM analyses.p-Chloroaniline was generated as the sole reaction product over all the Au catalysts with no evidence of C-Cl and/or C-NO2 bond scission and/or aromatic ring reduction. The specific hydrogenation rate increased with decreasing Au particle size (from 9 to 3 nm), regardless of the nature of the support. This response extends to a reference Au/TiO2 catalyst provided by the World Gold Council. A decrease in specific rate is in evidence for smaller particles (< 2 nm) and can be attributed to a quantum size effect. The results presented establish the basis for the design and development of a versatile catalytic system for the clean continuous production of high value amino compounds under mild reaction conditions.
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Mark A. Keane is Professor of Chemical Engineering at Heriot-Watt University. Previously, he was Professor of Chemical & Materials Engineering, University of Kentucky (2000–2005) and Senior Lecturer in Chemical Engineering, University of Leeds (1995–2000). He is the author of over 130 papers dealing with selective hydrogenation/ hydrogenolysis, kinetic modeling, catalytic growth of structured carbon and synthesis/characterization of new generation catalysts, e.g. carbides/ nitrides and lanthanide/transition metal systems applied to clean synthesis and environmental catalysis. The development of gold catalysts falls into the latter research activity.
Fernando Cárdenas-Lizana is currently a PhD student in the Chemical Engineering Department at Heriot-Watt University. His research activities are focused on the preparation, characterization and application of supported gold-based catalysts in the continuous gas phase catalytic hydrogenation of nitroarenes as a viable, clean high throughput route to commercially important aromatic amines. He graduated as a Chemical Engineer from the University of Granada (Spain) in 2000 and obtained his MSc in “Sustainable Process Management” from Heriot-Watt University (2004).
Santiago Gómez-Quero is currently a PhD student at Heriot-Watt University. His PhD thesis deals with the catalytic hydrotreament of toxic halogenated phenols, studying fundamental aspects with applications in raw material recycle. He graduated as a Chemical Engineer from Castilla-La Mancha University (Spain) in 2005 and has a strong interest in environmental engineering, where heterogeneous catalysis has proved to be an effective tool.
Noémie Perret is currently a student at the Engineering School of Electrochemistry at Grenoble (ENSEEGINPG). Her final dissertation research project was on oxide supported gold catalysts for selective nitro-group reduction. She will shortly begin her PhD studies in Chemical Engineering at Heriot-Watt University.
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Cárdenas-Lizana, F., Gómez-Quero, S., Perret, N. et al. Support effects in the selective gas phase hydrogenation ofp-chloronitrobenzene over gold. Gold Bull 42, 124–132 (2009). https://doi.org/10.1007/BF03214922
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DOI: https://doi.org/10.1007/BF03214922