Details of Grant 

EPSRC Reference:	GR/S87300/01
Title:	Fundamental studies as a route towards greener nitrogen insertion chemistry
Principal Investigator:	Hargreaves, Professor JSJ
Other Investigators:
Researcher Co-Investigators:
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Department:	School of Chemistry
Organisation:	University of Glasgow
Scheme:	Standard Research (Pre-FEC)
Starts:	01 October 2004	Ends:	30 September 2007	Value (£):	89,945
EPSRC Research Topic Classifications:	Catalysis & Applied Catalysis Materials Characterisation
EPSRC Industrial Sector Classifications:	Manufacturing Chemicals
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Summary on Grant Application Form
in this study, we will probe the ability of nitrides and oxynitrides to act as catalysts for the activation of nitrogen and its incorporation into organic molecules. Nitrides and oxynitrides have been chosen as candidate catalysts because they contain activated nitrogen in their structures. This nitrogen may be able to function as a reactant in its own right, leaving lattice vacancies which can subsequently be replenished by gas phase N2, thereby completing the catalytic cycle. Alternatively, they may demonstrate the ability to form reactive surface nitrogen species directly from the gasphase. Both of these possibilities have analogies in oxidation catalysis catalysed by oxides. Although it is true that nitrogen is generally a relatively inert molecule, some of the catalysts to be tested here are known to activate nitrogen under the conditions to be employed - for example, one class of material to be studied has been demonstrated to cleave N2 to form a surface nitride at room temperature and ambient pressure and another class, the ternary nitrides, display relatively high ammonia synthesis activity at ambient pressure and temperatures <500C. The mode of nitrogen activation will be probed by using isotopic exchange measurements wherein it will be possible to distinguish and quantify the activity of lattice nitrogen and adsorbed nitrogen species. These studies will also be undertaken to assess the parameters of importance for reactivity, which will be used to further develop more active catalysts. Studies of the stability/lifetime of performance will also be undertaken as these will be significant in terms of the application of any catalyst for direct nitrogen activation and incorporation. Nitrogen isotopic studies are uesful probes since nitrogen activation is expected to be the rate limiting step in these types of reaction .Catalysts will then be applied to a model target nitrogen insertion reaction - the direct amination of benzene to form aniline. This is currently practised on an industrial scale using a series of reactions which involve sequentially hydrogenating nitrogen, oxidising the resultant ammonia to form nitric acid, which is then added to concentrated sulfuric acid and used to nitrate benzene, with the nitro group of the resultant nitrobenzene then being selectively re-reduced to form an amime group. This process is therefore inefficient in nitrogen and energy utilisation. Direct aproaches to aniline formation by reaction with ammonia have been limited by the need to remove the co-product hydrogen and this has limited catalyst stability. We will adopt a novel approach to this reaction. In our model target reaction, we will attempt the direct addition of activated nitrogen to benzene with co-feeding hydrogen as a reactant, rather than having to remove it as a product.
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