DFT-D3 study of molecular N2 and H2 activation on Co3Mo3N surfaces

Zeinalipour-Yazdi, C. D., Hargreaves, J. S.J. and Catlow, C. R. A. (2016) DFT-D3 study of molecular N2 and H2 activation on Co3Mo3N surfaces. Journal of Physical Chemistry C, 120(38), pp. 21390-21398. (doi: 10.1021/acs.jpcc.6b04748)

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Cobalt molybdenum nitride (Co3Mo3N) is one of the most active catalysts for ammonia synthesis, although the atomistic details of the reaction mechanism are currently unknown. We present a dispersion-corrected (D3) DFT study of the adsorption and activation of molecular nitrogen and hydrogen on Co3Mo3N-(111) surfaces to identify possible activation sites for ammonia synthesis. H2 was found to adsorb both molecularly on the Mo3N framework and dissociatively on Co8 clusters or Mo3 clusters that were exposed due to N-vacancies. We find that there are two possible activation sites for N2 where both N2 and H2 can coadsorb. The first is a Mo3 triangular cluster that resides at 3f nitrogen vacancies, and the second is a surface cavity where N2 is activated by a Co8 cluster, the second being a more efficient activation site. N2 was found to adsorb in three adsorption configurations: side-on, end-on, and an unusual tilt end-on (155°) configuration, and the existence of these three adsorption configurations is explained via MP2 calculations and the sphere-in-contact model.

Item Type:Articles
Additional Information:The authors acknowledge EPSRC funding (EP/L026317/1, EP/L02537X/1). Via our membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202/1).
Glasgow Author(s) Enlighten ID:Hargreaves, Professor Justin
Authors: Zeinalipour-Yazdi, C. D., Hargreaves, J. S.J., and Catlow, C. R. A.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:Journal of Physical Chemistry C
Publisher:American Chemical Society
ISSN (Online):1932-7455
Published Online:24 August 2016
Copyright Holders:Copyright © 2016 American Chemical Society
First Published:First published in Journal of Physical Chemistry C 120(38): 21390-21398
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
652781First principles design of novel ammonia synthesis catalystsJustin HargreavesEngineering & Physical Sciences Research Council (EPSRC)EP/L02537X/1CHEM - CHEMISTRY