Journal
JOURNAL OF MATERIALS CHEMISTRY
Volume 19, Issue 33, Pages 6015-6022Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/b904250d
Keywords
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Funding
- Natural Sciences and Engineering Research Council (NSERC) of Canada
- Alberta Ingenuity
- University of Alberta
- NRC
- CIHR
- University of Saskatchewan
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Mixed-metal variants (Ni1-xM'(x))(2)P (M', Cr, Fe, Co; 0 <= x <= 1) of the binary phosphide Ni2P, a well-known hydrodesulfurization and hydrodenitrogenation catalyst, have been examined by X-ray photoelectron (XPS) and absorption (XANES) spectroscopy. The P 2p(3/2) binding energies and K-edge absorption energies in (Ni1-xCrx)(2)P, (Ni1-xFex)(2)P, and (Ni1-xCox)(2)P are lower than in Ni2P, with the shifts becoming more pronounced with greater difference in electronegativity between P and Ni/M'. These shifts are influenced primarily by intraatomic effects. However, secondary interatomic effects are also implicated in the Ni 2p(3/2) XPS spectra, which show enhanced satellite intensities, and in the Ni K- and L-edge absorption spectra, indicating a charge transfer from M' to the more electronegative Ni atoms. This phenomenon was confirmed in the metal L-edge XANES spectra, which revealed lower Ni and higher M' L-edge absorption energy as the degree of charge transfer increases. The Ni K-edge XANES spectra also show a pre-edge feature whose intensity decreases from Ni2P to (Ni0.8Cr0.2)(2)P, supporting the occurrence of charge transfer from Cr to Ni.
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