XPS spectra of uranyl minerals and synthetic uranyl compounds. II: The O 1s spectrum |
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Authors: | M Schindler FC Hawthorne PC Burns |
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Institution: | a Department of Geological Sciences, University of Manitoba, Winnipeg, Man., Canada R3T2N2 b Department of Chemistry, University of Manitoba, Winnipeg, Man., Canada R3T2N2 c Department of Civil Engineering and Geological Sciences, University of Notre Dame, IN 46556-0767, USA |
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Abstract: | The O 1s spectrum is examined for 19 uranyl minerals of different composition and structure. Spectra from single crystals were measured with a Kratos Axis Ultra X-ray Photoelectron Spectrometer with a magnetic-confinement charge-compensation system. Well-resolved spectra with distinct maxima, shoulders and inflections points, in combination with reported and measured binding energies for specific O2− species and structural data of the uranyl minerals are used to resolve the fine structure of the O 1s envelope. The resolution of the O 1s spectra includes, for the first time, different O2− bands, which are assigned to O atoms linking uranyl with uranyl polyhedra (UOU) and O atoms of uranyl groups (OUO). The resolved bands in the O 1s spectrum occur at distinct ranges in binding energy: bands for (UOU) occur at 529.6-530.4 eV, bands for (OUO) occur at 530.6-531.4 eV, bands for O2− in the equatorial plane of the uranyl polyhedra linking uranyl polyhedra with (TOn) groups (T = Si, S, C, P, Se) (TO) occur at 530.9-532.2 eV; bands for (OH) groups in the equatorial plane of the uranyl polyhedra (OH) occur at 532.0-532.5 eV, bands of (H2O) groups in the interstitial complex of the uranyl minerals (H2Ointerst) occur at 533.0-533.8 eV and bands of physisorbed (H2O) groups on the surface of uranyl minerals (H2Oadsorb) occur at 534.8-535.2 eV. Treatment of uranyl minerals with acidic solutions results in a decrease in UOU and an increase in OH. Differences in the ratio of OH : OUO between the surface and bulk structure is larger for uranyl minerals with a high number of UOU and TO species in the bulk structure which is explained by protonation of underbonded UO, UOU and TO terminations on the surface. The difference in the ratio of H2Ointerst : OUO between the bulk and surface structures is larger for uranyl minerals with higher percentages of H2Ointerst as well as, with a higher number of interstitial H2O groups that are not bonded to interstitial cations, resulting in easier dehydration of interstitial H2O groups in uranyl minerals during exposure to a vacuum. |
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