XPS determination of Mn oxidation states in Mn (hydr)oxides

Journal Article · Tue Mar 01 04:00:00 EST 2016 · Applied Surface Science

DOI:https://doi.org/10.1016/j.apsusc.2015.12.159· OSTI ID:1254570

Ilton, Eugene S.; Post, Jeffrey E.; Heaney, Peter J.; Ling, Florence T.; Kerisit, Sebastien N.

Hydrous manganese oxides are an important class of minerals that help regulate the geochemical redox cycle in near-surface environments and are also considered to be promising catalysts for energy applications such as the oxidation of water. A complete characterization of these minerals is required to better understand their catalytic activity. In this contribution an empirical methodology using X-ray photoelectron spectroscopy (XPS) is developed to quantify the oxidation state of hydrous multivalent manganese oxides with an emphasis on birnessite, a common layered structure that occurs readily in Nature but is also the oxidized endmember in biomimetic water-oxidation catalysts. The Mn2p3/2, Mn3p, and Mn3s lines of near monovalent Mn(II), Mn(III), and Mn(IV) oxides were fit with component peaks; after the best fit was obtained the relative widths, heights and binding energies of the components were fixed. Unknown multivalent samples were fit such that binding energies, intensities, and widths of each oxidation state, composed of a packet of correlated component peaks, were allowed vary. whereas widths were constrained to maintain the difference between the standards. Both average and individual mole fraction oxidation states for all three energy levels were strongly correlated with close agreement between Mn3s and Mn3p, whereas Mn2p3/2 gave systematically more reduced results. Limited stoichiometric analyses were consistent with Mn3p and Mn3s. Further, evidence indicates the shape of the Mn3p line was less sensitive to the bonding environment than Mn2p. Consequently, fitting the Mn3p and Mn3s lines yields robust quantification of oxidation states over a range of hydrous Mn oxide polytypes and compositions. In contrast, a common method for determining oxidation states that utilizes the multiplet splitting of the Mn3s line is not appropriate for birnessites.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1254570
• Report Number(s): PNNL-SA-113206; 47509; 48389; KC0302060
• Journal Information: Applied Surface Science, Journal Name: Applied Surface Science Vol. 366; ISSN 0169-4332
• Publisher: Elsevier
• Country of Publication: United States
• Language: English

Related Subjects

Environmental Molecular Sciences Laboratory
Manganese
birnessite
oxidation state
XPS
methodology