Insight into pH-Dependent Formation of Manganese Oxide Phases in Electrodeposited Catalytic Films Probed by Soft X-Ray Absorption Spectroscopy.

MnOx films electrodeposited under basic, neutral, and acidic conditions from an ionic liquid were investigated by means of X-ray absorption spectroscopy at the manganese L2,3 -edges and the oxygen K-edge. Such films can serve as catalysts for the water oxidation reaction. Previous studies showed that the catalytic activity could be controlled by varying the deposition parameters, which influence the formation of MnOx phases and the film composition. Herein the film compositions are investigated in detail, indicating different ratios of MnOx structural phases in the films. All films in the series predominately consist of varying proportions of three MnOx phases-Mn2 O3 , Mn3 O4 , and birnessite, while an increase of the average Mn oxidation state in the film is identified when going from basic to acidic conditions during electrodeposition. The contribution of these three phases shows a systematic dependency on the pH during electrodeposition. While no specific single MnOx phase was found to dominate the composition of samples that were previously found to show high catalytic activity, the X-ray spectroscopic results revealed the compositions of those samples prepared under close to neutral conditions to be most sensitive to changes in pH.

On the Origin of the Improvement of Electrodeposited MnOx Films in Water Oxidation Catalysis Induced by Heat Treatment.

Manganese oxides (MnOx ) are considered to be promising catalysts for water oxidation. Building on our previous studies showing that the catalytic activity of MnOx films electrodeposited from aqueous electrolytes is improved by a simple heat treatment, we have explored the origin of the catalytic enhancement at an electronic level by X-ray absorption spectroscopy (XAS). The Mn L-edge XA spectra measured at various heating stages were fitted by linear combinations of the spectra of the well-defined manganese oxides-MnO, Mn3 O4 , Mn2 O3 , MnO2 and birnessite. This analysis identified two major manganese oxides, Mn3 O4 and birnessite, that constitute 97 % of the MnOx films. Moreover, the catalytic improvement on heat treatment at 90 °C is related to the conversion of a small amount of birnessite to the Mn3 O4 phase, accompanied by an irreversible dehydration process. Further dehydration at higher temperature (120 °C), however, leads to a poorer catalytic performance.

Local energy gap opening induced by hemin dimerization in aqueous solution.

The local electronic structure of the hemin Fe center has been investigated by X-ray absorption and emission spectroscopy (XAS/XES) for hemin in aqueous solution where hemin dimerization occurs. The XAS and XES spectra of the hemin dimer were then compared with those of the hemin monomer we previously studied in dimethyl sulfoxide solution. A local energy gap opening at the Fe sites was observed for the hemin dimer, with the occupied valence states shifted to lower binding energies, while the unoccupied valence states share the same energies as the hemin monomer. Such a gap opening is argued to originate from the Fe 3d orbital localization induced by hemin dimerization in aqueous solution.

Enhancing catalytic activity by narrowing local energy gaps--X-ray studies of a manganese water oxidation catalyst.

Changes in the local electronic structure of the Mn 3d orbitals of a Mn catalyst derived from a dinuclear Mn(III) complex during the water oxidation cycle were investigated ex situ by X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) analyses. Detailed information about the Mn 3d orbitals, especially the local HOMO-LUMO gap on Mn sites revealed by RIXS analyses, indicated that the enhancement in catalytic activity (water oxidation) originated from the narrowing of the local HOMO-LUMO gap when electrical voltage and visible light illumination were applied simultaneously to the Mn catalytic system.