Synthesis and characterization of a new family of electroactive alkali metal doped mesoporous Nb, Ta, and Ti oxides and evidence for an Anderson transition in reduced mesoporous titanium oxide

Recently we reported that mesoporous niobium oxide can be chemically reduced by Na-naphthalene while fully retaining its mesostructure. This was the first report of a molecular sieve acting as a stoichiometric electron acceptor. Herein we expand on the initial work by presenting a detailed study on Li-, Na-, K-, Rb-, and Cs-reduced samples of mesoporous Nb oxide, as well as Li-reduced mesoporous Ta and Ti oxides. While the Nb- and Ta-based materials fully retained their structure on reduction as determined by X-ray diffraction (XRD) and nitrogen adsorption, the Li-reduced Ti material retained high surface area and narrow pore size distribution, but lost its diffraction pattern, indicating an increased level of disorder in this material. X-ray photoelectron spectroscopy (XPS) and UV-visible reflectance spectroscopy revealed that all reduced mesoporous oxides studied have a similar electronic structure, corresponding to the presence of a disordered impurity band in the material lying between the valence band and the conduction band. Electron paramagnetic resonance (EPR) studies suggest that the electron in this impurity level is unpaired and best described as a free electron, only loosely bound to the alkali or transition metal. SQUID magnetometry showed that all reduced materials are paramagnetic, further confirming the presence of unpaired electrons in the structure. All materials in this study were insulating with the exception of the Li-reduced mesoporous Ti material, which was highly conducting, possibly due to an Anderson transition. Electrochemical studies on the unreduced mesoporous oxides demonstrated that while the Ta and Nb materials are capacitors with only a small degree of reversible electrochemical behavior in the bulk sample, the Ti material was an electrical conductor with fully reversible redox behavior.