Porous manganese oxide octahedral molecular sieves and octahedral layered materials.

This Account first gives a historical overview of the development of octahedral molecular sieve (OMS) and octahedral layer (OL) materials based on porous mixed-valent manganese oxides. Unique properties of such systems include excellent semiconductivity and porosity. Materials that are conducting and porous are rare and can offer novel properties not normally available with most molecular sieve materials. The good semiconductivity of OMS and OL systems not only permits potential applications of the conductivity of these materials but also allows characterization of these systems where charging effects are often a problem. Porous manganese oxide natural materials are found as manganese nodules, and these materials when dredged from the ocean floors have been used as excellent adsorbents of metals such as from electroplating wastes and have been shown to be excellent catalysts. Rational for synthesis of novel OMS and OL materials is related to the superb conductivity, microporosity, and catalytic activity of these natural materials. The natural systems are often found as mixtures, are poorly crystalline, and have incredibly diverse compositions due to exposure to various aqueous environments in nature. Such exposure allows ion exchange to occur. Preparation of pure crystalline OL and OMS systems is one of the very significant goals of this work. The status of this research area is one of moderate development. Opportunities exist for preparation of a multitude of novel materials. Some applications of these materials have recently been achieved primarily in the area of catalysis and membranes, and others such as sensors and adsorptive systems are likely. Characterization studies are becoming more sophisticated as new materials and proper preparation of materials for such characterization studies are being done. The research area involved in this work is solid state chemistry. The fields of materials synthesis, characterization, and applications of materials are all important in developments of this field. Researchers in chemistry, chemical engineering, materials science, physics, and biological sciences are actively pursuing research in this area. The most significant results found in this work are related to the novel structural and physical properties of porous manganese oxide materials. Variable pore size materials have been synthesized using structure directors and with a variety of synthetic methodologies. Transformations of tunnel materials with temperature and in specific atmosphere have recently been studied with in situ synchrotron methods. Conductivities of these materials appear to be related to the structural properties of these systems with more open structures being less conductive. Catalytic properties of these OMS and OL materials have been shown to be related to the redox cycling of various oxidations states of manganese such as Mn2+, Mn3+, and Mn4+. Chemists interested in synthesis of new materials, the chemistry of solids, enhancing the rates of catalytic reactions, and finding new applications of materials would be interested in these novel materials. Fundamental properties of electron transfer are critical to this research. Concepts of nonstoichiometry, defects, oxygen vacancies, and intermediates are fundamental to many of the syntheses, characterization, and applications such as fuel cells, catalysis, adsorption, sensors, batteries, and related applications.