Direct Transformation of Metal Oxides into Metal-Organic Materials Using Mechanochemical Milling and "Accelerated Aging" Techniques

"One of the principal goals of modern industry is to minimize the environmental impact and increase the materials- and energy-efficiency of transforming raw materials into valuable products. This paper will highlight our latest laboratory-scale research in low-energy, low-solvent reactivity of metal oxides and their conversion into popular metal-organic frameworks (MOFs), zeolitic imidazolate frameworks (e.g. Basolite® Z1200 component ZIF-8), and metallodrugs (e.g. bismuth subsalicylate, active component of Pepto-Bismol®). Mechanochemical ion- and liquid-assisted grinding (ILAG) and ""accelerated aging"" techniques will be presented, along with novel low-energy and solvent-free approaches, inspired by geological weathering processes, for converting metal oxides into metal-organic materials. INTRODUCTIONThe development of environmentally-friendly processes, which would in the same time be more materials- and energy-efficient than the existing ones, is one of the central concerns of modern chemical research. In that sense, the focus of the chemist has been mainly on the preparation of carbon-based organic molecules and adaptation of traditional organic synthesis to the recently delineated ideals of Green Chemistry. However, there is a growing realization within the chemistry community that significant energy, materials, and ecology-related benefits can be achieved and, indeed, targeted in the transformations of materials that are typically associated with inorganic chemistry and minerals processing. The principal aim of this highlight contribution is to illustrate how, through the use of approaches associated with solventfree chemistry and mechanochemistry (James et al., 2012), one can develop a clean and efficient system of chemical and materials transformations involving oxide precursors that normally belong to the realm of inorganic chemistry and mineral processing. In particular, this contribution will provide an overview of the recently developed mechanochemical and solvent-free reactivity of metal oxides towards small organic molecules. These mechanochemical reactions, including the methods of liquid-assisted grinding (LAG, Frišcic & Jones, 2009) and ion- and liquid-assisted grinding (ILAG, Frišcic, 2010), have so far provided a radically different means to construct advanced metal-organic materials (e.g. porous metal-organic frameworks, [MOFs] or metallodrugs) by rehabilitating metal oxides as precursors, eliminating the use of bulk organic solvents, and avoiding the use of high temperatures."