Inorganic and Materials Chemistry

Inorganic Materials Chemistry at Rice University is aimed at the synthesis of new nanomaterials, the investigation of the chemical reactivity of nanoparticles as a route to their application in materials systems and the development of applications of nanomaterials in macroscopic applications. Research in the group of Andrew Barron is aimed at the synthesis and chemical characterization of ceramic nanoparticles, in particular the investigation by surface NMR techniques as to the suitability and reactivity of surface bound ligands. Applications of these nanoparticles range from components in composite systems for medical, aerospace and automotive applications, their use as precursors for ceramic materials with controlled porosity and pore chemistry, and as components in MEMS fabrication.

To help prepare graduate students for careers in entrepreneurial organizations the Department of Chemistry, through Barron, offers in conjunction with the Jesse H. Jones Graduate School of Management an entrepreneurial management curriculum focusing on providing an introduction to entrepreneurship for technical students at Rice University. The program consists of two courses held sequentially within an academic year. The courses are team taught in modular format by management faculty, entrepreneurs, and entrepreneurial service providers.

Valery Khabashesku is using high temperature/high pressure techniques, solid state and solution phase synthesis and the reactions of elemental fluorine for the preparation/characterization of new materials. Currently, the properties of C₃N₄ solids (which can be graphitic or diamond-like) are being studied. The preliminary results suggest that it may be possible to prepare a "super-diamond" form of C₃N₄ at high pressures. The other materials under investigation include polyfullerenes, nanodiamond, and carbon nanotubes.

Fluorination of carbon nanotubes yields fluoronanotubes which are unique precursors for subsequent derivatization since the fluorine sites can react with RLi or Grignard reagents to form methyl, ethyl, ..., hexyl, undecyl-nanotubes, or terminal diamine, e. g., ethylenediamine, etc. to yield a variety of new nanotube derivatives. These are soluble in many organic solvents (THF, DMF, chloroform, etc.) and offer new opportunities for mechanical reinforcing polymer or metallic composite systems.

Understanding how main group elements and transition metals interact is of fundamental importance in inorganic chemistry and bears significantly upon the commercially important subjects of catalysis and materials science. For example, salts of main group elements are often added to transition metal catalysts and promoters or selectivity enhancers, and a number of transition metal/main group element alloys have interesting electrical and magnetic properties. Kenton Whitmire's research group is contributing to the understanding of these systems by examining discrete compounds where transition metal-main group bonding patterns can be well-defined and more readily studied.

In one area of research main group elements are observed to alter the conventional structure, bonding and reactivity patterns of transition carbonyl clusters. Interesting trends emerge when changes are made in the main group and/or transition metal composition of the clusters. Extensive efforts have been made to develop the systematic syntheses of these compounds and to examine their interaction with organic substrates. These complexes are also examined for their usefulness in performing catalytic transformations of organic molecules such as cabonylation, hydroformylation, hydrogenation, etc.

A second area of interest is metal alkoxide complexes. These compounds are important to the Sol-gel synthesis of important homo- and heterometallic metal oxide materials that find uses in electronic and magnetic materials such as the high temperature superconductors. Especially important and very challenging is the production of heterometallic alkoxides that have the appropriate metal stoichiometries for direct conversion into desirable materials. Of particular importance to this field is selective oxidation of key organic molecules, and production of high oxidation state main group and main group/transition metal complexes that might be useful in that regard is being investigated.