Precursor Routes to Inorganic Materials

Traditionally solid-state synthetic methods use high temperatures to facilitate chemical reaction between relatively stable and inert solid-state starting materials. These are very successful in many commercial materials growth processes, but are often limited to the production of thermodynamic phases with long-range structural order and crystallinity in the multimicrometer range. Lower temperature strategies (chimie douce - "soft chemistry") for materials synthesis using reactive or tailored precursors have been under extensive development for the past several decades. These approaches can provide access to inorganic and organic extended materials with unprecedented manipulation of a materials size, composition, and structure at atomic and nanoscale levels. The Gillan group is pursuing several synthetic materials chemistry research projects that involve precursor-based synthetic approaches to technologically interesting inorganic and organic materials, particularly main-group and transition-metals combined with Group 13 (B), Group 15 (N, P), and Group 16 (O, S) elements.

Broad goals are to develop facile reactive precursor decomposition strategies that produce new materials with kinetically stabilized porous structures having useful and functional physical properties, that crystallize in metastable chemical compositions or structures that exhibit tunable optical, magnetic or catalytic properties, and may provide access to unusual morphologies such as nanoscale geometries (particles, rods) or thin coatings on macroporous supports.

Potential technological utility (applied/practical) for our precursor-synthesized inorganic and organic materials are in areas related to alternative energy materials such as catalysts (electro and/or photo) and cooperative catalyst supports and photovoltaic light absorbing materials. Other potential applications relate to hard structural materials from biomorphous architectures, and new magnetic and magneto-optical structures for data storage. In addition to synthesis and physical/structural characterization of systems listed below, we are actively studying several of these systems in photochemical and electrochemical contexts (collaboration with Professor Leddy - UI Chemistry) and are interested in using computationally derived surface adsorption energies to help better understand observed differences in the catalytic activity of non-metal rich surface structures.

Ongoing Projects

  1. Thermochemically Driven Metal Phosphide and Phosphide-Sulfide Growth from Elemental Phosphorus (solid-state and solution strategies).
  2. Rapid and Exothermic Solid-State Metathesis Reactions Targeting Tunable Formation of Crystalline Metal Borides, Solid-Solutions, and Composites
  3. Reactive Triazine and Heptazine Molecular Precursor Routes to Extended Carbon Nitride Network Structures (including those with engineered macroporosity and with photodeposited noble metals)

Other Recent Projects

  1. Solvothermal Metal Azide Decomposition Chemistry for Metastable Metal Nitride Microparticle and Nanoparticle Growth in Superheated Organic Solvents (e.g., toluene, THF, hexadecane).
  2. Rapid Solid State Metathesis (SSM) Routes to Crystalline and Doped TiO2 and ZrO2 for Photocatalytic and Structural Applications.
  3. SSM Routes to MOCl Materials (M = Bi, La, Gd) and Non-Aqueus Solution Metathesis Route to TiO2 Nanoparticles.
  4. Chemically Dehydrated Botanical Structures as Templates for Biomorphous Metal Oxide and Non-Oxide Porous Structures.
  5. Mechanochemically Induced Solid-State Metathesis Reactions Enabling Growth of Crystalline ZSM-5 Zeolites Without Solvents or Templating Agents