Grant: Discovery Grants Program - Individual

The ultimate goal of this research is to initiate sustainable free radical and radiation-induced processes to develop novel materials with potential applications in technology. The different stages of this research are: 1) microscopic studies with particle-accelerator-based and computational methods; 2) ?wet lab? work at Mt. Allison, optimized using our microscopic understanding gained by spectroscopic and theoretical analysis from 1; 3) characterization of the products of the wet lab syntheses with a variety of physical methods, including particle-accelerator based methods if need be (e.g. studies of magnetic or electronic structure properties of the material). This cycle calls for multifaceted research that will be performed with following foci: 1) free radical and radiation chemistry in green solvents; 2) using sustainable feedstock or waste products of industries or nature to develop value-added materials by free radical and radiation chemistry; and 3) studying the energy efficiency of such processes with or without external fields. We will minimize the impact of our free radical methods on the environment by finding the most energy-efficient, environmentally friendly solvents. We will experiment with the effects of temperature, pressure, and external fields (such as lasers or microwave (MW)) on free radical reactions to find the most efficient methodology, and to understand the effects of such external fields on the mechanism of free radical reactions. The novel materials that we plan to make will be: 1) material from free radical reactions in protic ionic liquids dissolved CO2 We have expertise in ionic liquids (ILs), supercritical CO2, high temperature chemistry and reactive free radicals. Therefore a natural extension of our previous studies is to dissolve CO2 in thermally stable ILs then perform free radical reactions on the system. We will focus on modifying our recently synthesized thermally stable protic ILs, but with modified anions (anions with fluorine substitutions have good miscibility with CO2) to polarize CO2, use high temperatures, and free radical precursors to transform CO2 by free radical reactions to commodity chemicals. These may have potential applications in batteries, fuel cells, components of monomers for ionic polymers for batteries or fuel cells or other applications. 2) Novel nanocomposites based on free radical reactions on the surface of metal or metal oxide nanoparticles. We hope to understand these systems, since free radicals are intermediates in many catalytic processes and for making polymer nanocomposites. The benefits of these studies will include understanding how to: control or generate new structures on the surface of nanoparticles, tune the electronic and magnetic properties on the surface of nanoparticles, and evaluate the effects of nanoparticles on radiation chemistry. 3) Novel materials based on free radical reactions with enol forms of acids from either biomass or waste products. We will do free radical reactions (e.g. bromination and polymerization) on enol type forms of material in biomass or intermediates in the process of biomass conversion to fuel. The impacts of our studies are the following: 1) The in situ studies of the effects of MW on free radical reactions have never been done before and we will open the field by our studies. This will help to solve the controversies regarding non thermal effects of MW. 2) Opening the field of in situ free radical transformation of enols in equilibrium with ketones to transform acids (or any compound with C=O or C=N group) from biomass to valuable material. 3) For the first time probing the electronic structures and reactivity of reactive free radicals on the surface of nanoparticles.