This Is AuburnElectronic Theses and Dissertations

Redox Reactions in Polymeric Systems




Black, James

Type of Degree



Chemistry and Biochemistry


Reduction-Oxidization (redox) reactions performed in polymeric environments resulted in the reversible formation of stable silver nanoparticle and two reductive radicals. The reversible formation of stable silver nanoparticles in polyvinyl alcohol (PVA) and polyacrylic acid (PAA) crosslinked polymer films containing silver ions was achieved by electrochemical methods for potential applications in electrochromic devices. Cyclic voltammetry and galvanostatic methods were used to reversibly generate silver particles while the particle formation and decay optical absorption spectra were used to evaluate reversibility, relative particle size and minimum cycle speeds. Mechanisms for the formation and decay of particles are discussed with electron microscopy data determining actual size of generated silver particles. Light activated polymeric radicals produced from sulfonated polyether ether ketone (SPEEK) with PVA or SPEEK with sodium formate solutions were generated using 350 nm photons. The mechanism of radical generation is discussed for potential application for dehalogenating a well known environmental hazard carbon tetrachloride (CCl4). The reaction of the generated radicals with CCl4 was followed by ion selective electrode specific for chlorine allowing for the attainment of kinetic data and reaction mechanisms. The degradation of CCl4 was observed in both SPEEK/PVA and SPEEK/formate solutions but the kinetic data revealed SPEEK/formate to be more efficient. The success of SPEEK radicals in dechlorinating CCl4 lead to the investigation of polymeric blends, films and solution of SPEEK and polyamines for the generation of SPEEK radicals with a higher redox potential. SPEEK/polyamine radicals were generated by exposing polymer blends to 350 nm photons. Optical and electron spin resonance (ESR) spectra confirmed the generation of the anionic radical with a higher reducing potential. Kinetic data was obtained for selected system by following the formation and decay of the optical and ESR signatures. The reactions leading to the generation of highly reductive radicals is discussed.