Chain Reduction of CHCl(3) Photocatalyzed by SPEEK/PVA Films Swollen in Air-Saturated HCO(2)Na Solutions

Thin cross-linked films containing sulfonated poly(ether etherketone), SPEEK, and poly(vinyl alcohol), PVA, served as efficient photocatalysts for the reduction of CHCl(3) when swollen in air-saturated solutions of formate buffers were photolyzed with 350 nm photons. The phototransformation generated CH(2)Cl(2), CO(2) and Cl(−) as products. The utilization of the continuous extraction method coupled with in situ potentiometry enabled kinetic determinations of the reaction progress. Quantum yields of halide ion formation, ϕ(Cl(−)), larger than 1 were obtained in the presence of air. These findings, together with the occurrence of a post-irradiation Cl(−) formation, indicated that the photoreduction took place via a chain process. Reductions photoinitiated by swollen films exhibited ϕ(Cl(−)) values between 3 and 20 times higher than the reactions induced in solutions containing the two polymers. Also, the dependencies of ϕ(Cl(−)) on CHCl(3) or HCO(2)(−) concentration diverged significantly from the trends observed using solutions. Most findings are consistent with the occurrence of a reaction mechanism involving SPEEK radicals, •CO(2)(−) and •CHCl(2) as chain carriers.