Role of Electronegativity in Environmentally Persistent Free Radicals (EPFRs) Formation on ZnO.

Environmentally persistent free radicals (EPFRs), a group of emerging pollutants, have significantly longer lifetimes than typical free radicals. EPFRs form by the adsorption of organic precursors on a transition metal oxide (TMO) surface involving electron charge transfer between the organic and TMO. In this paper, dihalogenated benzenes were incorporated to study the role of electronegativity in the electron transfer process to obtain a fundamental knowledge of EPFR formation mechanism on ZnO. Upon chemisorption on ZnO nanoparticles at 250 °C, electron paramagnetic resonance (EPR) confirms the formation of oxygen adjacent carbon-centered organic free radicals with concentrations between 10 16 and 10 17 spins/g. The radical concentrations show a trend of 1,2-dibromobenzene (DBB) > 1,2-dichlorobenzene (DCB) > 1,2-difluorobenzene (DFB) illustrating the role of electronegativity on the amount of radical formation. X-ray absorption spectroscopy (XAS) confirms the reduction of the Zn 2+ metal center, contrasting previous experimental evidence of an oxidative mechanism for ZnO single crystal EPFR formation. The extent of Zn reduction for the different organics (DBB > DCB > DFB) also correlates to their polarity. DFT calculations provide theoretical evidence of ZnO surface reduction and exhibit a similar trend of degree of reduction for different organics, further building on the experimental findings. The lifetimes of the EPFRs formed confirm a noteworthy persistency.