RESUMO
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 1016 and 1017 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 Zn2+ 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.
RESUMO
Environmentally persistent free radicals (EPFRs) are a class of toxic air pollutants that are found to form by the chemisorption of substituted aromatic molecules on the surface of metal oxides. In this study, we employ X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) to perform a temperature-dependent study of phenol adsorption on α-Fe2O3(0001) to probe the radical formation mechanism by monitoring changes in the electronic structure of both the adsorbed phenol and metal oxide substrate. Upon dosing at room temperature, new phenol-derived electronic states have been clearly observed in the UPS spectrum at saturation coverage. However, upon dosing at high temperature (>200 °C), both photoemission techniques have shown distinctive features that strongly suggest electron transfer from adsorbed phenol to Fe2O3 surface atoms and consequent formation of a surface radical. Consistent with the experiment, DFT calculations show that phenoxyl adsorption on the iron oxide surface at RT leads to a minor charge transfer to the adsorbed molecule. The experimental findings at high temperatures agree well with the EPFRs' proposed formation mechanism and can guide future experimental and computational studies.
