Anion radicals of [60]fullerenes. An EPR study

Photochemically induced electron transfer in homogeneous systems (using triethylamine donor) and heterogeneous systems (using photoexcited TiO2 suspension) was applied in in situ reduction of [60]fullerene. The anion radicals generated were characterized by means of EPR and VIS/near-lR spectroscopy. Narrow EPR lines were found. Radical A with gA = 2.0000 and peak-topeak width, PPA = 0.09 mT was observed as the primary product; followed by its consecutive product B with gB = 2.0006, PPB = 0.04 mT, and in some cases product C with gc = 2.0009 and PPc < 0.1 mT.Radical A was assigned to [60]fullerenc mono-anion, also characterized by a near-IR band at 1077 nm.B is presumably di-anion or a dimeric tbrm of mono-anion. Identical results were also obtained using cathodic in situ reduction. Applying these generation techniques to [60]fullerene derivatives produced narrow EPR lines analogous to those described for pristine [60]fullerene. This was the case not only in organic solvents, but also in aqueous solutions. The results obtained present a contrast with the original ex situ EPR investigations describing [60]fullerene mono-anion with wide lines. According to the results presented here, the narrow and wide EPR lines do not represent contradictory phenomena,but are an integral part of the relatively complicated manifestations of various fullerene states and both will have to be seriously considered in the future

EPR investigations of polymeric and H2O2 -modified C3N4 -based photocatalysts

The C3N4 -based nanopowders prepared by thermal condensation of melamine (MCN) with subsequent thermal etching (MCN-TE) and H2O2 -treatment were investigated by Q- and X-band EPR spectroscopy in dark and upon in situ UVA or visible-light exposure. Lorentzian signal at g = 2.003, more pronounced in the case of the thermally etched material, dominates EPR spectra of MCN and MCN-TE. More complex spectra were found for H2O2 -treated photocatalysts revealing the presence of signals attributed to the radicals produced via H2O2 interaction with C/N sites in the C3N4 polymeric network. The X-band spectra monitored upon in situ irradiation of the C3N4 -based photocatalysts evidenced the intensity growth of the single line at g = 2.0033 indicating the photoinduced generation of electrons in localized paramagnetic states with the Curie dependence on temperature in the temperature range 100–180 K. The response towards UV or visible-light exposure was significantly limited in the case of H2O2 -treated photocatalysts. EPR spin trapping experiments performed in aqueous suspensions demonstrated the formation of HO2[rad] and HO [rad] spin-adducts, and the increased stability of the primary photogenerated O2 javax.xml.bind.JAXBElement@3a251187 – in aprotic media was well documented by the irradiation of the photocatalysts in the dimethylsulfoxide/water mixed solvent. The highest activities in the production of the non-persistent radical species spin-adducts were found for the thermally etched and pristine photocatalysts, confirming the negative effect of H2O2 -treatment