FEN_P05

Production Profile of Perhydroxyl Radical In Fenton-like Reaction

Driven By 1,2-Dihydroxybenzene and Its Role In Fe(III) Reduction
Gabriel Perez-Gonzalez1,2; Camila Méndez1; Victoria Melin1,2;
Natalie Moreno1,2; David Contreras1,2.

1 University
of Concepción, Concepción-Chile,
2 Millenium Nuclei on Catalytic Processes towards Sustainable

Chemistry (CSC), gperezg@udec.cl

INTRODUCTION
Fenton systems (Fe(II)/Fe(III) and H2O2) are the main reactions in the advance oxidations processes
for several enviromental applications1. These systems are known to produce reactive oxygen
species like hydroxyl radical (•OH), perhydroxyl radical (HO2•), and singlet oxygen as well as ferryl
ions (Fe(IV))2. The ability of recicle Fe(II) from Fe(III) from 1,2-dihydroxybenzene as catechol
enhance the reactivity of these systems known as chelator mediated Fenton reaction (CMF).
Perhydroxyl radical also has the Fe(III) reduction ability and its has been proposed to be generated
from Fenton systems but the profile for this radical has not been informed2,3.

Determine the amount of HO2• generated in situ in the CMF systems is important since it have
been reported by several author their ability to reduce Fe(III) in similar systems where the radical is
generated either by photogeneration or xantine oxidase4,5.

METHODOLOGY

FIGURE 3 – Fe(III) reduction plots, n=3. mean ± SD at pH 3. (A) Reduction curves; Fe(III) (),
Fe(III) / catechol (), Fe(III) / catechol / H2O2 (), Fe(III) / catechol / H2O2 / POBN ().
(B) percentage of total Fe(III) reduced at 10 minutes. * p > 0,0078; ** p > 0,69.

When POBN- O2•

signal, catechol
FIGURE 1 - Methodology diagram. concentration and
Fe(II) generated by
RESULTS AND DISCUSSION HO2•-dependent
mechanism are
compared, the
increase of Fe(II)
generated agrees with
the increase of the
adduct signal until 4.5-
5 minutes. Moreover, Figure 4. Comparison between POBN- O2• adduct signal in
CMF system (solid line), catechol concentration in CMF system
it also agrees with an without catechol (dashed line) and the difference in Fe(II)
increase in catechol produced between CMF and HO2•-restricted CMF systems
concentration. () at pH 3.0 and different reaction time. * p > 0,83; ** p >
FIGURE 2 - Contour plot of POBN-O2 EPR signal of (A) Fenton systems, (B) Fenton-like 0,49; *** p > 0,033
systems, (C) CMF systems. Color scale represent the intensity of left peak in the center These results suggest a recycling mechanism of catechol by HO2• which will
doublet of the spectra.
promote Fe(III) reduction and could explain the reported enhanced effect of
From figure 2 its observed that HO2• was detected in all systems. Fenton system DHB in Fenton reaction
show the greater radical generation at pH 3 (0.223 ± 0.013 mmol L-1). Fenton-like
and CMF shows no differences in the maximum production (0.193 ± 0.003; 0.195 REFERENCES
± 0.004 mmol L-1), each system has a unique profile in time and pH range. 1Parson S., (book) Advanced Oxidation Processes for Water and Wastewater treatment, (2004).
2Salgado P., et al. App. Catal B. (2018)22; 93-102. 3Barb W., et al. Nature. (1950)163; 692-694.
4Gutteridge J., et al. Biochem J. (1990)269; 169-174. 5Liochev S., et al. IUBMB Life. (1999)48;
Figure 3 shows an increase of 7% in Fe(III) reduction in CMF systems when
157-161.
compared to catechol-only Fe(III) reduction, but no Fe(III) reduction in Fenton-like
systems. The addition of POBN to CMF systems (HO2•-restricted CMF systems) ACKNOWLEDGMENTS
shows Fe(III) reduction to catechol-only systems. The authors thanks FONDECYT proyect 1160100 for the funding for the deveplopment of this
project and the funding from Millennium Science Initiative of the Ministry of Economy,
This suggest the participation of HO2• in the reduction of Fe(III) but through an Development and Tourism, grant Nuclei on Catalytic Processes towards Sustainable Chemistry
indirect mechanism. (CSC).