Elucidating the catalytic degradation of enrofloxacin by copper oxide
nanoparticles through the identification of the reactive oxygen species
Ishai Dror
a, *
, Lea Fink
a, c
, Lev Weiner
b
, Brian Berkowitz
a
a
Department of Earth and Planetary Sciences, Weizmann Institute of Science, Rehovot, 7610001, Israel
b
Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 7610001, Israel
c
Currently at the Institute of Chemistry and Center for Nanoscience and Nanotechnology, Edmond J. Safra Campus, Givat Ram, The Hebrew University of
Jerusalem, Jerusalem, 9190401, Israel
highlights graphical abstract
CuO nanoparticles degrade persistent
organic contaminants in aqueous
solutions.
The reaction mechanism and cata-
lytic cycle of CuO nanoparticles is
elucidated.
ESR study demonstrates production
of reactive oxygen species by CuO
nanoparticles.
The distribution of radical species
shows high production of superoxide
radicals.
The CuO nanoparticle catalytic cycle
mimics superoxide dismutation
enzyme activity.
article info
Article history:
Received 24 February 2020
Received in revised form
22 April 2020
Accepted 29 May 2020
Available online 5 June 2020
Handling Editor: Jun Huang
Keywords:
Reactive oxygen species
Enrofloxacin
Oxidation
Superoxide dismutase
Superoxide radicals
abstract
Copper oxide nanoparticles (CuO-NPs) have been suggested as effective catalysts to degrade many
persistent organic contaminants. In parallel, CuO-NPs are considered toxic to soil microorganisms, plants
and human cells, possibly because they induce oxidative stress and generation of reactive oxygen species
(ROS). However, the mechanism of the catalytic process and the generated ROS are poorly understood.
Here we discuss the reaction mechanism of CuO-NPs during the catalytic degradation of enrofloxacin e
an antibiotic pharmaceutical used in this study as a representative persistent organic compound. The
degradation of an aqueous solution of the enrofloxacin exposed to CuO-NPs and hydrogen peroxide was
studied showing fast removal of the enrofloxacin at ambient conditionsns. ROS production was identified
by electron spin resonance and a spin trapping technique. The distribution of the free radical species
indicated production of a high percentage of superoxide (O
2
.
) radicals as well as hydroxyl radicals; this
production is similar to the “radical production” activity of the superoxide dismutase (SOD) enzyme in
the presence of hydrogen peroxide. This activity was also tested in the opposite direction, to examine if
CuO-NPs show reactivity that potentially mimics the classical SOD enzymatic activity. The CuO-NPs were
found to catalyze the dismutation of superoxide to hydrogen peroxide and oxygen in a set of laboratory
experiments.
© 2020 Elsevier Ltd. All rights reserved.
* Corresponding author.
E-mail address: ishai.dror@weizmann.ac.il (I. Dror).
Contents lists available at ScienceDirect
Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere
https://doi.org/10.1016/j.chemosphere.2020.127266
0045-6535/© 2020 Elsevier Ltd. All rights reserved.
Chemosphere 258 (2020) 127266