Oxidation of o-phenylenediamine to 2,3-diaminophenazine in the presence of cubic ferrites MFe2O4 (M = Mn, Co, Ni, Zn) and the application in colorimetric detection of H2O2

Article abstract of DOI:10.1002/aoc.4465

Metal ferrites nanocrystallites, MFe₂O₄ (M?=?Mn, Co, Ni, Zn) were prepared by coprecipitation method and characterized by a combination of physico-chemical and spectroscopic techniques. MFe₂O₄ nanoparticles having particle size in the range 10–35?nm were tested as catalysts in the oxidation of o-phenylenediamine (OPD) to 2,3–diaminophenazine (DAP) using hydrogen peroxide as oxidant at room temperature. Kinetic data was collected for the catalytic oxidation of OPD to DAP by monitoring the UV–vis absorbance at 415?nm and fit well to the Michaelis–Menten model yielding kinetic parameters K_m (Michaelis–Menten constant) and V_max (maximum rate of reaction). MnFe₂O₄ nanoparticles provide the highest catalytic activity in the oxidation of OPD to DAP at room temperature. A colorimetric method was developed based on the MnFe₂O₄/OPD system for the detection of H₂O₂ in reaction solution. The method has a detection limit of 30 μM for H₂O₂ and wide linear range.

Full text of DOI:10.1002/aoc.4465

Received: 24 January 2018
DOI: 10.1002/aoc.4465
Revised: 13 April 2018
Accepted: 21 May 2018
F U L L P A P E R
Oxidation of o‐phenylenediamine to 2,3‐diaminophenazine
in the presence of cubic ferrites MFe O (M = Mn, Co, Ni,
2
4
Zn) and the application in colorimetric detection of H O
2
2
1
1
2
Fahime Vetr | Zeinab Moradi‐Shoeili
| Saim Özkar
1
Department of Chemistry, Faculty of
Metal ferrites nanocrystallites, MFe O (M = Mn, Co, Ni, Zn) were prepared by
2 4
Sciences, University of Guilan, P.O. Box
4
2
1335‐1914, Rasht, Iran
coprecipitation method and characterized by a combination of physico‐chemi-
Department of Chemistry, Middle East
cal and spectroscopic techniques. MFe O nanoparticles having particle size in
2
4
Technical University, 06800 Ankara,
Turkey
the range 10–35 nm were tested as catalysts in the oxidation of o‐
phenylenediamine (OPD) to 2,3–diaminophenazine (DAP) using hydrogen
peroxide as oxidant at room temperature. Kinetic data was collected for the
catalytic oxidation of OPD to DAP by monitoring the UV–vis absorbance at
415 nm and fit well to the Michaelis–Menten model yielding kinetic parame-
ters Km (Michaelis–Menten constant) and Vmax (maximum rate of reaction).
MnFe O nanoparticles provide the highest catalytic activity in the oxidation
Correspondence
Zeinab Moradi–Shoeili, Department of
Chemistry, Faculty of Sciences, University
of Guilan, P.O. Box 41335–1914, Rasht,
Iran.
Email: zmoradi@guilan.ac.ir
2
4
Funding information
Turkish Academy of Sciences; University
of Guilan
of OPD to DAP at room temperature. A colorimetric method was developed
based on the MnFe O /OPD system for the detection of H O in reaction
2
4
2 2
solution. The method has a detection limit of 30 μM for H O and wide linear
2
2
range.
KEYWORDS
hydrogen peroxide detection, kinetic analysis, o‐phenylenediamine, oxidation reaction
1
| INTRODUCTION
Since the oxidation of OPD by H O or O proceeds
2
2
2
very slowly, the reaction needs to be catalyzed, for
example by using transition metal ions. The resultant
solution of DAP has an orange–red color and exhibits
an orange‐yellow fluorescence when irradiated by ultravi-
The oxidation of aromatic amines, especially o‐
phenylenediamine (OPD), has already been utilized for
various applications such as detection of metal ions,
preparation of conducting polymers, pesticides and
dyes.
which can be oxidized by molecular oxygen or hydrogen
peroxide in the presence of metal ions, forming 2,3–
diaminophenazine (DAP) as the main oxidation product
[
1–3]
[
7]
olet light. The concentration of DAP is usually deter-
mined by using UV–vis electronic absorption
spectroscopy. After the first report of OPD oxidation to
[4,5]
OPD is a colorless, nonfluorescent compound
[8]
DAP using iron(III) chloride by Griess in 1871, many
transition metal complexes have been tested as catalysts
[9]
in this oxidation reaction using H O or O as oxidant.
[6]
2
2
2
(Equation 1).
The oxidation of OPD to DAP is of great importance in
immunoassay determination of enzyme‐catalyzed reac-
tions such as oxygenase/oxidases and peroxidases. For
instance, this oxidation reaction has been used for mea-
suring the catalytic activity of the multi‐copper contain-
[
10]
(1)
ing oxidase (Laccase)
and the horseradish peroxidase
Appl Organometal Chem. 2018;e4465.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
1 of 10
https://doi.org/10.1002/aoc.4465

2
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VETR ET AL.
[11]
(HRP).
Zhang et al. have developed a new method for
spectroscopy. Moreover, we showed that MnFe O /OPD
2
4
the determination of hemoglobin (Hb) based on its enzy-
system can be used for the detection of H O in solution
2 2
under the optimized conditions.
[
12]
matic activity for the oxidation of OPD to DAP.
In
addition, this chromogenic oxidation reaction has
attracted much interest in the spectrophotometric deter-
mination of H O using horseradish peroxidase as well
2
2
| EXPERIMENTAL
2
2
[13]
as peroxidase inspired complexes.
Recently, a variety
.1 | Materials and Methods
of inorganic nanomaterials with peroxidase‐like activity
[
14]
[15]
[16,17]
such as Fe O
Co O ,
CuS,
Pd‐Ir core shell nanocubes,
were proved to be highly efficient
Mn‐coordinated
All materials were obtained from commercial sources and
used as received without further purification. Powder X‐
ray diffraction (PXRD) data were collected with a Philips
pw 1830 diffractometer (Cu‐Kα X‐radiation, λ = 1.54 Å).
FT–IR spectra of samples in the form of KBr pellets were
recorded using an Alpha‐Bruker FT‐IR spectrophotome-
ter. The scanning electron microscopy (SEM) images
were taken on a KYKY–EM3200 scanning electron micro-
scope. Transmission electron microscopy (TEM) analysis
was carried out using a Zeiss‐EM10C microscope operat-
ing at 80 kV or a JEM‐2100F (JEOL) microscope operat-
ing at 200 kV. Samples were examined at magnification
between 400 and 700 K. The elemental analysis was
recorded with an energy dispersive X‐ray (EDX) analyzer,
MIRA3 FEG–SEM series. The time dependence of the
absorbance at 415 nm was recorded on a Photonix
Ar2017 UV–Vis spectrophotometer.
3
4,
3 4
[
18]
[19]
histidyl self‐assembly,
Au/CuS composite
[
20]
catalyst in OPD oxidation but the reaction kinetic param-
eters have not been measured in most cases.
Ferrites can be considered as promising candidates in
catalyzing the oxidation of OPD to DAP using O or
2
H O . Spinel ferrites with a general formula of MFe O
2 4
2
2
(M is a divalent transition metal ion) are among a group
of magnetic nanomaterials which have been widely used
as magnetic diagnostic, drug delivery, magnetic recording
materials, electrical generators, microwave devices, power
transformers in electronic and telecommunication appli-
[21,22]
cations.
Other applications of spinel ferrites include
their use as heterogeneous catalysts in Fenton reactions,
photocatalysis, and treatment of heavy metal containing
[23,24]
waste, gas sensors, and pigments.
These materials
crystallize into a cubic closed−packed structure of oxygen
ions. The cations occupy two types of interstitial sites
known as tetrahedral (A) site and octahedral (B) site.
The distribution of cations at tetrahedral and octahedral
sites depends on the site stabilization energies of divalent
2
.2 | Synthesis of the magnetic MFe O
2 4
ferrites (M = Mn, Co, Ni, Zn)
The superparamagnetic spinel ferrites were synthesized
following the procedure described elsewhere
100 mL aqueous solution of CoCl ·6H O (1.19 g, 5 mmol),
MnCl ·4H O (0.99 g, 5 mmol), NiCl .6H O (1.19 mg,
5 mmol) or ZnNO .6 H O (1.48 mg, 5 mmol) was added
to 30 ml aqueous solution of FeCl ·6H O (2.7 g, 10 mmol)
in water. The mixtures were heated at 80 °C for 1 h. Subse-
quently, 20 ml of NaOH solution (6 M) was added under
vigorous mechanical stirring (pH 11–12). A black precipi-
tate formed immediately, and stirring was continued for
1 h at 100 °C. After that time, the reaction mixtures were
cooled to room temperature, and the solid materials were
magnetically separated, washed with distilled water and
ethanol, respectively and dried in an oven at 100 °C for 1 h.
[25]
[29]
and trivalent ions in spinel structures. Many important
properties of nanoferrites are sensitive to their structure,
method of preparation, shape and size of particles, and
the nature of the cation distribution. The experimental
results have shown that the introducing Cr, Mn, Co, Ti
and V to magnetite can modify its catalytic activity and sta-
. Briefly,
2
2
2
2
2
2
3
2
3
2
[26–28]
bility while maintaining the spinel structure.
Herein, we report the results of a thorough investiga-
tion on the chromogenic oxidation of OPD to DAP in the
2+
presence of nanostructured ferrites having Fe
ions
2+
2+
2+
2+
replaced by Mn , Co , Ni and Zn ions. To the best
of our knowledge, there exists no report on the catalytic
performance of metal substituted ferrites and especially
kinetic parameters in the oxidation of OPD to DAP.
Spinel ferrite nanoparticles of MFe O (M: Mn, Co, Ni
2
4
2
.3 | General procedure for catalytic
and Zn) were synthesized using a co‐precipitation
method and characterized by a combination of physico‐
chemical and spectroscopic techniques. Spinel ferrite
nanoparticles were employed as catalyst in the oxidation
of OPD to DAP. Our report includes the results of inves-
tigation on the catalytic oxidation of OPD to DAP
depending on the cation type and kinetic study of the cat-
alytic reaction using UV–vis electronic absorption
oxidation of o–phenylenediamine
In a typical experiment, 0.6 mg MFe O nanoparticles was
dispersed in a reaction mixture of 10 mL buffer solution
(0.1 M citrate–phosphate buffer, pH = 7.0 ± 0.1) with
10
substrate, then 80 μL H O (30%) was added as oxidant.
The progress of reaction was monitored by UV–vis
2
4
−
2
M
concentration of o–phenylenediamine as
2
2

VETR ET AL.
3 of 10
spectroscopy. Absorption spectra were recorded with time
in the range 300–800 nm at room temperature, for a period
of 30 min. A new band at 410–415 nm starts to increase in
the presence of MFe O4 indicating the formation of
2
oxidation product (DAP). The reaction was followed by
recording the absorbance of reaction product (DAP) at
4
15 nm with a time interval of 3 min. Then, the data was
converted to the corresponding concentration of DAP by
using the molar extinction coefficient of DAP
4
−1
−1 [30,31]
(
ɛ = 1.67 × 10 M cm ).
The reaction rates were
determined from the concentration versus time plots in
the initial stage of the catalytic reaction. The kinetic curves
followed the typical Michaelis–Menten equation: ν = V
0
max
max
[
S]/(K + [S]) where ν is the initial rate of reaction, V
m
0
is the maximum reaction rate, Km is the Michaelis
constant and [S] is the concentration of substrate. Kinetics
parameters were determined by nonlinear least‐squares
data fitting (NLSF) in a Microsoft Excel worksheet using
[32]
a protocol described previously by Kemmer et al.
FIGURE 1 Powder XRD patterns of the synthesized samples of
2 4 2 4 2 4 2 4
MnFe O , CoFe O , NiFe O and ZnFe O
2
.4 | H O detection using the MnFe O
2 2 2 4
nanoparticles as peroxidase mimetics
A typical colorimetric analysis was realized as follows: In
a 10 ml phosphate buffer solution of OPD (15 mM),
All the XRD patterns show the typical diffraction peaks
corresponding to the reflection planes (220), (311),
(222), (400), (422), (511) and (440) that can be indexed
0
.6 mg MnFe O nanoparticles, and various volumes of
2 4
working solution of H O were added. Then, the mixed
to the face–centered cubic phase of ferrite. For CoFe
NiFe and ZnFe samples a new minor phase of
Fe with the reflection 2θ around 33° (JCPDS card
2 4
O ,
2
2
solution was allowed to stand at room temperature for
0 min. The mixture was used for absorption spectros-
copy measurement at 415 nm.
2
O
O
2 3
4
O
2 4
3
no.: 79–1741) appears suggesting that besides the face–
centered cubic phase of ferrite, some Fe cations exist as
Fe O in the samples. However, from the XRD pattern
2
3
3
3
| RESULT AND DISCUSSION
characteristics, the content of cubic phase of ferrite in
these samples is obviously in the majority. The diffraction
patterns of the characteristic peaks are in good agreement
.1 | Preparation and characterization of
spinel ferrite nanoparticles
[
34]
with data presented previously
and therefore, it can
2+
The MFe O nanoparticles where M represents a divalent
be concluded that the substitution of Fe ion in ferrite
by the divalent transition metal ions (Co , Ni , Mn ,
Zn ) does not alter the lattice of spinel ferrites. High
intensity and sharpness of XRD characteristic peaks indi-
2
4
2+
2+
2+
Mn, Co, Ni and Zn transition metals were prepared via
aqueous co‐precipitation route which is known as low
cost and less time‐consuming method for the synthesis
of water‐dispersible nanoferrites in high yields especially
2+
cate the good quality crystalline structure of MFe
O
2 4
[33]
for industrial scales.
The methodology employed in
nanoparticles. The size of the MFe nanoparticles were
O
2 4
this study provides an eco‐friendly route without
using any surfactant, hazardous solvents, high reaction
temperature or pressure.
calculated from the most intense peak (311) by the
Scherrer's equation: D = kλ/βcosθ, where, D is the aver-
age crystalline size, k the Scherrer constant (0.89), λ the
X‐ray wavelength used, β the angular line width at half
maximum intensity and θ is the Bragg's angle in degrees
The spinel ferrite nanoparticles were characterized by
XRD, SEM, TEM, SEM–EDX and FT–IR spectroscopy.
Figure 1 displays the powder XRD patterns for all the
MFe O samples with M = Mn, Co, Ni, and Zn. The
[
35]
unit
12.3, 8.6 and 7.2 nm for MnFe
and ZnFe , respectively.
Figure 2 illustrates SEM images of MFe
. The calculated average crystallite sizes are 14.3,
, CoFe , NiFe O
2 4
O
2 4
O
O
2
2
4
2
4
4
XRD characteristic of all the samples mostly corresponds
to the standard card of ferrites (JCPDS: 79–1744 for
MnFe O , JCPDS: 22–1086 for CoFe O , JCPDS:
O nanoparti-
2 4
cles which show that the nanoparticles are of nano‐
dimensions in the size range of 20–40 nm and have
2
4
2 4
7
4–2081 for NiFe O and JCPDS: 82–1049 for ZnFe O ).
2
4
2 4

4
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VETR ET AL.
2 4
FIGURE 2 SEM images of MFe O nanoparticles
2 4
FIGURE 3 TEM images of MFe O nanoparticles
almost spherical shape. The morphology and particle size
of the nano‐ferrite samples were also investigated by
transmission electron microscopy (TEM). Figure 3 shows
TEM images of MFe O nanoparticles. The approximately
particles are present in the samples. The average particle
sizes estimated from the TEM images were about 18, 15,
35 and 10 nm for MnFe O , CoFe O , NiFe O and
2
4
2
4
2 4
ZnFe O , respectively, which are in good agreement with
2
4
2 4
spherical as well as some moderately agglomerated
XRD and SEM techniques.

VETR ET AL.
5 of 10
2 4
FIGURE 4 EDX Images of synthesized MFe O nanoparticles (M = Mn, Co, Ni and Zn)
[
37]
To provide further information about the elemental
composition of the metal substituted ferrites, the samples
were characterized by energy dispersive X‐Ray (EDX)
analysis (Figure 4). Results clearly demonstrated the
purity of the synthesized MnFe O , CoFe O , NiFe O
the octahedral−metal stretching vibrations.
However,
some researchers consider the presence of an intense
band at about 550 cm to be sufficient proof for the for-
The typical FT–IR mea-
surements for the prepared MFe O4 nanoparticles
−
1
[
38]
mation of the spinel structure.
2
4
2
4
2
4
2
and ZnFe O .
(M = Mn, Co, Ni and Zn) exhibit two absorption peaks
2
4
−
1
−1
Figure 5 displays the FT‐IR spectra of all the
in the range of 410–420 cm
and 580–600 cm
MnFe O , CoFe O , NiFe O and ZnFe O nanoparticles.
(Figure 5) which assigned to the stretching frequency of
the tetrahedral metal–oxygen bond and the metal–oxygen
vibration at the octahedral sites in spinel compounds,
respectively. The wavenumbers and intensity of the two
characteristic bands corresponding to spinel ferrites are
2
4
2
4
2
4
2 4
Spinel ferrites are expected to show two characteristic
−
1
bands in the region of 400–600 cm in their infrared
[
36]
spectra.
The band (υ ) with higher wave number,
1
−
1
−1
observed from 500 cm to 600 cm , corresponds to the
intrinsic stretching vibrations of the metal at the tetrahe-
[
34,36,39]
comparable with that reported previously.
Strong
−
1
dral site. The band (υ ) with lower wave number, which
bands around 3400–3370 and 1595 cm appeared in
FT–IR spectra of the nanoparticles corresponding to the
vibrational modes of O−H stretching and bending vibra-
tions of surface hydroxyl groups and physisorbed water
molecules.
2
−
1
−1
is observed from 385 cm to 450 cm , corresponds to
3
.2 | Peroxidase‐like activity of MFe O
2
4
nanoferrites
MFe O (M = Mn, Co, Ni, Zn) nanoparticles show the
2
4
peroxidase–like catalytic activity in oxidation of the chro-
mogenic substrate OPD to DAP in the presence of H O .
2
2
The catalytic oxidation reaction was followed by monitor-
ing the variation in the UV–vis electronic absorption
spectra during the reaction. Measuring the absorbance
of the product DAP molecule at 415 nm can be used to
follow the catalytic oxidation reaction in the presence of
ferrite nanoparticles (Figure 6). The results reveal that
the relative catalytic activity of ferrite nanoparticles in
the oxidation of OPD to DAP depends on the divalent
FIGURE 5 FT–IR spectra of (a) MnFe
2 4 2 4
O , (b) CoFe O , (c)
NiFe , (d) ZnFe nanoferrites taken from KBr pellets
2
O
4
2 4
O

6
of 10
VETR ET AL.
of H O oxidant. From the experimental results given in
2
2
Figure 7 one can conclude that MnFe O nanoparticles
2
4
have peroxidase like catalytic activity in the oxidation of
OPD to DAP in the presence of H O as oxidant at room
2
2
temperature.
Kinetics of the catalytic oxidation of OPD to DAP
using MnFe O nanoparticles as catalyst and H O as oxi-
2
4
2 2
dant were studied depending on the pH of the reaction
solution and concentrations of oxidant and catalyst. The
concentration versus time data was then converted to
FIGURE 6 Absorption versus time plot measured at 415 nm in
the UV–vis electronic absorption spectra during the oxidation of
OPD in the presence of MFe
2
O
4
nanoparticles at room
(0.06 mg.
2 2
ml ), and H O (60 mM) in 0.1 M buffer solution of citrate–
temperature. Assay conditions: OPD (12.5 mM), MFe
2 4
O
−1
phosphate (pH 7.0) at room temperature
cation in MFe O . The quantitative evaluation of the
2
4
absorption versus time plots in Figure 6 gives the follow-
ing order for the peroxidase‐like activity of spinel ferrite
nanoparticles
in
the
oxidation
of
OPD:
MnFe O > CoFe O > NiFe O ~ ZnFe O .
2
4
2
4
2
4
2 4
To compare the catalytic performance of MFe O4
2
nanoparticles, several experiments were performed
within a suitable range of OPD and H O concentrations.
2
2
Experimental results, given in Figure 7, show that the
oxidation of OPD is negligible in the presence of H O2
2
without spinel MnFe O nanoparticles. A slow oxidation
2
4
is observed when MnFe O nanoparticles are added to
2
4
the solution of OPD in the absence of H O ; i.e. OPD is
2
2
slowly oxidized by O in the presence of MnFe O nano-
2
2 4
particles. However, MnFe O nanoparticles catalyze sig-
2
4
nificantly the oxidation of OPD to DAP in the presence
FIGURE 8 Dependence of the peroxidase activity on (a) pH
while keeping the H
60 mM and 0.06 mg/ml, respectively, (b) the concentration of
MnFe nanoparticle catalyst while keeping the
[H ] = 60 mM and pH = 7.0 ± 0.1 and (c) the concentration of
while keeping the amount of MnFe at 0.06 mg/mL and
2 2 2 4
O and MnFe O concentrations constant at
FIGURE 7 Time‐dependent absorbance changes at 415 nm of
OPD oxidation in different reaction systems: (a) OPD
2 4
O
(
15 mM) + H
2
O
2
(60 mM), (b) OPD (15 mM) + MnFe
0.06 mg.ml ) and (c) OPD (15 mM) + MnFe (0.06 mg.ml
(60 mM) in 0.1 M buffer solution of citrate–phosphate
pH 7.0) at room temperature
2
O
4
2 2
O
−
1
(
−
2
O
4
H
2
O
2
2 4
O
1
)
+ H
2
O
2
pH = 7.0 ± 0.1 constant. The OPD concentration was 7.5 mM and
the experiments were carried out at room temperature
(

VETR ET AL.
7 of 10
[
32,40]
the rate of oxidation reaction by using the initial rate
method. Thus, Figure 8 shows the plots of initial rate ver-
sus pH, concentration of catalyst or concentration of oxi-
dant. The catalytic activity of MnFe O nanoparticles in
nonlinear least‐squares fitting (NLSF).
The
Michaelis–Menten constant (K ) and maximum rate of
reaction (Vmax) values for MFe O nanocatlysts are given
m
2
4
in Table 1. Vmax is an indicator of catalytic activity while
Km indicates the affinity of the catalyst for the substrate.
In principle, lower Km value indicates a higher affinity
of catalyst for the substrate. Inspection of the results
listed in Table 1 indicates that (i) NiFe O and ZnFe O
2 4
2
4
the oxidation of OPD by H O depends on pH of the reac-
2
2
tion solution as shown in Figure 8a. MnFe O nanoparti-
2
4
cles (0.06 mg/mL) provide the highest reaction rate for
the oxidation of OPD at a pH value of 7.0. As shown by
the plots in Figures 8b and 8c, the peroxidase–like activity
of MnFe O nanoparticles in the oxidation of OPD to
2
4
nanoparticles have lower catalytic activity in oxidation
of OPD compared to those of MnFe O and CoFe O
2 4
2
4
2
4
DAP increases with the increasing concentrations of both
the catalyst and H O up to certain values range. Consid-
nanoparticles, (ii) MnFe O4 nanoparticles provide the
highest activity among all the ferrites used in the present
study.
2
2
2
ering the rate of oxidation reaction, the saturation values
are obtained when the concentration of MnFe O nano-
The effect of incorporation of transition metals on the
catalytic activity of ferrites in oxidation processes has
2
4
particles is 0.06 mg/ml and the H O concentration is
2
2
[
41]
6
0 mM (1:8 ratio of OPD:H O ).
been investigated in the previous reports.
The reported
2
2
The kinetic data were evaluated to obtain the kinetic
results reveal that the catalytic activity of substituted fer-
rite nanoparticles depends on various factors including
the particle size, reduction potential of metal substitute
parameters for the catalytic oxidation of OPD to DAP
using the MFe O nanoparticles as catalyst and H O as
2
4
2 2
oxidant at an optimized pH of 7.0 ± 0.1. Figure 9 shows
the plots of initial rate versus concentration of OPD for
the catalytic oxidation of OPD to DAP using H O as oxi-
TABLE 1 Comparison of the apparent Michaelis–Menten con-
2
2
stant (K
m
) and maximum reaction rate (V
m
) for OPD as substrate
dant (60 mM) and each of four spinel ferrite nanoparti-
cles (0.06 mg/ml) MnFe O , CoFe O , NiFe O , and
2
4
2
4
2
4
Catalyst
MnFe CoFe NiFe
2
O
4
2
O
4
2
O
4
2 4
ZnFe O
ZnFe O at pH = 7.0 ± 0.1 and room temperature.
2
4
K
V
m
(mM)
27.5 ± 2.6 32.7 ± 1.9
8.4 ± 1.0 22.6 ± 2.4
The experimental data obtained by using each of four
—
8
m
× 10
10.4 ± 1.77 7.8 ± 1.03 0.86 ± 0.17 0.82 ± 0.18
MFe O nanoparticle catalysts fit well to the Michaelis–
2
4
−
1
(
Ms )
Menten equation. Kinetic parameters calculated by
FIGURE 9 Plots of initial rate versus concentration of OPD for the catalytic oxidation of OPD to DAP using H
four spinel ferrite nanoparticles (0.06 mg/ml) (a) MnFe , (b) CoFe , (c) NiFe , and (d) ZnFe at pH = 7.0 ± 0.1 and room
temperature. The solid lines show the fit of data to the Michaelis–Menten equation yielding the kinetic parameters
2 2
O as oxidant and each of
2
O
4
2
O
4
2
O
4
2 4
O

8
of 10
VETR ET AL.
2
+
2+
as well as the nature, valence state, and number of substi-
introduction of Mn and Co remarkably improved
[27]
2+
2+
tution.
In addition, the catalytic activity depends on
the catalytic activity of magnetite, while Ni and Zn
showed an inhibitory effect.
were explained by the fact that the Co and Mn
obviously increase the H O decomposition to produce
OH for organic oxidation, while Ni
inhibited this process.
[
26,45–47]
the distribution of metal cations among tetrahedral and
octahedral sites of the cubic spinel lattice. Since the
octahedral sites were almost exclusively exposed at the
surface of spinel structures, the metal ions present in
These observations
2+
2+
2
2
•
2+
2+
and Zn
have recently
[
42]
[28]
[48]
the octahedral sites play a crucial role in catalysis.
Lago et al.
Moreover, the incorporation of transition metals changes
the surface properties of ferrites such as the amount of
surface hydroxyl group and specific surface area.
reported the results of a comparative study on the
effects of Co, Mn, and Ni substitution in Fe3–xM O on
x
4
[
28,41]
the catalytic activity in heterogeneous Fenton reactions.
They concluded that the incorporation of Mn and Co
remarkably increased the activity while, the presence
of Ni led to a great inhibition of the process. The cata-
lytic performances of MFe O nanoferrites in oxidation
Such factors would affect the interaction of ferrite surface
with the substrate or oxidant, which may have influence
on the catalytic activity of substituted ferrite nanoparti-
cles in oxidation reactions. Although the fundamental
mechanism responsible for oxidation catalytic activity of
ferrites is still unclear, several studies also proposed that
the oxidation mechanism corresponds to the free radical
production through Fenton or Fenton−like reac-
2
4
of OPD to DAP are consistent with the results of the
previous studies emphasizing the benefit of using the
transition metal substituted ferrite nanoparticles in oxi-
dation processes.
[14,43]
tions.
Results showed that the strong Fenton−like
activity of substituted ferrites originates mainly from fer-
rous or transition metal ions at the surface of nanoparti-
3
.3 | Detection of H O using MnFe O as
2 2 2 4
catalyst and OPD as substrate
[27]
cles.
A primary reduction of the metal ion occurs
first. H O2 would then cleavage to hydroxyl radical.
Finally, the formed hydroxyl radical ( OH) plays an
Detection of H O is a common analysis in biomedicine
2 2
2
•
[49]
diagnosis.
As the catalytic activity of the MnFe O
2 4
important role in the oxidation of chromogenic peroxi-
nanoparticles in oxidation of OPD to DAP is dependent
on the concentration of H O below saturation value
[20,44]
dase substrates.
Previous results showed that the
2
2
2 2 2 4
FIGURE 10 Linear calibration plot for H O determination using MnFe O /ODP system
2 2
TABLE 2 Comparison of various peroxidase mimicking nanomaterials for the detection of H O
Catalyst
MnFe
Substrate
Detection limite (mol/l)
Linear range (mol/l)
References
−
5
−4
2
O
4
OPD
OPD
OPD
OPD
OPD
DPD**
3 × 10
1 × 10 –0.015
−6
This work
[13]
−
−
−
−
8
6
5
7
−5
FeTSPC*
7.4 × 10
1.5 × 10
1.5 × 10
1.1 × 10
5.0 × 10 –8.0 × 10
−3
−6
[52]
[15]
[16]
[53]
Cu/Au complex
10 – 10
−5
−3
−3
Co
CuS
Magnetoferritin
3
O
4
2.9 × 10 – 5.8 × 10
−6
1.0 × 10 – 1.0 × 10
−
3
−2
not reported
5.8 × 10 – 8.82 × 10
*
iron‐tetrasulfonatophthalocyanine.
*
*N,N‐diethyl‐p‐phenylenediamine sulfate.

VETR ET AL.
9 of 10
−
4
(
Figure 8c), the peroxidase‐like catalytic activity of
The calibration curve has a linear range 1 × 10 –
1.5 × 10 mol/L for the H O detection.
2 2
−
2
MnFe O nanoferrite in this oxidation reaction can be
2
4
used for colorimetric detection of H O . The catalytic
2
2
activity of MnFe O nanoparticles in oxidation of OPD
2
4
ACKNOWLEDGEMENTS
can be measured by monitoring the absorbance of DAP
at 415 nm using a spectrophotometer under the opti-
mized conditions. Figure 10 shows a calibration curve
for the absorbance measured at 415 nm versus the con-
centration of H O present in the reaction solution. It
The authors are grateful to the University of Guilan for
financial support. Partial support by Turkish Academy
of Sciences is gratefully acknowledged.
2
2
shows that H O can be detected in concentration as
2
2
ORCID
low as 30 μM in the reaction solution. The calibration
curve is linear in the concentration range from 100 μM
to 15 mM H O . Table 2 gives a comparison of the
Zeinab Moradi‐Shoeili
9566
http://orcid.org/0000-0001-5315-
2
2
detection limit and efficiency of the MnFe O /OPD sys-
Saim Özkar http://orcid.org/0000-0002-6302-1429
2
4
tem in detection of H O with other catalytic systems
2
2
reported in literature. These results show that the detec-
tion limit for MnFe O /OPD system is the same order of
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