Journal of Molecular Liquids 337 (2021) 116429

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Efficient Dye Degradation via Catalytic Persulfate Activation using

Iron Oxide-Manganese Oxide Core-Shell Particle Doped with Transition
Metal Ions
C. Anushree, D. Nanda Gopala Krishna, John Philip ⇑
Corrosion Science and Technology Division, Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research, HBNI, Kalpakkam, Tamil Nadu 603102, India

a r t i c l e i n f o a b s t r a c t

Article history: Organic-pollutants released into water bodies pose serious concerns because of its detrimental effects in
Received 25 February 2021 aquatic biota, environment and economy. Water remediation using persulfate based advanced oxidation
Revised 23 April 2021 process is one of the emerging techniques. In this study, we have developed iron oxide-manganese oxide
Accepted 4 May 2021
core–shell nanoparticles doped with transition metal ions for the efficient degradation of bromophenol
Available online 11 May 2021
blue dye, for the first time. Here, the transition metal ion doped MnOx shell enables efficient persulfate
activation while the magnetic core facilitate in the effective recovery of used particles. The synthesized
Keywords:
particles were characterized by X-ray powder diffraction, transmission electron microscopy, X-ray pho-
Magnetic nanoparticles
Persulfate activation
toelectron spectroscopy and vibrating sample magnetometer. The presence of dopants is found to signif-
Amorphous manganese oxide icantly change the ratio of Mn3+ to Mn4+, reactivity and mobility of lattice oxygen in doped samples. Silver
Dye removal ion doped MnOx showed the highest dye degradation efficiency of ~91% with 1.8 wt% nanoparticles, due
to the enhanced reactivity and mobility of lattice oxygen activity of the core–shell nanoparticle in pres-
ence of Ag ions in persulfate activation. From the experimental results, the mechanism of activation of
persulfate by nanoparticles is elucidated. Our findings provide a new platform for efficient water reme-
diation using dual functional core shell magnetic nanoparticles.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction eration capability without secondary pollution [4,13,14]. Further,

Magnetic nanoparticles, particularly superparamagnetic nano-
particles and their dispersions exhibit interesting magnetic
stimulus dependent physio-chemical properties that are widely
exploited for applications in heat transfer [1–4], oil removal [5],
defect sensors [6], cancer therapy [7], mechanical sealants [8],
cation sensors [9], MRI contrast agents [10] magnetic emulsions
[11] and tunable dampers [12]. For the aforementioned applica-
tions, the long term stability of dispersions and the compatibility
of surface functionalization moieties with dispersing media are
important. Superparamagnetic iron oxide nanoparticles, exhibiting
high saturation magnetization, zero or negligible coercivity and
remanence are ideal candidate material for high gradient magnetic
separation technology for waste water treatment. The superpara-
magnetic particles do not settle under gravitational field owing
to their ultra small size, non-aggregation under strong fields, avail-
ability of a variety of surface functionalization options and regen-
⇑ Corresponding author at: Head, Smart Materials Section & Corrosion Science
and Technology Division.
E-mail address: philip@igcar.gov.in (J. Philip).
superparamagnetic particles and their dispersions have been a
wonderful model system probe fundamental phenomena [15–17]
and molecular conformational changes at interfaces [18].
Among various water treatments, advanced oxidation pro-
cesses such as Fenton, photochemical, electrochemical, ultrasonic
and persulfate (peroxymono sulfate and peroxydisulfate) based
oxidation, ozonation, gamma ray/electron beam etc. are efficient
approaches in oxidizing or degrading organic effluents from
industrial wastes [19]. Every year ~0.8 million ton of different
dyes are produced worldwide, of which 10–15% are discharged
in water bodies [20]. These effluents pose a serious threat to
human health, environment and mammalians, if untreated. Any
physiochemical method that increases the efficiency of oxidation
capacity is termed as persulfate based advanced oxidation pro-
cess, where the main oxidant involved is insitu generated sulfate
radical or singlet oxygen [21]. There are also reports on reaction
pathways, without any radical for oxidation. Persulfate based oxi-
dation is found to be more economical due to the lower material
cost, availability of a wide variety of metal oxides suitable for
persulfate activation, higher yield and less stringent operational
parameters.

https://doi.org/10.1016/j.molliq.2021.116429
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
C. Anushree, D. Nanda Gopala Krishna and J. Philip
In most of the magnetic systems used for persulfate activa-
tion, till date, have been utilizing iron oxide or iron oxide with
a combination of mesoporous silica or carbon allotropes
[22–26]. Hung et al. [24] synthesized a Fe3O4-carbon black
nanostructures of particle size ranging 10–50 nm using precipi-
tation method and used for remediation of polycyclic aromatic
hydrocarbons (PAHs) from marine sediments using persulfate.
Song et al. [22] prepared persulfate activated Fe3O4 nanoparti-
cles through ultrasonic-assisted reverse co-precipitation for
removal of Cr(VI) and triclosan from aqueous solutions. Liang
et al. [27] synthesized the Fe3O4 particles loaded on mesoporous
silica spheres for degradation of methylene blue using persulfate
activation. Xie et al. [25] developed mesoporous CoFe2O4/SiO2
for degradation of chlorpyrifos by combining ultrasonic treat-
ment and persulfate activation. Liu et al. [23] investigated the
degradation of azo dye using Fe3O4@activated carbon along with
heat and ultrasound treatment. One of the major problems with
these approaches is that on activation of persulfate (without
shell), Fe2+ is converted to Fe3+ and leaches into the solution,
thereby loosing the magnetic properties which makes retrieving
the particles from the water bodies difficult. Further, the excess
of Fe2+ quenches SO
 4 radicals that reduces the efficiency of
degradation [27].
The main objective of this work was to develop an innovative
strategy to overcome the drawbacks associated with the current
approaches and to enable persulfate activation at room tempera-
ture to make the process more energy efficient. In this context,
we have developed an iron oxide-MnOx core–shell system for
persulfate activation at 30 °C and demonstrated its efficient dye
degradation. The dye used in the study is bromophenol blue
which is an anionic dye, comes under the class of triarylmethane
dye (TAM). TAM dyes are synthetic dyes, extensively used in tex-
tile, paper and leather industries due to its low cost [28]. It is a
teratogen, carcinogenic and hence banned in aquaculture applica-
tions [29].
MnOx was chosen because manganese oxide based magnetic
materials have been found to have applications in treatment of
dyes [30,31], gaseous pollutants [32], heavy metal ion extraction
[33], Lithium storage [34] and microwave absorption [35].
Although the use of transition metal ion doped manganese oxide
in advanced oxidation process was studied [36], the controlling
of MnOx thickness over iron oxide, without loosing of magnetic
properties of the core, remained as a challenge, which is very
important to separate particles after the catalysis. In the dual func-
tional nanoparticles, MnOx is used for activation of persulfate
while the iron oxide core is used for imparting magnetic property
for the easy separation of particles after the use. Further, transition
metal ions such as Ag+ and Zn2+ were doped in MnOx to achieve
better dye degradation efficiency through increased oxygen
activity.
2. Materials and methods
2.1. Materials
Carboxymethyl cellulose sodium salt (CMC) (Mw = 90000,
degree of substitution = 0.7) was obtained from Sigma Aldrich
(Merck Co., Germany). Bromophenol blue (BPB) and potassium
nitrate (KNO3) were purchased from Himedia (Himedia Laborato-
ries, Mumbai, India). Ferrous sulfate (FeSO47H2O), potassium
hydroxide (KOH), potassium permanganate (KMnO4) and
hydrochloric acid (HCl) were obtained from Lobachemie (Loba
Chemie Pvt. Ltd., Mumbai, India). All reactants were analytical
grade, and used without any treatment. Milli-Q water with resis-
tivity of 18 MXcm was used.
2
Journal of Molecular Liquids 337 (2021) 116429
2.1.1. Synthesis of iron oxide-MnOx core–shell nanoparticles
The stock solution of carboxymethyl cellulose sodium salt was
prepared by dissolving 3.75 g of polymer in 500 ml of Milli Q water.
For the synthesis of magnetic nanoparticle coated with CMC,
400 ml of stock CMC solution was transferred to 1 l flask. The solu-
tion was heated to 85 °C under constant stirring at 600 rpm. Then,
a solution containing 3.6 g of FeSO47H2O in 160 ml of water was
added to the reaction medium, thereby generating a yellow Fe
(II)-CMC complex. In a separate 100 ml beaker, 3.36 g of KOH
and 0.15 g of KNO3 were solubilized in water and heated to
85 °C. The hot solution was quickly transferred to the reaction
medium containing the Fe(II)-CMC complex, and kept stirring at
600 rpm for 30 min. Finally, the suspension was cooled to the room
temperature to obtain magnetic Fe3O4@CMC particles that were
separated with an external magnet. The isolated nanoparticles
were dried at room temperature.
Iron oxide coated MnOxnanoparticles were synthesized using
hydrothermal approach [37]. A homogeneous dispersion of Fe3-
O4@CMC was made by adding 1.25 g of dried nanoparticles in
10 ml of Milli-Q water, followed by sonication. Then, an aqueous
solution of KMnO4 was added into the reaction solution. To this
0.15 ml of HCl was added drop wise, to produce a dark brown solu-
tion. The entire solution was then transferred to a Teflon lined
stainless steel autoclave and was heated at 100 °C for two hours.
After the reaction was complete, the obtained black precipitate
was collected using an external magnet and washed with Milli-Q
water. The iron oxide coated MnOx nanoparticles obtained after
drying in an oven at 85 °C is named as S0 hereafter.
2.1.2. Synthesis of iron oxide-transition metal ion doped manganese
oxide nanoparticles
Fe3O4@CMC (1.25 g), AgNO3 (0.102 g) and KMnO4 (0.425 g)
were dissolved in 200 ml Milli Q water. HCl (0.15 ml) was added
to the solution drop wise and was transferred to a para polyphenol
liner. The resulting solution was heated in an autoclave at 100 °C
for 2 h to obtain a brown colored suspension, which was trans-
ferred into a beaker and was washed with Milli Q water. The
nanoparticles was separated using a magnet and dried at 60 °C
to obtain maghemite core with manganese oxide shell doped with
Ag ion (hereafter referred as SA). The same procedure was used to
prepare Zn2+ doped manganese oxide shell (hereafter referred as
SZ) where 0.18 g ZnNO3 is used instead of AgNO3.
2.2. Characterization
Powder XRD measurements were performed using Rigaku
Ultima IV instrument, in the h range of 20 to 80° at 2°/min in the
Bragg-Brentano geometry with a Cu Ka source (k = 1.5418 Å).
The acquisition and preliminary analysis of the data were per-
formed using the PDXL software. High Resolution Transmission
Electron Microscope (HRTEM) images of magnetic nanoparticles
were performed by drop casting nanoparticles on top of a
carbon-coated 300 mesh copper grid using JEOL JEM 2100 with a
field emission gun operating at 200 kV. M
H loop was recorded
at room temperature in the field range of
1T to 1T, using a Cryo-
gen free VSM (M/s Cryogenics, UK). Surface chemical and phase
composition characterization was carried out using XPS (SPECS
Surface Nano Analysis GmbH, Germany) with Al Ka X-ray
(1486.7 eV) source operated at 315 W power. Zeta nanosizer (Mal-
vern ZEN3600) was used for zeta potential measurement of the
suspension.
2.3. Catalytic degradation experiments
Dye degradation studies were performed using a Synergy HTX
multi-mode microplate reader. The stock solution was prepared
C. Anushree, D. Nanda Gopala Krishna and J. Philip
by the addition of 0.05 g of dye in 100 ml of Milli Q water and 0.1 g
of persulfate in 3 ml of Milli Q water. For all the degradation exper-
iments, the dye concentration used is 200 mg/l, based on the detec-
tion limits. S0/SA/SZ concentration was used in the steps of one
from 1 to 9 g/l. Persulfate concentration is 16.5 mg/l and was kept
constant [25]. The dye solution was diluted with appropriate con-
centration from the stock solution for the calibration purpose.
From the stock solution, dye, persulfate and the desired concentra-
tion of S0/SA/SZ were added into 10 ml beakers. After 10 min, the
S0/SA/SZ was separated and collected using a magnet. The super-
natant solution containing left over bromophenol blue was mea-
sured using a UV–Vis spectrometer. Using the calibration graph,
the concentration of residual bromophenol blue was calculated.
The percentage of degradation was determined using the following
equations:
Co
C Ao
A
Degradation % ¼  100 ¼  100
Co Ao
where Co is the initial concentrations (mg/l), C is the concentration
after time t (mg/l), Ao is the initial absorbance, A is the absorbance
after a time interval t at maximum absorption (kmax) of bromophe-
nol blue dye.
3. Results and discussion
3.1. Crystal structure and morphology of iron oxide-MnOx
nanoparticles
Fig. 1 shows the XRD pattern of maghemite core with man-
ganese oxide shell without doping (S0), maghemite core with man-
ganese oxide shell doped with Ag ion (SA) and Zn2+ ions (SZ) doped
nanoparticles. The diffraction peaks at 2h values of 30.1, 35.6, 43.2,
53.4, 57.1 and 62.9° corresponds to the reflection from the planes
(2 0 0), (3 1 1), (4 0 0), (4 2 2), (5 1 1), and (4 4 0), of maghemite
(c-Fe2O3) which has a cubic spinal structure (JCPDS card no.
39-1346). Sample S0 showed a broad peak at 21.4°, indicating
the existence of an amorphous MnOx layer on iron oxide [34]. In
silver and Zn doped samples (SA and SZ), the MnOx peak at 21.4°
was significantly lower. c-Fe2O3-MnOx core–shell nanoparticles
were further characterized using HRTEM and XPS (discussed later).
The crystallite size (d) of c-Fe2O3 core of nanoparticles, calculated
using Scherrer equation (d ¼ bcosh 0:9k
, where k = 1.54 Ao, h is the
diffraction angle and b is the full width half maximum of highest
Fig. 1. Room temperature XRD pattern of undoped, Ag and Zn2+ ion doped
maghemite-manganese oxide core–shell nanoparticles, S0, SA and SZ, respectively.
Journal of Molecular Liquids 337 (2021) 116429
intense peak), were 25.3 ± 2, 25.7 ± 2 and 29 ± 2 nm for S0, SA
and SZ, respectively. The slight change in the crystallite size of SZ
may be due to the lowering of edge free energy due to doping that
can promote crystal growth [38]. The metal ions can affect the for-
mation of structure and surface, and when ions adsorbed to the
high-energy surface it can promote growth [39].
The size and morphology of the synthesized particles were
studied using TEM. Fig. 2(a–b) shows TEM and HRTEM images of
S0, respectively. The morphology of the particles were roughly
square shaped. The observed lattice fringe spacing of 0.243 nm,
corresponding to the (3 1 1) plane of c-Fe2O3. The HTREM does
not show a sharp contrast of presence of MnOx over c-Fe2O3 since
the difference in the atomic number Z of the two materials is only
one unit. To further quantify the core–shell structure of the parti-
cle, image processing of HRTEM of Fig. 2(b) was carried out. Fig. 2
(c) shows the pseudo-colored HRTEM image of S0, where MnOx
ð1Þ shell of thickness of ~2.9 nm was clearly distinct from the crys-
talline core of c-Fe2O3. The MnOx shell was seen with a diffuse
diffraction pattern, without any sharp fringes, which is a character-
istic of amorphous materials. Fig. 2(d) shows intensity variation in
gray scale across the length of the cross sections of c-Fe2O3/MnOx
regions (shown by pink and blue lines of Fig. 2(c)), where the thick-
ness of the MnOx layer was ~2.9 nm. Fig. 2(e) shows the EDX spec-
tra of S0 with its elemental composition. The five elements present
in S0 are C, O, Mn, Fe and Cu. The 2.90 atom% of Mn confirm that
the presence of formation of MnOx over c-Fe2O3. The Cu and C orig-
inate from the carbon coated Cu grid (Cu
10.25 atom %) and the
oxidized fragments of carboxymethyl cellulose, respectively. The
average particle size obtained from the histogram distribution of
S0 was found to be 36 ± 4 nm (Fig. 2(f)). The larger particle size
obtained from TEM as compared to the crystallite size is due to
presence of MnOx over the surface of c-Fe2O3.
3.2. X-ray photoelectron spectroscopy analysis
In order to confirm the incorporation of Ag and Zn dopants into
the MnOx, X-ray photoelectron spectroscopy (XPS) analyses were
performed on S0, SA and SZ. The elements observed from the sur-
vey spectrum (Fig. 3) of S0 are iron (Fe 2p
710 eV) manganese
(Mn 2p
640 eV), carbon (C 1s
285 eV) and oxygen (O 1s

530 eV) with atomic concentration in the ratio of 5.3 : 9.4 : 39.4 :
45.9, respectively. In the case of SA, the elements observed in
the survey spectrum are: iron, manganese, silver (Ag 3d

370 eV), oxygen and carbon with atomic concentration ratio of
3.6:10.4:4.2:44.3:37.5, respectively. For SZ, the elements observed
from the survey spectrum of the sample are: iron, manganese, zinc
(Zn 2p3/2–1020 eV), oxygen and carbon with atomic concentration
in the ratio of 5.2:8.9:4.5:48.0:33.4, respectively.
The high resolution spectra of S0 (Fig. 4) showed that the man-
ganese is present in both Mn3+ and Mn4+ states while the iron is
found only in the Fe3+ state. The relative concentration of Mn3+:
Mn4+ states is 6:4. The O 1s region showed the bonding states of
OAFe/Mn (67%), OAH (16%), OAC (13%) and H2O (4%), while the
C 1s region showed the bonding states of CAC/H (77%), CAO
(11%) and C@O (12%), respectively. The carbon in the nanoparticles
originate from the oxidized fragments of the carboxymethyl cellu-
lose polymer
The deconvolution of the Mn and Fe 2p peaks in SA nanoparti-
cles (Fig. 5), with multiplet structure shows that the manganese is
present in both Mn3+ (63%) and Mn4+ (37%) states while the iron is
present only in the Fe3+ state. The Ag 3d region is deconvoluted
with a single broad symmetric doublet peak structure at 367.2
(3d5/2) and 373.2 eV (3d3/2), suggesting that the silver is present
as silver oxide. The O 1s region showed the bonding states of
OAM (64.8%), OAH (21.2%), OAC (11.4%) and H2O (2.6%), where
‘‘M” corresponds to Fe/Mn/Ag, respectively. In the case of SZ
3
C. Anushree, D. Nanda Gopala Krishna and J. Philip Journal of Molecular Liquids 337 (2021) 116429

Fig. 2. (a) TEM and (b) HRTEM image of S0 showing the c-Fe2O3 with a lattice fringe spacing of 0.243 nm, corresponding to the (3 1 1) plane and an amorphous layer of MnOx
of ~2.9 nm (c) Pseudo-colored image processing of HRTEM image of figure (b),(d) intensity variation in gray scale across the length (pink and blue lines) of core–shell regions
of figure (c), (e) Energy dispersive X-ray spectrum and (f) particle size distribution of S0.

nanoparticles (Fig. 6), the manganese and iron are present in only
Mn3+ and Fe3+ states, respectively. The Zn 2p3/2 region is deconvo-
luted with a single broad symmetric peak at 1020.9 eV, suggesting
zinc is present as Zn2+. The O 1s region showed the bonding states
of OAM (63.3%), OAH (21.5%), OAC (10.7%) and H2O (4.5%), where
‘‘M” corresponds to Fe/Mn/Zn. The change in the carbon bonding
states in SA and SZ, as compared to S0 was very meager. Table. 1
shows the summary of the results from XPS analysis with details
of the percentage of Fe/Mn, OAH, OAC and H2O of S0, SA and SZ.
In all the core–shell nanoparticles (S0, SA and SZ), Fe was in +3
oxidation state, indicating that the phase is c-Fe2O3. The absence of
any shift in the binding energy of Fe peaks in doped samples indi-
cates that the dopants were not present in the c-Fe2O3 core. How-
ever, Mn showed distinct variation in its oxidation state on doping:
the ratio Mn3+/Mn4+ in S0 and SA were 1.5 and 1.7, respectively
that indicate the doping with Ag had increased the Mn3+ content
in SA as compared to S0. Ran et al. [40] studied the structural
and magnetic properties of pure and Co-doped Fe3O4 films and
found that the reduction of Fe2+/Fe3+ ratio from 0.5 (for Fe3O4) to
0.2, indicate the incorporation of Co2+ in Fe3O4 lattice. Deng et al.
[41] studied the role of structural defects in MnOx by Ag doping
and observed that incorporation of silver via hydrothermal route
caused an increase in the Mn3+ concentration by 7.5 to 20%. The
binding energy peak Oad (~530.9 eV) indicate the presence of
surface adsorbed oxygen (O


2 or O ), OH groups and oxygen
vacancies [42]. Oad was ~5.2% more in SA, as compared to S0. The
~5.2% increase in Oad in SA, as compared to S0 is due to replace-
ment of Mn4+ by Mn3+, which causes the removal of O2– in the
lattice (Olatt) and formation of vacancy or OH on the surface of
the nanoparticles, which can be represented by the equation

4
C. Anushree, D. Nanda Gopala Krishna and J. Philip
Fig. 3. XPS survey spectrum of undoped, Ag and Zn2+ion doped maghemite-
manganese oxide core–shell S0, SA and SZ, respectively.
3þ 2


Mn4þ1
a
b Mnb O2
4a
b OH4aþb , where ’a’ corresponds to fraction of
Mn missing in the lattice and ’b’ is the fraction of Mn4+ replaced
4+
by Mn3+[43]. This was further evident in the binding energy
peak ~ 529.8–530.1 eV, which is ascribed to lattice oxygen Olatt
(O2

2 ), where the metal–oxygen bond is reduced from 67 to 64.8%
in SA as compared to S0. Similarly Zn doping in SZ causes Olatt to
drop to 63.3% and Oad to increase to 21.5%. The absence of Mn4+
state, indicate the possibility of formation of amorphous Zn doped
MnOOH/Mn2O3. Grangeon et al. [44] studied Zn sorption on dMnO2
and reported that the amount of Zn loading impacts the coordina-
tion environment as well as crystallinity of MnOx. Since MnOx
Fig. 4. High resolution spectra of S0 with deconvolution after Shirley type background subtraction for (a) Fe 2p3/2 (with multiplet structure), (b) Mn 2p3/2 (with multiplet
structure), (c) O 1s and (d) C 1s core levels.
5
Journal of Molecular Liquids 337 (2021) 116429
capping on c-Fe2O3 was amorphous, obtaining further insight into
its structure was not possible.
3.3. Magnetic properties of maghemite- manganese oxide core–shell
The room temperature magnetic properties of nanoparticles S0,
SA and SZ are shown in Fig. 7(a). The room temperature magneti-
zation curves do not show significant magnetic hysteresis. The
remanence (and coercivity) of sample S0, SA and SZ are 5.76
(0.0075), 7.1 (0.0077) and 8.17 (0.01) emu/g (T), respectively. The
saturation magnetization values of the S0, SA and SZ were found
to be ~58 ± 0.6, 49 ± 0.5 and 59 ± 0.6 emu/g, respectively, as shown
in Fig. 7(b). Addition of dopants caused a change in the vacancies
and structural distortions in the nanoparticles, which influences
the magnetic properties slightly. Mandal et al. [45] studied the
effect of vacancy concentration on the magnetic properties of
NiO core–shell system and reported that the magnetic moment
was affected by the interacting vacancies in the material and distri-
bution of vacancies in the particle volume. This was attributed to
the vacancy migration from the bulk, static disorder and change
in coordination number near the surface region. It was reported
that the oxygen vacancies and structural distortions causes the
weakening of hybridization of oxygen and the transition metal,
thereby weakening the double exchange interaction [46]. SA
showed the lowest magnetic moment, among the three samples,
suggesting that Ag doping caused a change in Oad and structural
distortion (due to the large size of silver ion) that resulted in a
weakening the double exchange interaction. The addition of
dopants also caused a change in the Mn3+/Mn4+ ratio as described
earlier. The outer shell electronic configuration of Mn3+ and Mn4+
ions consists of unpaired electrons i.e.3d4 and 3d3, respectively.
The larger the Mn3+/Mn4+, the higher the magnetic moment, due
C. Anushree, D. Nanda Gopala Krishna and J. Philip Journal of Molecular Liquids 337 (2021) 116429

Fig. 5. High resolution spectra of SA with deconvolution after Shirley type background subtraction for (a) Fe 2p3/2 (with multiplet structure), (b) Mn 2p3/2 (with multiplet
structure), (c) O 1s and (d) Ag 2p3/2 core levels.

Fig. 6. High resolution spectra of SZ with deconvolution after Shirley type background subtraction for (a) Fe 2p3/2 (with multiplet structure), (b) Mn 2p3/2 (with multiplet
structure), (c) O 1s and (d) Zn 2p3/2 core levels.

6
C. Anushree, D. Nanda Gopala Krishna and J. Philip
Table 1
Summary of the results from XPS analysis with the percentage of Fe/Mn, OAH, OAC
and H2O of S0, SA and SZ.
Catalyst S0 SA
Fe/Mn% 67 64.8
OAH% 16 21.2
OAC% 13 11.4
H2O% 4 2.6
the one extra electron of Mn3+ [47]. However, no clear trend was
observed with regards to the ratio of Mn3+/Mn4+ or vacancies in
the three systems, which may be due to the amorphous nature of
MnOx. The highest magnetic moment was 58.5 emu/g in SZ, which
was slightly more than that of S0. Due to the doping with Zn in SZ,
the oxidation state of manganese in the core–shell nanoparticles
was +3 alone. c-Fe2O3 and Mn2O3 are ferrimagnetic and antiferro-
magnetic, respectively. At the interface of c-Fe2O3 and MnOx, there
exists a non uniform intermixed layer, which may contains broken
bonds and uncompensated spins and hence the exchange interac-
tions at the interfacial layer can lower the magnetization value
[48]. Wang et al. [49] studied the magnetic properties in Mn2O3/
Mn3O4 nanoclusters and reported that magnetization originates
from both the phases Mn2O3 and Mn3O4, and uncompensated sur-
face moments of antiferromagnetic Mn2O3. Therefore, the presence
of uncompensated interfacial moments in SZ, may be responsible
for a slightly higher magnetic moment compared to SA and S0.
4. Dye degradation studies
The dye degradation and removal capability of S0, SA and SZ
were studied using BPB dye. The degradation of BPB via persul-
phate activator using the samples S0, SA and SZ were studied using
UV–Vis spectroscopy by varying the wt% of the catalyst (S0, SA and
SZ). Fig. 8(a) shows two peaks 436 and 592 nm for 0.1ɸ and 0.5ɸ of
SA (ɸ = 0.33 wt%) i.e. at very low concentration of SA catalyst. The
peaks at 436 nm and 592 nm were due to chromophore of the BPB
dye. With increase in the weight percentage, the peak at 592 disap-
pears and the maximum absorption peak was shifted to a lower
wavelength ~400 nm (hypsochromic shift), due to the breakage
of the BPB structure. Li et al. [50] studied the electochemical degra-
dation of BPB using boron doped diamond anode and reported a
faster decrease of 592 nm, peak intensity as compared to other
peak during electrolysis due to the rupture of benzene rings. Jones
et al. [51] studied the Rhodamine B dye degradation by Ta3N5/
W18O49 nanostructures and observed a hypsochromic shift from
554 to 532 nm, which was attributed to the removal of ethyl
groups of Rhodamine B molecules. Sydorchuk et al. [52] developed
Fig.7. (a) Room temperature magnetization curves of maghemite- MnOx nanoparticles S0, SA and SZ and (b) Enlarged view of the boxed region.
Journal of Molecular Liquids 337 (2021) 116429
clinoptilolite enriched with iron to study the photocatalytic degra-
dation of Rhodamine B and observed gradual blue shift of peak
from 553 nm, due to rupture of the chromophore rings in
SZ Rhodamine B. In the current case, the loss of 592 peak and
63.3 hypsochromic shift followed by decolourization unambiguously
21.5 confirm the successful degradation of BPB. Similar behavior was
10.7 observed for S0 and SZ as shown in Fig. 8(b). From Fig. 8(c), it
4.5
can be seen that among the three samples, SA showed the highest
degradation efficiency, indicating the better persulfate activation
efficiency of SA. The degradation percentage of SA, S0 and SZ with
1.8 wt% particles are 91, 61 and 51%, respectively. With increase in
the weight percentage of particle, the degradation efficiency also
increased in all the cases, due to increase in the activation sites.
SZ showed a lowest degradation efficiency with weight percentage
because of absence of multiple oxidation state of Mn. The catalytic
activity of Mn oxides depends on the oxygen mobility in the lattice
(Olatt) which allows a better oxidative transformation between var-
ious Mn oxidation states, density of exposed reactive adsorption
sites like vacancies and facets (Oad), presence of multiple valence
of Mn and its corresponding redox potential, specific surface area,
and degree of crystallinity [53]. In the case of S0, SA and SZ, the rel-
ative surface oxygen composition (Oad/Olatt) were 23.9, 32.7 and
33.9, respectively. The higher relative surface oxygen composition
in SA and SZ is attributed to the change in coordination, vacancies
and variation in oxidation state in Mn due to Ag and Zn doping.
Mountapmbeme et al. [54] studied the effect of addition of Co in
NiACo oxide to study the oxidation of unsaturated hydrocarbons
and found that increase in Co content increased the relative surface
oxygen composition (Oad/Olatt) in the oxide. The absence of multi-
ple oxidation state in SZ (only +3) can be the reason for the lowest
degradation efficiency in this sample. Fig. 8(d) shows the plot of ln
(A/Ao) as a function of time. Langmuir–Hinshelwood mechanism
explains the kinetics of heterogeneous catalytic processes, repre-
sented by [55]
dC kKC
r¼ ¼ ð2Þ
dt 1 þ KC
where r is the degradation rate of dye (mg/l min), concentration of
dye (mg/l), t is time, K is the adsorption coefficient of the dye (l/mg)
and k is the reaction rate constant (mg/l min). Under limiting con-
ditions, when KC1, the rate of degradation follows pseudo first
order kinetics and the equation is given by
dC
¼
kKC ¼
kapp C ð3Þ
dt
where kapp = kK represents apparent first order rate constant. Fur-
ther absorbance (A) is proportional to concentration (C) given by
the equation
7
C. Anushree, D. Nanda Gopala Krishna and J. Philip
Fig. 8. (a) Absorbance of BPB containing different wt% of SA (ɸ= 0.33 wt%) (b) Absorbance spectra of S0, SA and SZ at 1 and 3ɸ (c) percentage of degradation of S0, SA and SZ
with different wt% at equilibrium and (d) plot of ln(A/Ao) as a function of time; Inset of (d) shows the structure of bromophenol blue.
A sis of doping with silver) in SA to determine the maximum
ln ¼
kapp t
Ao
The kapp value obtained from the best fit is 0.0364 min
1 with
R2 = 0.95. The obtained kapp value is comparable with other reports
[23,56]. The structure of BPB is shown in Fig. 8(d) inset. BPB con-
tains two hydroxyl groups and at low pH, the hydroxyl groups
remain neutral. With increase in pH, one of the hydroxyl groups
is deprotanated and becomes anionic in nature. At very high pH,
both OH groups exist as dianionic form [57]. The BPB stock solution
was prepared at neutral pH. After the addition of persulfate and the
nanoparticles, the pH has changed to ~3.82, which indicate the
attributed to activation of persulfate. This causes the production
of SO
 +
4 which reacts with the solvent (water) and releases H there
by reducing the pH,[23] as shown by the equation (5)
SO
  þ 2

4 þ H2 O ! OH þ H þ SO4
No additional pH adjustment was done and the solution was
used as such. In Fenton and in most of the advanced oxidation pro-
cesses, the optimal pH used in the reaction ranges from 2 to 4. Liu
et al. [23] studied the degradation of acid red 73 by activated per-
sulfate using Fe3O4@activated carbon in an ultrasonic bath at 50 °C
and reported that the decolourization reaction rate was fast when
pH was 3. At pH > 7, more hydroxyl radicals are generated from
sulfate radicals, which is followed by the scavenging reaction
between hydroxyl radical and sulfate radicals.
Experiments were also performed using SA nanoparticles con-
taining different KMnO4:AgNO3 reactant ratio (used in the synthe-
Journal of Molecular Liquids 337 (2021) 116429
ð4Þ
percentage of degradation efficiency of BPB. Fig. 9(a) shows that
the percentage of degradation for various KMnO4:AgNO3 reactant
ratio of SA nanoparticles. The dye percentage of degradation using
1.6 wt% of SA nanoparticles containing 1:0.1, 1:0.25, 1:0.5, 1:0.75
of KMnO4:AgNO3 (0.2, 0.6, 1.3, 1.9 mmol of AgNO3, respectively)
were 75, 90.6, 92.4 and 64%, respectively. The degradation percent-
age of BPB is found to increase with SA when doped with silver
using 1:0.5 KMnO4:AgNO3 reactant. Further increase in silver
nitrate led to a reduction of degradation percentage. Fig. 9(b)
shows that with increase in weight percentage using SA nanopar-
ticles, containing increasing concentration of silver nitrate reac-
tant, the percentage of degradation also increases. However, SA
nanoparticles containing 1:0.5 and 1:0.75 of KMnO4:AgNO3 reac-
tant does not follow a regular trend with increase in wt%, which
can be due to reduced dispersion stability as compared to lower
ð5Þ
doping of silver. Fig. 9(c) showed the zeta potential of SA of differ-
ent doping of silver. The zeta potential of SA containing 1:0.1,
1:0.25, 1:0.5, 1:0.75 of KMnO4:AgNO3 were
35,
38,
20 and

19 mV, respectively. The system with higher the zeta potential
values are better electrostatically stabilized against the attractive
forces where agglomeration and flocculation are minimal. In addi-
tion, magnetic nanoparticles have a tendency to aggregate due to
dipolar interactions and zeta potential greater than ± 30 mV are
considered stable. The highest zeta potential (-37.7 mV) was seen
for SA prepared with 1:0.25 KMnO4:AgNO3 reactant. It should be
noted that SA nanoparticles used in all other experimental analysis
contained 0.6 mmol of silver nitrate reactant i.e. 1:0.25 of KMnO4:
8
C. Anushree, D. Nanda Gopala Krishna and J. Philip
Fig. 9. (a) Percentage of degradation of BPB with 1.6 wt% of SA catalyst using various KMnO4:AgNO3 reactant ratio used in the synthesis (b) percentage of degradation of BPB
with wt% using SA nanoparticles containing different concentration of silver nitrate reactant (c) zeta potential of SA and (d) percentage of degradation on recycling using
1.8 wt% of SA (1:0.25 KMnO4:AgNO3).
AgNO3 reactant because of its excellent stability. To study the
reusability of the SA nanoparticles for BPB degradation, recycling
experiments were performed. The SA nanoparticles were reused
by washing nanoparticles using hexane and ethanol. Fig. 9(d)
showed the BPB degradation efficiency for different cycles using
1.8 wt% of SA (0.6 mmol of silver nitrate). BPB degradation effi-
ciency after cycles 1–5 was ~91, 58.3, 35.6, 30.9 and 29.5%, respec-
tively. This reduction degradation efficiency was attributed to the
leaching of silver ions on repeated use. Degradation studies were
also performed using other dyes like Rhodamine B and crystal vio-
let. But on degradation, multiple peaks were observed indicating
the formation of complex intermediates. Further studies are
required to understand the intermediates.
4.1. Mechanism of dye degradation
To obtain further insight into the mechanism of activation of
persulfate by the nanoparticles, XPS analysis was performed on
the core–shell nanoparticles (SZ and SA) after the degradation of
BPB dye. SZ and SA were recycled 4 times before performing the
analysis.
The elements observed from the survey spectrum (Fig. 10(a)),
after the degradation of BPB dye through activation of persulfate
of SA are: iron, manganese, oxygen and carbon with atomic con-
centration in the ratio of 6.1:7.9:44.9:41.1, respectively. The ele-
ment silver was not observed, which indicates that silver was
fully leached into the solution after the experiment. In the case
of SZ shown in Fig. 10(b), the elements observed from the survey
spectrum of the sample are: iron, manganese, zinc, oxygen and car-
9
Journal of Molecular Liquids 337 (2021) 116429
bon with atomic concentration in the ratio of 6.2:8.3:1.0:47.7:36.8,
respectively. The Zn 2p3/2 region is deconvoluted with a single
broad symmetric peak at 1020.9 eV is shown in Fig. 10(c). The
amount of Zn was reduced from 4.5 to 1% in SZ nanoparticles
due to leaching after the dye degradation through persulfate
activation.
Fig. 11(a&b) shows the high resolution spectra of SA after dye
degradation through activation of persulfate of Mn 2p3/2 (with
multiplet structure) and O 1s core levels, respectively. The man-
ganese was present in both Mn3+ (72%) and Mn4+ (28%) states.
The O 1s region showed the bonding states of OAM (58.5%),
OAH (25.1%), OAC (13.4%) and H2O (3.0%), where ‘‘M” corresponds
to Fe/Mn. Fig. 11(c&d) showed that the manganese is present in
both Mn3+ (79%) and Mn4+ (21%) states while zinc is found to be
only in Zn2+ states. The O 1s region showed the bonding states of
OAM (60.3%), OAH (23.9%), OAC (12.0%) and H2O (3.8%), where
‘‘M” corresponds to Fe/Mn/Zn. The oxidation state of iron was
retained Fe3+ state in both the cases.
Table. 2 shows the summary of the XPS analysis of peak
~529.8–530.1 eV, where the percentage of lattice oxygen Olatt
(O2

2 ), Oad (~530.9 eV), percentage of Mn
3+/4+
of SA and SZ, before
and after dye degradation is listed. SA and SZ showed a change of
Olatt of ~6.3 and 3%, respectively. This findings suggest an
enhanced reactivity and mobility of lattice oxygen activity in SA
as compared to SZ and Oad corresponding to surface adsorbed
oxygen (O


2 or O ), OH groups and oxygen vacancies in SA,
(3.9% as compared to 2.4%) in SZ. This indicates that surface oxy-
gen species in the vicinity of AgAOAMn entities are more active
than those near ZnAOAMn entities [41]. Deng et al. [41] studied
C. Anushree, D. Nanda Gopala Krishna and J. Philip Journal of Molecular Liquids 337 (2021) 116429

(c)

2.0x104

1.9x104

1023 1020
Binding energy (eV)

Fig. 10. XPS survey spectrum of (a) SA (b) SZ after the degradation of bromophenol blue dye through persulfate activation and (c) high resolution spectra of Zn 2p3/2 core
levels of SZ with deconvolution after Shirley type background.

Fig. 11. High resolution spectra of SA and SZ after dye degradation through activation of persulfate with deconvolution after Shirley type background subtraction for (a&c)
Mn 2p3/2 (with multiplet structure) and (b&d) O 1s core levels, respectively.

Table 2
Results of XPS analysis of peak ~ 529.8–530.1 eV. The percentage of lattice oxygen Olatt (O2

2 ), Oad (~530.9 eV), percentage of Mn
3+/4+
of SA and SZ, before and after dye degradation
are given.

Pristine nanoparticles After dye degradation

Catalysts Olatt(%) Oad(%) Mn3+(%) Mn4+(%) Olatt(%) Oad(%) Mn3+(%) Mn4+(%)
SA 64.8 21.2 63 37 58.5 25.1 72 28
SZ 63.3 21.5 100 0 60.3 23.9 79 21

the O3 decomposition by Ag doped MnOx and reported that silver
addition can activate the lattice oxygen mobility due to decrease
in the coordination number with MnAO. Hou et al. [58] studied
the effect of benzene oxidation with and without doping of K+
cryptomalene sieves and observed that doping caused an increase
10
in lattice oxygen activity. This was because the addition of dopant
reduces the energy for the removal of lattice oxygen compared to
undoped ones. Therefore, it is concluded that the observed higher
catalytic activity of SA, as compared to SZ, is due to better redox
cycling of Mn3+/4+, higher activity of lattice oxygen and surface
C. Anushree, D. Nanda Gopala Krishna and J. Philip
oxygen species. Further, the single oxidation state of Mn (3+) of
SZ and the ZnAO bond in MnOx (thermodynamically favorable)
would have reduced the overall mobility and active surface sites
on the MnOx surface in SZ [59]. Therefore, the possible mecha-
nism of activation of persulfate on S0, SA and SZ nanoparticles
is adsorption of persulfate ion on Oad site. The presence of Oad
sites is one of the prerequisites for the proximity of persulfate
to adsorb on the surface [60]. Oad sites are formed due to insuffi-
cient coordination in the metal oxide lattice [43]. Such sites have
lower lattice stabilization energy and higher chemical reactivity.
In the nanoparticles, Mn3+ oxidizes to Mn4+ and transfer the elec-
tron to persulfate ion as shown schematically in Fig. 12(a). The
peroxide bond and the hydroxyl bond of persulfate is cleaved to
form SO
 
4 and OH radicals. To maintain the charge balance, the
lattice oxygen converts to O2 by donating electrons to two Mn4+
to form Mn3+. This results in decrease in Olatt, formation of
vacancy or OH
, which in described by the equation by the equa-
3þ 2


tion Mn4þ 1
a
b Mnb O2
4a
b OH4aþb , where ’a’ corresponds to fraction
of Mn missing in the lattice and ’b’ is the fraction of Mn4+
4+
replaced by Mn3+. This causes an increase in the Oad site, which
is in agreement with the XPS results.
Fig. 12(b-d) shows the photographs of samples showing dye
degradation steps using iron oxide-Ag doped MnOx(SA) magnetic
nanoparticles. Fig. 12(b) shows the photograph of BPB at pH 7.
Addition of magnetic nanoparticles and persulfate turns the solu-
tion to dark brown as shown in Fig. 12(c). The formation of bubbles
on top of the vial is due to gaseous products formed due to BPB dye
degradation. Fig. 12(d) shows the complete discoloration of dye,
indicating the efficient degradation of dye by SA nanoparticles.
These results suggest that the present approach is a facile and
robust way for degradation of BPB dye and easy separation of par-
ticles using a magnet.
(a)
S2O8
O2-
O2
(b) (c)
Fig. 12. (a) Schematic depicting the core–shell structure and the dye degradation mechanism. Photographs of the samples showing different steps involved in the dye
degradation:(b) BPB solution alone (c) dispersion of SA nanoparticles and persulfate into dye solution (d) separation of nanoparticles after dye degradation using a magnet.
11
Journal of Molecular Liquids 337 (2021) 116429
5. Conclusion
Iron oxide capped MnOx core–shell type nanoparticles, doped
with transition metal ions(Ag, Zn) were synthesized using
oxidation-precipitation followed by hydrothermal synthesis. The
iron oxide core with diameter of ~25–29 nm with an amorphous
MnOx shell of ~2.9 nm is prepared using this approach. The core–
shell structure without doping (S0), doping with Ag (SA) and
Zn2+ ion (SZ) were tested for their efficacy in dye degradation
through activation of persulfate. XPS analysis revealed that doping
of transition metal ions caused the change in the ratio Mn3+:Mn4+
with the order S0 < SA < SZ, where SZ showed only Mn3+ state. Sim-
ilarly the saturation magnetization values was highest for SZ
(58.5 emu/g) because of exchange interactions at the interfacial
layer. All the nanoparticles showed superparamagnetic behavior
with negligible coercivities and remanence, making them ideal
for magnetic separation. Efficiency of dye degradation was tested
using bromophenol blue dye. SA, S0 and SZ showed degradation
percentage of 91, 61 and 51% with 1.8 wt% of nanoparticles. SZ
showed the lowest degradation efficiency due to lack of multiple
oxidation state of Mn. The kinetics of degradation was determined
using Langmuir-Hinshelwood plot where the apparent first order
rate constant value is found to be 0.0364 min
1. The XPS analysis
revealed that the activity of SA catalyst is due to enhanced reactiv-
ity and mobility of lattice oxygen in doped samples. This approach
provides a new platform for efficient water remediation using dual
function magnetic nanoparticles.
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
2- CO2+ byproducts
SO4
.
(d)
C. Anushree, D. Nanda Gopala Krishna and J. Philip Journal of Molecular Liquids 337 (2021) 116429

CRediT authorship contribution statement [22] X. Song, C. Ren, Q. Zhao, B. Su, Simultaneous removal of Cr(VI) and triclosan
from aqueous solutions through Fe3O4 magnetic nanoscale-activated
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Omega 5 (2020) 13739–13750.
Formal analysis. John Philip: Conceptualization, Supervision, Writ-
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ultrasonic treatment for degradation of chlorpyrifos, ACS Omega 4 (2019)
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