Magnetically recyclable Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.

05O nano-photocatalyst:
Structural, optical, magnetic and photocatalytic properties

Mohd Qasima,

Khushnuma Asghara, b,

Braj Raj Singhb,

Sateesh Prathapania, 1,

Wasi Khanb,

A.H. Naqvib,

Dibakar Dasa, ,
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DOI: 10.1016/j.saa.2014.09.039

Highlights

Egg albumen assisted synthesis of novel visible light active Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O nano
photocatalyst.

Structural, optical, magnetic and photocatalytic properties have been studied.

Enhanced photo-decoloration of the Rhodamine B dye molecules under solar light irradiation.

Photo-decoloration through the production of reactive oxygen species (ROS).

The enhancement has been explained by reduced electronsholes recombination.

Abstract

novel

visible

light

active

and

magnetically

separable

nanophotocatalyst,

Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O (denoted as NZF@Z), with varying amount of Ni0.5Zn0.5Fe2O4, has

been synthesized by egg albumen assisted sol gel technique. The structural, optical, magnetic,
and photocatalytic properties have been studied by powder X-ray diffraction (XRD),
transmission electron microscopy (TEM), field emission scanning electron microscopy
(FESEM), fourier transform infrared spectroscopy (FTIR), UVvisible (UVVis) spectroscopy,
and vibrating sample magnetometry (VSM) techniques. Powder XRD, TEM, FTIR and energy
dispersive spectroscopic (EDS) analyses confirm coexistence of Ni 0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O
phases in the catalyst. Crystallite sizes of Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O in pure phases and
nanocomposites, estimated from DebyeScherrer equation, are found to be around 1525 nm.
The estimated particle sizes from TEM and FESEM data are (22 6) nm. The calculated
energy band gaps, obtained by Tauc relation from UVVis absorption spectra, of Zn0.95Ni0.05O,
15%NZF@Z, 40%NZF@Z and 60%NZF@Z are 2.95, 2.72, 2.64, and 2.54 eV respectively.
Magnetic measurements (field (H) dependent magnetization (M)) show all samples to be superparamagnetic in nature and saturation magnetizations (M s) decrease with decreasing ferrite
content in the nanocomposites. These novel nanocomposites show excellent photocatalytic
activities on Rhodamin Dye.

Graphical abstract

Figure options

Keywords
Nanocomposite;
Structural property;
Magnetic property;
Optical property;

 Photocatalysis

Introduction
The increasing extent of waste water generation from textile and other industries is posing a
serious threat to environmental remediation [1]. Constant disposal of noxious organic pollutants
lead to unrealizable side effects, since the mineralization efficiency of these pollutants by
conventional mineralization methods is inadequate [2]. The use of nanoparticles as catalysts in
organic transformations has attracted considerable interest in recent years, because of their
larger surface area-to-volume ratio [3]. Among them multifunctional fluorescent magnetic
nanocomposites have become the subject of intensive research due to their interesting multi
physicalchemical properties and potential applications in photocatalysis [4], antimicrobial
activities[5], magnetic resonance imaging (MRI), hyperthermia, bioseparation, drug delivery,
and cell labeling [6], [7],[8] and [9]. Semiconductor nanoparticles offer photocatalytic properties,
which are used to degrade organic pollutants in water under UV or solar light. Among them
ZnO is a well known photoluminescent semiconductor with wide band gap (3.4 eV), and large
excitonic binding energy (60 meV) at room temperature. It has widely been used as
photocatalyst due to its biocompatibility, ease of preparation, and stability. Unfortunately, ZnO,
being a wide band gap semiconductor, requires ultraviolet irradiation for its band gap
excitation [1] and [2]. The band gap of the photocatalyst determines the particular wavelength
of light that can be absorbed. Many commonly used photocatalysts have wide band gaps
(>3.1 eV) and can absorb only small portion of the solar light (UV light). It is worth mentioning
here that solar light contains 50% visible light and only 5% UV light. Thus, to utilize the
maximum solar light a photocatalyst that can absorb visible solar energy should be used [10].
The band gap of ZnO can be engineered by suitable doping in the ZnO lattice making them
suitable for visible light absorption [11], [12] and [13]. However, recovery of these ZnO catalyst
particles after the photocatalytic process is difficult. Fast recombination of the generated
electronhole pairs is another major drawback of pure semiconductor photocatalysts, which can
be avoided by combining P-type and N-type semiconductors, as it facilitates charge
migration [14], [15], [16] and [17].

Thus

commonly

used

non

magnetic

semiconductor

photocatalysts suffer from three main drawbacks, viz. less visible light activity, poor recovery,
and fast recombination of the generated electronhole pairs. Ferrite nanoparticles having band
gap 2 eV offer several advantages including visible light absorption, magnetic separability,
and enhanced photocatalytic efficiency due to the presence of extra catalytic sites in their
crystal structures [18]. Independently ferrites have rarely been used in photolocatalysis due to
its lower valence band potential and poor photocatalytic conversion efficiency [19].

Nanocomposite photocatalysts made up of semiconductor and magnetic materials, such as

ZnFe2O4/ZnO, CoFe2O4/ZnO, Fe2O3/ZnO, and Fe3O4/ZnO, are gaining increasing importance
because of their recyclability and higher photocatalytic activity than pure ferrites or ZnO [8].
Incorporation of ferrite in ZnO helps in improving the quantum yield of ZnO by slowing down the
recombination of photogenerated electrons and holes [20]. Since pure ZnO is not suitable for
absorption and utilization of visible region of the solar spectrum, in this study Ni doped ZnO
(Zn0.95Ni0.05O) with a band gap of 2.95 eV and Ni0.5Zn0.5Fe2O4 (band gap 2.2 eV) have been
chosen to prepare nanophotocatalysts for visible light active, magnetically separable, and
recyclable photocatalytic activity. Numerous surfactants and stabilizing agents, including
ethylene glycol, sodium dodecyl sulfate (SDS), and citric acid, have been used to control the
size and shape of ZnO NPs during synthesis [21]. These chemicals have varying degree of
toxicity and are difficult to remove from nanoparticle surfaces even after repeated washing.
Recently, natural bioresources with excellent biocompatibility are increasingly being used as
templates for synthesis of nanomaterials. Egg albumen offers several advantageous including
gelling, foaming, emulsifying, water solubility, heat setting and good binding capacity with metal
ions [22]. In the present investigation, Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O nanocomposites have been
prepared, for the first time, using egg albumen as biotemplate, which is environment friendly
and cost effective. In this study freshly extracted egg albumen was used because of its good
water solubility, metal binding ability, simple processing condition, amphiphilic nature, easy
availability and low cost. No external surfactant or stabilizing agent has been used to prepare
nanocomposites. The proteins of egg albumen, which have different functional groups, provide
not only stable suspension of ferrite in water but also may enhance selective deposition of
coating materials by virtue of its metal binding capacity. It plays an active role in ZnO synthesis
process by forming complex with Zn precursor and can provide nanoparticles with specific
morphologies and high surface area [21], [22] and [23]. The structural, optical, magnetic, and
photocatalytic properties of the composites have been studied by XRD, TEM, FESEM, FTIR,
UVVis spectroscopy, and VSM techniques.

Materials and methods

Materials
All reagents used in this synthesis were of analytical grade. Zinc nitrate (>98% Zn(NO 3)2.6H2O),
nickel nitrate (>98% Ni(NO3)2.6H2O), iron nitrate (>98% Fe(NO3)3.9H2O) from Sigma Aldrich and
citric acid, ammonia from SRL, India were used in this synthesis without any purification. Egg
white was obtained from fresh egg available in the market.

Ni0.5Zn0.5Fe2O4 NPs synthesis

Ni0.5Zn0.5Fe2O4 NPs were synthesized by gel-combustion method reported earlier [4]. Nickel
nitrate, zinc nitrate and iron nitrate with a molar ratio of 1:1:4 were dissolved in 100 ml of water.
Citric acid was added to the above nitrate precursor solution with citric acid: nitrate molar ratio
of 1:1. The resultant sol was continuously stirred at 90 C for 1 h. The gel so formed was
subjected to combustion at 300 C. A reddish brown powder was obtained, which was
grounded in mortar and pestle for subsequent use.

Synthesis of Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O nanocomposites

Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O nanocomposites were synthesized in two steps. First, a stable
dispersion of Ni0.5Zn0.5Fe2O4 nanoparticles in egg albumen solution, which served as seeding
materials, was obtained. Secondly, coating of Zn0.95Ni0.05O on Ni0.5Zn0.5Fe2O4 nanoparticle
surfaces was realized on the basis of chemical precipitation method. A typical synthesis
procedure is as below. Appropriate amount of Ni0.5Zn0.5Fe2O4 nanoparticles were dispersed in
20 ml of water taken in a beaker and 30 ml freshly extracted egg albumen was added to it
(beaker 1). In another beaker appropriate amount of zinc nitrate and nickel nitrate were
dissolved in 50 ml water (beaker 2). Both beakers were sonicated separately for 15 min to
ensure proper mixing. Stable dispersion of Ni0.5Zn0.5Fe2O4 nanoparticles was obtained in beaker
1. Aqueous solution of zinc nitrate and nickel nitrate, from beaker 2, was added drop wise to
the stable dispersion of Ni0.5Zn0.5Fe2O4 (NZF) in beaker 1 with continuous stirring. 30 min
vigorous stirring of the resultant solution followed by addition of 23 ml ammonia resulted in
brown color precipitate. Obtained precipitate was centrifuged, washed with alcohol & water and
dried at 50 C in oven. The dried NZF@Z precursor was calcined at 600 C for 3 h. Pure
Zn0.95Ni0.05O nanoparticles were prepared by the same method except the addition of ferrite
nanoparticles. Different nanocomposites were prepared by adding different percentages of
ferrite (Ni0.5Zn0.5Fe2O4) nanoparticles, 15%, 40% and 60% with Zn0.95Ni0.05O and labeled as
15%NZF@Z, 40%NZF@Z and 60%NZF@Z respectively. Obtained nanocomposites were
stored in glass vials at room temperature for further characterization.

Characterization
The X-ray diffraction (XRD) patterns of the powder samples were recorded with a MiniFlexTM II
benchtop XRD system (Rigaku Corporation, Tokyo, Japan) operating at 40 kV. Particle sizes
and morphology of the samples were measured by Transmission electron microscope (FEI
Tecnai T20G2 S TWIN TEM) and field emission scanning electron microscope (Carl Zeiss Ultra
55 FESEM). For both TEM and FESEM a pinch of nanoparticles were dispersed and sonicated
in alcohol and a drop of suspension was placed on carbon coated copper grid (for TEM) and
carbon tape pasted on stub (for FESEM) respectively. The elemental analysis of the sample
was carried out by Energy dispersive spectroscopy (EDS) attached with the FESEM. The

electronic absorption behavior at room temperature was analyzed using a UVVIS

spectrophotometer (Perkin Elmer Lambda 35). A suspension was prepared by dispersing
1 mg of nanopowder in 5 ml distilled water. Water was used as reference. The spectra was
recorded in the wavelength rang of 200800 nm from the aqueous suspension of the sample.
Fourier transformed infrared (FT-IR) analysis of the samples was conducted using Perkin-Elmer
2000 FT-IR spectrometer in the wavenumber range of 5004000 cm1. The magnetic
characterization of the sintered (800 C) pellets was performed using a Lakeshore (Model
7407) Vibrating Sample Magnetometer (VSM) in magnetic fields up to 1.5 T at ambient
temperature (298 K). The accuracy of the magnetization measurement was within 1%.

Photocatalytic activity measurement

The photocatalytic activities of the samples were estimated using Rhodamine B (RhB) dye
under solar light irradiation. All photocatalytic experiments were carried out under similar
conditions on sunny days between 11 am and 3 pm. In the photocatalytic experiment, 50 g/ml
of Zn0.95Ni0.05O, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4 catalysts were
added to 50 ml dye solution (of concentration 20 g/ml). Before irradiation the suspensions
containing

RhB

dye

and

Zn0.95Ni0.05O,

15%NZF@Z,

40%NZF@Z,

60%NZF@Z,

and

Ni0.5Zn0.5Fe2O4 were stirred in dark for 60 min to ensure the establishment of an

adsorption/desorption equilibrium. 5 ml aliquots were magnetically filtrated at a fixed time
interval (60 min) and was analyzed for the variation in maximum absorption band (
max

553 nm) using a UVvis spectrophotometer. The photo-decoloration of the RhB dye via the

photocatalytic

activities

of

Zn0.95Ni0.05O,

15%NZF@Z,

40%NZF@Z,

60%NZF@Z,

and

Ni0.5Zn0.5Fe2O4 was calculated following the formula:

Turn MathJaxon

where Co is the RhB dye initial concentration before photo-decoloration and C is the
absorbance after different time intervals. The role of active reactive oxygen species (ROS)
generated in the photocatalytic conversion was confirmed by trapping them with tert-butyl
alcohol (C4H10O) and disodium ethylenediaminetetraacetate dehydrate (EDTA-Na2;
C10H14N2Na2O82H2O) [4].

Results and discussion

XRD analysis

Powder XRD patterns of Ni0.5Zn0.5Fe2O4, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and

Zn0.95Ni0.05O recorded in the 2 range 2080 are shown in Fig. 1.

Fig. 1.
XRD pattern of Ni0.5Zn0.5Fe2O4, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z and Zn0.95Ni0.05O {Ni0.5Zn0.5Fe2O4 (Marked
with ), Zn0.95Ni0.05O (marked with #)}.
Figure options

Diffraction peaks (marked with ) centered around 30, 35, 37, 43, 53, 57, 62, and 74 can
be assigned to reflections obtained from (2 2 0), (3 1 1), (2 2 2), (4 0 0), (4 2 2), (5 1 1), (4 4 0),
and (5 3 3) planes, respectively, of crystalline Ni0.5Zn0.5Fe2O4 nanoparticles. The observed
diffraction pattern is found to be similar to the characteristics of the spinel cubic structure of
Ni0.5Zn0.5Fe2O4 {space group: Fd3 m (2 2 7), JCPDS card No. 520278}. The diffraction peaks
(marked with #) at 2 = 31.1, 33.7, 35.5, 46.8, 55.9, 62.2, 65.7, 67.3, 68.4, 72, and
76.3Corresponding to reflections from (1 0 0), (0 0 2), (1 0 1), (1 0 2), (1 1 0), (1 0 3), (2 0 0),
(1 1 2), (2 0 1), (0 0 4) and (2 0 2) planes, respectively, are of crystalline Zn0.95Ni0.05O
nanoparticles, which is representative of the hexagonal wurtzite structure {space group:
P63mc9(186), JCPDS card No. 790207}. XRD patterns of nanocomposites, 15%NZF@Z,
40%NZF@Z and 60%NZF@Z show characteristic peaks of both materials, which confirmed the
formation of crystalline nanocomposites. The X-ray intensity of the ferrite peaks increases with
increasing weight fraction of ferrites in the composites, similar to results reported by
Roychowdhury et al. [6]. No impurity peak is detected in the XRD patterns of these composites.
The average crystallite sizes of Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O were estimated from the full width
at half maximum (FWHM) of the corresponding most intense diffraction peaks, ((3 1 1) for
ferrite and (1 0 1) for Zn0.95Ni0.05O) using the DebyeScherrer equation, D = 0.9/cos ,
where is the wavelength of X-ray (Cu K = 1.540598 A), is the broadening of the diffraction

line measured at half of its maximum intensity in radians and is the Braggs diffraction angle.
The crystallite sizes of Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O were found to be 1625 nm and 22
27 nm respectively. XRD peaks broadening may also be due to lattice strain. The contributions
of lattice strain and crystallite size to diffraction peak broadening have been separated out
using WilliamsonHall equation, cos = 0.9/D + 4Sin , [24], where D is effective crystallite
size and is effective strain. The WilliamsonHall plot (cos vs Sin ) for a representative
sample, 40%NZF@Z, is shown in Fig. 2. From the linear fit to the experimental data the
crystalline size was estimated from the y-intercept, and the strain from the slope of the fitted
line. Lattice strains, , in Zn0.95Ni0.05O and Ni0.5Zn0.5Fe2O4 phases were found to be 0.006 to
0.004, both in pristine phases and nanocomposites. Similar strain values have been reported in
the literature for Fe3O4/ZnO nanocomposite and ZnO nanoparticle [6] and [24]. A shift in (1 0 1)
peak position in the diffraction pattern of Zn0.95Ni0.05O can be attributed to the presence of strain
in the crystal lattice. The effective crystallite sizes, calculated by WilliamsonHall method, were
1727 nm and 2030 nm for Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O respectively. The estimated
crystallite sizes obtained from both the methods (DebyeScherrers and WilliamsonHall) were
in good agreement. The obtained lattice parameters, estimated by Powder X-ray software,
area = b = 3.27 A, c = 5.24 A for Zn0.95Ni0.05O and a = b = c = 3.387 A for Ni0.5Zn0.5Fe2O4.

Fig. 2.
WilliamsonHall plot of 40%NZF@Z sample.
Figure options

Analysis of microstructure and phase composition

The FESEM images of NZF (a) and 40%NZF@Z (b) with corresponding EDS spectra (c and d)
and TEM images of NZF (a) and 40%NZF@Z (b) with corresponding diffraction patterns are
shown in Fig. 3 and Fig. 4respectively. It has been observed from FESEM and TEM images
that particle sizes in NZF are more uniform than those in 40%NZF@Z nanocomposite. NZF
nanoparticles are nearly spherical with particle sizes 22 6 nm measured both by FESEM
and TEM, as shown in Figs. 3(a) and 4(a) respectively. The distribution of particle sizes has

been shown in the insets of the respective Figs. 3(a) and 4(a). The distribution is broader in
pure NZF compared to that in 40%NZF@Z. The bigger particle sizes in composites compared
to those in pure Ni0.5Zn0.5Fe2O4 could be due to the coating of Zn0.95Ni0.05O around the surface of
Ni0.5Zn0.5Fe2O4 nanoparticles. The average particle sizes for 40%NZF@Z was 70 17 nm,
measured by FESEM & TEM. Fig. 3(b) shows the formation of agglomerates of 40%NZF@Z
nanoparticles but the distribution of particle sizes is narrower (as shown in inset of Fig. 3(b))
than that in pure NZF, as shown in inset of Fig. 3(a). The smaller particle sizes (22 nm) of
40%NZF@Z in Fig. 3(b) could be due to uncoating of Ni0.5Zn0.5Fe2O4 nanoparticles as also
observed by other researcher [25]. In TEM image of 40%NZF@Z the NZF particles (appear
dark) are seen to be surrounded by Zn0.95Ni0.05O particles (appear grey) confirming the coating of
the former by the later. Since ferrite is magnetic in nature it absorbs more electron than
Zn0.95Ni0.05O and hence appear darker than ZnO in the TEM image (Fig. 4(b)) [26].

Fig. 3.
FESEM images with particles size distribution histogram of Ni 0.5Zn0.5Fe2O4 (a), 40%NZF@Z nanocomposite (b) and
corresponding EDS spectra (c and d).
Figure options

Fig. 4.
(a) TEM image of Ni0.5Zn0.5Fe2O4 nanoparticles with inset shows the particles size distribution, (b) TEM image of
40%NZF@Z nanocomposite. (c) Indexed SAED pattern of spinel cubic Ni 0.5Zn0.5Fe2O4 (JCPDS card No. 520278).
(d) Indexed SAED pattern of 40%NZF@Z nanocomposite which shows both spinel cubic Ni 0.5Zn0.5Fe2O4 and
hexagonal Zn0.95Ni0.05O present in the sample (JCPDS card No. 790207).
Figure options

The EDS spectra (Fig. 3(c) and (d)) of Ni0.5Zn0.5Fe2O4 and 40%NZF@Z samples show only the
presence of Fe, Ni, Zn, and O in stoichiometric ratio, without any impurity peak, confirming the
purity of the phases. In 40%NZF@Z the mass ratio of Fe to Zn is 0.37, which is close to the
expected value 0.365. In 40%NZF@Z the weight% of O, Fe, Ni, and Zn are found to 33.05,
16.65, 5.14, and 45.15 respectively.
Fig. 4(c) and (d) shows the selected area electron diffraction (SAED) patterns of
Ni0.5Zn0.5Fe2O4 and 40%NZF@Z samples. The SAED pattern of Ni0.5Zn0.5Fe2O4 shows distinct

dotted ring pattern, which confirms the polycrystalline nature of the cubic spinel
Ni0.5Zn0.5Fe2O4 nanoparticles. The SAED pattern was indexed for cubic structure by estimating
the d-spacing from the ring pattern and comparing with the JCPDS card No. 520278 for NZF.
40%NZF@Z sample was also observed to be polycrystalline in nature. The SAED pattern of
40%NZF@Z shows a complex and mixed dotted ring pattern, which is due to the presence of
both the phases, cubic Ni0.5Zn0.5Fe2O4 and hexagonal Zn0.95Ni0.05O [6]. Presence of both phases
have also been confirmed by indexing the SAED patterns of other nanocomposites investigated
in this study.

Role of egg albumen

The mechanistic aspect of the synthesis of NZF@Z nanocomposites using egg albumen can be
explained as follows.
Egg albumen contains different types of proteins such as 60% ovalbumin, 12%
Ovotransferrin, and 11% Ovomucoid. These proteins have polar-COOH (hydrophilic) and
nonpolar-alkyl (hydrophobic) groups. It is difficult to prepare stable dispersion of bare ferrite
nanoparticles due to its hydrophobic nature. When ferrite nanoparticles are sonicated along
with albumen these polymeric proteins wrap the surface of nanoparticles and the hydrophilic
parts of the protein interact with water giving rise to stability of the suspension. Ovotransferrin is
well known for its iron binding property. Ovotransferrin folds into two globular lobes, each
containing an iron binding site located within the interdomain cleft of each lobe [27]. These iron
binding sites may also provide affinity toward iron of ferrites and help in decoration of
ovotransferrin on ferrite nanoparticles leading to improved stability of the resultant suspension.
Ni0.5Zn0.5Fe2O4 nanoparticles dispersed in water with egg albumen (water:albumen ratio 2:3
and ferrite concentration 10 mg/ml) shows improved stability than only in water, as shown in
digital photograph in Fig. 5(a). Ni0.5Zn0.5Fe2O4nanoparticles in water are seen to settle within
12 min of dispersion, whereas with egg albumen it is stable up to 3 h. To find out the role of
albumen in the synthesis process TEM analysis of albumen treated Ni 0.5Zn0.5Fe2O4 nanoparticles
was carried out after repeated washing with water. Formation of 56 nm thick amorphous layer
of albumen around the crystalline Ni0.5Zn0.5Fe2O4 nanoparticles has been confirmed by HRTEM
analysis as shown in Fig. 5(b)(d). Ni0.5Zn0.5Fe2O4 nanoparticles decorated with albumen on its
surface provide nucleation sites for Zn0.95Ni0.05O deposition [20]. Metal binding tendency of
albumen may attract zinc precursor to selectively nucleate on it [28]. Zn(OH)2 is formed when
zinc nitrate reacts with H2O. Functional groups of egg protein chelate with Zn atom and form
protein-Zn(OH)2 complex, which subsequently converted to hyderozincite intermediate. On
calcination at 500 C the hyderozincite intermediate decomposes to ZnO [21]. In our previous

report the mechanistic aspect of synthesis of pure ZnO nanoparticles using egg albumin as
biotemplate has been discussed in detail [21].

Fig. 5.
(a) The digital photograph shows the stability of dispersed Ni 0.5Zn0.5Fe2O4 in water without-a and with egg albumen-b
with respect to time.(b) TEM image of egg albumen coated Ni0.5Zn0.5Fe2O4 nanoparticles.(c and d) HRTEM image of
crystalline Ni0.5Zn0.5Fe2O4 nanoparticle, covered with 5 nm thick amorphous albumen layer. Inverse Fast Fourier
transform from the framed part in (c) is shown in the (d).
Figure options

Optical properties
UVvisible absorption spectroscopy is a powerful technique to explore the optical properties of
semiconducting nanoparticles. The absorbance of a material depends on several factors such
as band gap, oxygen deficiency, surface roughness and impurity centers [29]. Fig. 6 shows
UVvisible absorption spectra of Ni0.5Zn0.5Fe2O4, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z and
Zn0.95Ni0.05O.

Fig. 6.
UVVis absorption spectra of all the samples (Ni 0.5Zn0.5Fe2O4, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and
Zn0.95Ni0.05O).
Figure options

A sharp absorption peak at 373380 nm has been observed for Zn0.95Ni0.05O and all
nanocomposites. This characteristic absorption peak can be assigned to the intrinsic band-gap
absorption of Zn0.95Ni0.05O nanoparticles due to the electron transitions from valence band to the
conduction band (O2pZn3d)[21] and [22]. Presence of absorbance peak corresponding to
Zn0.95Ni0.05O in all samples confirms the formation of nanocomposites. Decrease in the
absorbance after lamda max (at 380 nm) in Fig. 6 or a dip after 3.3 eV in Fig. 7, may most
likely be due to lesser number of available states (low density of states) to absorb photons of
those wavelengths. No sharp absorption peak corresponding to Ni0.5Zn0.5Fe2O4 was observed in
the wavelength range studied in this investigation.

Fig. 7.
Tauc plot depicting energy band gap of Ni 0.5Zn0.5Fe2O4, 15%NZF@Z, 40%NZF@Z in the main panel and
60%NZF@Z and Zn0.95Ni0.05O in the inset.
Figure options

Optical band gaps of all the samples were estimated using the Tauc relationship, h = A(h

Eg)n, where is the absorption coefficient, A is a constant, h is the Plancks constant, is the
photon frequency, and Eg is the optical band gap [30]. The value of n could be 1/2, 3/2, 2 or 3
depending on the nature of electronic transition responsible for absorption and n = is for
direct band gap semiconductor. An extrapolation of the linear region of plot ( h)2 vs h gives
the value of the optical band gap, Eg, as shown in Fig. 7. Energy band gaps of Zn0.95Ni0.05O,
15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4 were 2.98, 2.72, 2.64, 2.54, and
2.24 eV respectively. The observed energy band gap of Zn0.95Ni0.05O nanoparticles is much
lower than that reported for pure ZnO nanoparticles (3.5 eV for ZnO with 16 nm crystallite
size) [31]. Energy band gaps of the nanocomposites are found to decrease with increasing
Ni0.5Zn0.5Fe2O4 content in the nanocomposites. This is due to the reduced band gap energy of
Zn0.95Ni0.05O in the nanocomposites in presence of Ni0.5Zn0.5Fe2O4.This reduction in band gap
energy has been explained in the literature in terms of mixing of the 4s orbital of Fe and Zn and
formation of the conduction band of Zn 0.95Ni0.05O at lower energy[6] and [32]. It may also be due
to the formation of sub band/s within the band gap of Zn 0.95Ni0.05O due to doping of metal ions
from Ni0.5Zn0.5Fe2O4 resulting in lowering of band gap energy.
FT-IR

spectra

of

all

the

samples

are

shown

in Fig.

8.

The

IR

spectra

of

Ni0.5Zn0.5Fe2O4 nanoparticles shows two principle absorption bands in the wavelength range
400600 cm1, the first band is around 422 cm1 and the second around 577 cm1. These two
vibration bands can be attributed to the intrinsic lattice vibrations of octahedral and tetrahedral
coordination complexes in the spinel structure, respectively [33]. The broad absorption band

400600 cm1 in all samples could arise from the simultaneous presence and overlapping of ZnO vibration mode at 453 cm1 in ZnO and two above mentioned absorption bands i.e. at 577 cm
1

and 422 cm1 in ferrite [6]. In IR spectra of 15%NZF@Z, 40%NZF@Z and 60%NZF@Z

nanocomposites, presence of FeO vibration mode at 577 cm1 as shoulder has been
observed, which increases with increase in ferrite content in these samples. Therefore, IR
results also confirm successful formation of nanocomposites. In addition to these absorption
peaks, the absorption band centered at 1121 cm1 may be attributed to the vibration mode of
CO, which could indicate the presence of decomposition products of albumen as impurities in
the samples [34]. The absorption band at 2364 cm1 can be assigned to trace of adsorbed or
atmospheric CO2[35].

Fig. 8.
FTIR spectra of Ni0.5Zn0.5Fe2O4 nanoparticles, 15%NZF@Z, 40%NZF@Z and 60%NZF@Z nanocomposites.
Figure options

Magnetic properties
The field dependent magnetic behavior of all the samples is shown in Fig. 9. Different magnetic
properties such as, saturation magnetization (Ms), remanent magnetization (MR) and coercivity
(Hc) have been derived from the magnetization curves. The Ms values for Ni0.5Zn0.5Fe2O4,
60%NZF@Z, 40%NZF@Z, and 15%NZF@Z were 56, 33, 23, and 8 emu/gm respectively. It is
found that Ms decreases linearly with decrease in ferrite content in these composite samples
(Fig. 9 inset). The decreasing saturation magnetization (Ms) is consistent with the increasing
non-magnetic Zn0.95Ni0.05O content in these samples[6]. Magnetization behavior at lower field
shows all the samples to be super-paramagnetic in nature with very low remanent
magnetization and coercivity. Remanent magnetizations of all the samples are found to be
0.41.4 emu/gm. The coercivities are 37, 44, 48 and 54 Oe for Ni0.5Zn0.5Fe2O4, 60%NZF@Z,
40%NZF@Z and 15%NZF@Z respectively. The increasing coercivity of the samples with
increasing Zn0.95Ni0.05O content could be attributed to increasing domain wall pining by the non-

magnetic Zn0.95Ni0.05O phase in these composites. The superparamagnetic behavior of

Ni0.5Zn0.5Fe2O4 nanoparticles could be attributed to very small particle sizes (22 nm) of this
sample. The smaller size particles may be equivalent to single domain (magnetic) particles,
where thermal vibration surpass the energy barrier for its spin reversal leading to
superparamagnetic

behavior.

Magnetic

separation

ability

of

the

dispersed

nanocomposites/photocatalysts in water has also been demonstrated and shown as a digital

image in the other inset of Fig. 9 for 15%NZF@Z (10 mg/ml), (a) without magnet, and (b) near
the magnet. It is observed that prepared nanocomposite photocatalysts have good dispersibility
in water and can be easily separated out from the solution by applying an external magnetic
field even though the magnetization of the sample is not too strong (8 emu/gm for 15%NZF@Z,
for example). Thus, the photocatalysts could be used repeatedly and opens up a possibility of
recyclability.

Fig. 9.
Room temperature magnetization behavior (MH) of all the samples in an applied field upto15000 Oe. The inset at
the top shows linear variation of Ms as a function of varying weight percent (wt%) of Ni 0.5Zn0.5Fe2O4 in the
nanocomposites. Digital image, in the other inset shows dispersed 15%NZF@Z nanocomposite in water
(10 mg/ml), (a) without magnet and (b) near the magnet.
Figure options

Analysis of photocatalytic activity

Enhanced visible-light driven photo-activity has been observed for some heterostructure
semiconductor nanocomposites previously [1] and [35], which motivated us to study the
photocatalytic activity of NZF@Z nanocomposites. The high photocatalytic activity of metal
oxide nanocomposites was attributed to the enhanced separation efficiency of photoinduced

carriers (electrons and holes) through electronic interaction. Thus, photo-decoloration study of
RhB dye was performed under solar light irradiation using Zn 0.95Ni0.05O, 15%NZF@Z,
40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4 as photocatalysts. The photo-decoloration
experiments were performed after proper adsorption of RhB dye on the surface of Zn0.95Ni0.05O,
15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4 photocatalysts. The extent of
photo-decoloration of RhB dye by Zn0.95Ni0.05O, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and
Ni0.5Zn0.5Fe2O4under solar light irradiation, at 25 C, is shown in Fig. 10A. The obtained photodecoloration data, under solar light irradiation, shows the promise of photocatalytic activity of
Zn0.95Ni0.05O, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4. The control (RhB dye
solution without nanocomposites) does not exhibit significant photo-decoloration under solar
light irradiation up to 120 min. This suggests that the photo-decoloration of RhB dye takes
place only by photocatalysis and not by photosensitization [4]. All the nanocomposites have
shown better photocatalytic activity than pure Zn0.95Ni0.05O or Ni0.5Zn0.5Fe2O4.The enhanced
photo-decoloration rates of RhB dye, observed in this study, may be attributed to the lager
surface area of the photocatalysts and reduced carriers (photo-induced) recombination through
electronic interaction in these nanocomposites [4]. The reduced carrier recombination can be
understood as follows. When light is absorbed by a pure semiconductor particle, an electron is
excited from VB to CB and an e/h+ pair is formed. The generated e and h+ may travel to the
surface of the particle and react with adsorbed species resulting in the desired process
(degradation of dye for example), or they may recombine, which is an undesired process. The
holes react with surface hydroxyl groups (OH) and H2O, to form highly reactive OH radicals,
which degrade organic dye molecules. The undesired high e /h+ recombination slows down the
photocatalysis process, especially, in case of pure semiconductor photocatalysts. To increase
the photocatalytic efficiency the e/h+ recombination has to be minimized. A scheme to reduce
the

recombination

of

e and

h+ is

to

prepare

heterostructure/nanocomposite

with

hetrojunction [36]. The band potentials of the component materials in the nanocomposite form a
heterojunction with a straddling gap, which may facilitate the transfer of charge carriers and
retard the electron hole recombination, resulting in improved photocatalytic performance [35]. In
other word, combining two photocatalysts with different band gap positions effectively causes a
greater separation of e/h+ pairs, allowing more of the species to be available for surface
reactions leading to degradation of the organic species [10] and [37]. Thus, as a magnetic
semiconductor material, NZF might not only add recyclability and visible light activity to the
catalyst nanoparticles, but also offer some synergetic enhancement of the catalytic activity by
forming the hybrid structure [38].

Fig. 10A.
RhB dye photo-decoloration efficiency under solar light irradiation by Zn 0.95O0.05, 15%NZF@Z, 40%NZF@Z,
60%NZF@Z and Ni0.5Zn0.5Fe2O4 photocatalysts.
Figure options

The identification of the main active oxidant (reactive oxygen species) in the photocatalytic
reaction is of great importance to understand the mechanism of the photocatalytic conversion
process. The chemical interactions between the photocatalysts (Zn 0.95Ni0.05O, 15%NZF@Z,
40%NZF@Z, 60%NZF@Z, and Ni0.5Zn0.5Fe2O4) and the charged groups of RhB molecules lead
to significant adsorption followed by high photo-decoloration. The role of the active oxidants
generated in the photocatalytic reactions involving Zn0.95Ni0.05O, 15%NZF@Z, 40%NZF@Z,
60%NZF@Z, and Ni0.5Zn0.5Fe2O4 was ascertained by quenching the reaction mixture in disodium
ethylenediaminetetraacetate dehydrate (EDTA-Na2; C10H14N2Na2O82H2O) (hole scavenger)
and tert -butyl alcohol (C4H10O) (radical scavenger) [4]. The photo-decoloration of RhB under
ultraviolet light irradiation was supressed after the addition of t-BuOH and EDTA-Na2, as shown
in Fig. 10B, which suggests that both radicals and holes are active species in this system. The
absorption of photons with sufficient energy (2.98, 2.72, 2.64, 2.54, and 2.24 eV of
Zn0.95Ni0.05O, 15%NZF@Z, 40%NZF@Z, 60%NZF@Z, and Ni 0.5Zn0.5Fe2O4, respectively) is the
necessary condition for photochemical reactions to proceed on the photocatalyst surface. The
band edges positions (VB and CB) of the AB2O4 type ferrite (ZnFe2O4/NiFe2O4) lies above the
corresponding band edges positions of ZnO respectively [1], [10], [39] and [40]. Reported CB
and VB potential of ZnFe2O4 is nearly at 1.54 eV (vs NHE) and +0.38 eV (vs NHE)
respectively [38] and [41]. The CB and VB potentials of ZnO is nearly at 0.76 eV (vs NHE) and
+2.7 eV (vs NHE) respectively [39] and [42]. Fig. 10C shows the schematic of the possible
mechanism in this photocatalysis process. Under solar light irradiation, the electrons (e ) from
the filled valence bands (VB) of Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O will be excited to the respective
empty conduction bands (CB), separately giving an equal number of holes (h+) in the

corresponding VBs. The presence of Ni0.5Zn0.5Fe2O4 nanoparticles will favor the utilization of
visible region of the spectrum due to its narrow band gap (2.2 eV) thereby enhancing the
photocatalytic activity under visible light irradiation [10] and [35]. Moreover, the difference in
band structures of Ni0.5Zn0.5Fe2O4 and Zn0.95Ni0.05O will facilitate photoinduced electrons transfer
from the CB of Ni0.5Zn0.5Fe2O4 to that of Zn0.95Ni0.05O and holes transfer from the VB of Zn0.95Ni0.05O
to that of Ni0.5Zn0.5Fe2O4, respectively [1]. These processes will efficiently hinder the
recombination of photogenerated electronhole pairs and considerably enhance the
photocatalytic activity under solar light irradiation. The resulted electronhole pairs recombine
or migrated to the surface of the particles and retort either with H 2O or OH to form OH, which
have strong oxidation ability and can destroy the dye molecules completely. The electrons will
also react with adsorbed molecular oxygen to form superoxide radical anion,

ions, which

will further react with water to give OH [1].

Fig. 10B.
Photodecoloration analysis shows the protective effect of disodium ethylenediaminetetraacetate dehydrate (EDTANa2; C10H14N2Na2O8 2H2O) (hole scavenger) (Q1) and tert-butyl alcohol (C4H10O) (radical scavenger) (Q2) on RhB
dye in presence of Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O nanocomposites (Q1-Column1 and Q2- Column2).
Figure options

Fig. 10C.
Schematic diagram illustrating the mechanism of photo-decoloration of RhB dye on Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O
surface under exposure to solar light.
Figure options

Conclusions
A

novel,

visible

light

active

and

magnetically

separable

Ni0.5Zn0.5Fe2O4/Zn0.95Ni0.05O

nanocomposites have been synthesized successfully by a simple and cost effective sol gel
technique using egg albumen as biotemplate. Powder XRD, TEM, FESEM, FTIR, UVVis
spectrophotometer, and VSM techniques have been used to characterize their structural,
optical, and magnetic properties. The photocatalytic activity of these nanocomposites has been
investigated by photo-decoloration study of Rhodamine B dye molecules. Enhanced photodecoloration of the Rhodamine B dye molecules by NZF@Z photocatalysts, compare to that by
pure Ni0.5Zn0.5Fe2O4 or Zn0.95Ni0.05O, have been observed under solar light irradiation, through the
production of reactive oxygen species (ROS). Narrow band gap of Ni 0.5Zn0.5Fe2O4 (2.2 eV),
relatively low band gap of Zn0.95Ni0.05O (2.95 eV), and reduced electrons-holes recombination
through electronic interactions have contributed significantly to this visible light active
photocatalysis process. This novel visible light active and magnetically separable photocatalyst
may immensely contribute to environmental remediation.

Acknowledgement
M. Qasim greatly acknowledges the financial support obtained from University Grants
Commission (UGC) in the form of MANF fellowship in carrying out this research work. BRS
thanks to CSIR, India for awarding Scientists Pool Scheme (13(8595-A) 2012-Pool). The
technical support received from the Centre of Excellence in Materials Science (Nanomaterials)
Aligarh Muslim University, School of Engineering Sciences & Technology (SEST), Centre for
Nanotechnology, and School of Physics at the University of Hyderabad is greatly appreciated.

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particle size for ZnO quantum dots

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Current address: Department of Metallurgical Engineering and Materials Science, IIT Mumbai,
Mumbai, India.