Ceramics International 46 (2020) 786–794

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Facile synthesis of SnO2/NiO nano-composites: Structural, magnetic and T

catalytic properties
V.S. Suvitha, V.S. Devub, Daizy Philipa,∗
a
Department of Physics, Mar Ivanios College, Thiruvananthapuram, 695015, India
b
Department of Physics, N.S.S. College, Nilamel, Kollam, 691536, India

A R T I C LE I N FO A B S T R A C T

Keywords: Environmental pollution, one of the major challenges being faced by life forms on our planet, can be controlled
SnO2/NiO to some extent by degrading organic pollutants using heterostructured nanoparticles. This paper reports the
Nano-composites fabrication of SnO2/NiO nano-composites by a simple, environmentally benign and cost effective two – step
Ferromagnetism process via precipitation using tannic acid, a green reagent. Thermal analysis shows the optimum annealing
Catalysis
temperature as 500 °C.Fcc structured NiO and tetragonal SnO2 in the nanocomposite is confirmed from XRD
Methylene blue
EosinY
analysis. The interplanar spacing of 0.33 nm in SnO2 for (111) and 0.20 nm in NiO for (200) planes observed in
the HRTEM images confirms the composite formation. The synthesized composites characterized using UV–Vis
spectra give band gap energies of the samples. The elemental composition and oxidation states have been
supported by EDX and XPS analyses. VSM study carried out at room temperature show enhanced ferromagnetic
properties with increase in NiO content. The probe reactions degrading Methylene Blue and Eosin Yellow show
the effective catalytic potential of the synthesized SnO2/NiO nano-composite. Efficient degradation of 98% and
97% could be achieved in 14 and 20 min, respectively, showing suitability as a promising candidate in waste
water treatment.

1. Introduction Various methodologies have been employed in the synthesis of

Combination of two materials under ambient conditions is the
simplest method to enhance the deficient characteristics of a particular
material or to combine the attractive features of each material into one
[1,2]. Nickel Oxide and tin oxide nanostructures are being extensively
studied due to its wide range of potential applications. Tin oxide based
nano-composites incorporated by many other additives have been used
extensively in semiconductor gas sensors [3–5]. The fabrication of
oxide – diluted magnetic semiconductor (ODMS) by the addition of
transition metal ions such as Ni, Fe or Co offers ferromagnetic com-
pound having spintronics applications [6]. Nano-composite materials
have been subjected to extensive studies on photocatalysis and hy-
drogen production [7–9]. Coupling of semiconductors with different
band gap elements produces photocatalysts with high activity and
stability. The separation of photo-generated electron – hole pairs occurs
due to the excited electron transfer from high conduction band to the
low one. When n-type SnO2 is coupled with p-type NiO, SnO2/NiO
heterojunctions can be formed. Then the photogenerated electrons from
SnO2 can easily migrate to the NiO which favors the separation of such
electrons with holes thereby enhancing the photocatalytic activity [10].
nano-composites including sol-gel [11], pechini's method [12], thermal
decomposition method which requires toxic chemicals for the synthesis.
Here, co-precipitation method is employed for synthesizing nano-
composites in which no toxic reagents are used. The as-synthesized
nano-composites have been characterized using the various techniques.
TGA-DTA analysis is done to obtain the suitable annealing temperature
in which the samples undergo thermal decomposition from room tem-
perature to 900 °C. The phase purity and structural information's are
ascertained from XRD analysis. The surface morphology and elemental
composition are obtained from HRTEM and EDX, respectively. UV-VIS
spectroscopy is employed to obtain the band gap energy. The elemental
surface composition, the oxidation state and the chemical state of the
composites have been revealed from XPS analysis and the room tem-
perature magnetic property studied using VSM.
In the present study, catalytic potential of the synthesized SnO2/NiO
nano-composites in the chemocatalytic degradation of Methylene Blue
(MB) and Eosin – Yellow (EY) in the presence of excess Sodium
Borohydrate (NaBH4) is efficiently displayed. The degradation of both
the pollutants has been significantly enhanced with the incorporation of
nano-composites as catalysts. The rate of decrease in the intensity of the

∗
Corresponding author.
E-mail addresses: suvithv@gmail.com (V.S. Suvith), vsdevu@gmail.com (V.S. Devu), daizyp@rediffmail.com (D. Philip).

https://doi.org/10.1016/j.ceramint.2019.09.033
Received 6 August 2019; Received in revised form 3 September 2019; Accepted 3 September 2019
Available online 04 September 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
V.S. Suvith, et al. Ceramics International 46 (2020) 786–794

absorption band monitored using UV–Visible spectrophotometer shows

the degradation of the dye. The corresponding reaction rate constant
and the percentage of degradation are determined.

2. Materials and methods

Nickel (II) acetate, Tin (IV) Chloride and Tannic acid (TA) were
procured from Sigma Aldrich. Demineralized (DM) water was used as
the solvent. All the glass wares were washed thoroughly and rinsed
using aqua regia.
The two-step procedure for synthesizing SnO2/NiO nano-composites
is as follows. Initially, SnO2 nanoparticles were prepared by adding
0.01 M TA to the boiling solution of 0.01 M Tin (IV) Chloride under
constant stirring. The thick white precipitate thus formed was cen-
trifuged and washed several times with DM water followed by acetone.
The dried residue at room temperature was then annealed at 600 °C for
2 h to obtain the white colored SnO2 nanoparticles (S6). 100 mg of S6 Fig. 1. TGA-DTG curves of the nano-composite samples before annealing.
along with 0.01 M TA was mixed with the boiling solution of Nickel (II)
acetate under constant stirring. The precipitate was then washed
thoroughly with DM water and acetone and the residue was dried under
ambient conditions. The dried residue was then powdered with agate
mortar and pestle system and annealed at 500 °C for 3 h. The nano-
composite samples C1, C2 and C5 were synthesized by varying the
molarity of Nickel (II) acetate by keeping the molar ratios as 1:5, 1:10
and 1:25, respectively. For comparison, NiO nanoparticles (N6) were
also prepared with the same procedure as that for the synthesis of S6.
Thermogravimetric analysis (TGA) was done using PerkinElmer STA
6000 having TG sensitivity 0.2 mg and temperature accuracy ± 0.5 °C.
The crystalline phase of synthesized nanoparticles was obtained by X-
ray diffraction using XPERT PRO Diffractometer with Cu-Kα radiation
(λ = 1.54 0A). The UV–VIS absorption spectrum of the nano-compo-
sites were recorded using Varian, Cary 5000 Spectrophotometer having
a spectral range of 175 nm–3300 nm with an accuracy of ± 0.1 nm (UV-
VIS) and ± 0.4 nm (NIR). The morphology of the samples was studied
using Jeol/JEM 2100 High-Resolution Transmission Electron
Microscope having a magnification of 2000X to 1500000X. The surface
composition and chemical state of the samples were examined using
XRA–009 Thermo Scientific Nexsa XPS using Al Kα X-ray source with a
spot size of 10–400 Å. The room temperature magnetic behavior of the
sample were investigated using Lakeshore, USA, Model 7407 vibrating
sample magnetometer with a maximum magnetic field of 2.5 T and
dynamic moment range of 10−6 to 103 emu.
The catalytic property of C5nano-composite sample on the reduction
of organic dyes MB and EY by NaBH4 was investigated. 1 mM organic
dye and NaBH4 (1 mM) were mixed in DM water. Suitable quantities of
the synthesized nano-composite were added and mixed thoroughly. The
UV-VIS spectra of the mixture were recorded continuously at regular
intervals of time. The reaction rate constant was calculated from the
slope of the graph between ln (a/a0) and reaction time and the per-
centage of degradation was also determined.

3. Result and discussion Fig. 2. a)XRD pattern of synthesized nano oxides and nano-composite samples
b)Variation of calculated particle size for the prominent diffraction planes of Ni
Oand SnO2.
3.1. TGA-DTA analysis

TGA-DTA analysis is used to investigate the thermal change in the
decomposition of the as-prepared residues during annealing. The op-
timum annealing temperature for the nano complexes to get converted
into nano oxides is obtained from this. Fig. 1 shows the TGA-DTA of the
as-prepared nano-composite complexes carried out from room tem-
perature to 900 °C at a heating rate of 20 °C/min. The TGA curve ex-
hibits a three - step weight loss which is supported by the endothermic
peaks centered at 87 °C, 305 °C and 366 °C, respectively. The en-
dothermic peak at 87 °C showing a weight loss of 20.32% at the rate of
4.233%min−1 is associated with the evaporation of the adsorbed water
molecules in the sample. The major weight loss at 200–490 °C were
attributed to the conversion of the residue to the nanophase in two step
endothermic process at the rate of 8.308 %min−1 and 5.967 %min−1,
respectively. Further the TGA curve becomes stable with zero reduction
in the weight% indicating the complete conversion to the nano oxide
regime and hence the as-prepared samples were annealed at 500 °C to
get C1, C2 and C5 samples.
3.2. XRD analysis
The X-Ray Diffraction analysis of the SnO2/NiO samples C1, C2 and
C5 along with N6 and S6 were done for understanding the structural and

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Table 1
Structural parameters of NiO–SnO2nano-composites.
Sample hkl 2θ (0) dhkl (Å) Crystallite Size εstrain (x10−3)
Code (nm)

C1 NiO (111) 37.76 2.380 14.74 7.271

(200) 43.19 2.093 21.00 4.486
SnO2 (110)a 26.47 3.364 18.23 8.311
(101) 33.77 2.652 14.08 8.480

C2 NiO (111) 37.23 2.413 22.91 4.741

(200) 43.21 2.092 14.49 6.500
SnO2 (110)a 26.57 3.352 21.10 7.151
(101) 33.85 2.645 19.46 6.121

C5 NiO (111) 37.05 2.424 21.66 5.039

(200)a 43.09 2.097 20.99 4.498
SnO2 (110) 26.36 3.377 19.12 7.953
(101) 33.73 2.655 20.41 5.857

a
Preferential Plane Orientation.

phase purity. Fig. 2(a) shows the XRD pattern for the diffraction angles
from 200 to 900. All the diffraction peaks of N6 and S6 indexed in
Fig. 2(a) are broad showing the formation of NiO and SnO2 in the nano
regime. The Diffraction peaks of N6 are well matched with the JCPDS
card no. 00-73-1523 with face-centered cubic structure and that for S6
matches with JCPDS no. 00-041-1445 with tetragonal crystal system.
The crystallite size of both N6 and S6 calculated from the intense dif-
fraction peaks using Debye-Scherrer's formula [13]:

kλ
D=
βcosθ (1)

where k = 0.9 , is the shape factor, λ = 1.54 Å , wavelength of the X-Ray

used, β-the full-width half maximum of the diffraction peaks and θ the
corresponding diffraction angle. The crystallite size (D) calculated ac-
cordingly is obtained as ~11 nm and ~8 nm, respectively. The char-
acteristic peaks of N6 and S6 can be seen in the XRD pattern of C1, C2
and C5 samples which confirms the presence of NiO and SnO2 in it.
Furthermore, an increase in intensity of diffraction peaks of NiO can be
observed with increase in the molar ratio of the Nickel precursor.
Hence, it is clear that the synthesized nano-composites consists of cubic
Fig. 4. HRTEM images of C1(a, b) and C5(d, e) at different magnification c)
particle size distribution of C1f) particle size distribution of C5.
structured NiO and tetragonal structured SnO2 having preferential
plane orientation along (110) for samples C1 and C2 and along (200) for
the sample C5. The dhkl value calculated from XRD data are in good

Fig. 3. a) Absorbance spectra of nano-composites b) Diffuse Reflectance spectra of nano-composites c)K-M plot of the nano-composites.

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Fig. 5. Energy Dispersive X-ray Spectrum of the nanocomposites.

Table 2 agreement with the standard values of NiO (JCPDS no. 00-73-1523) and
Quantitative analysis of the nano-composites. SnO2 (JCPDS no. 00-041-1445). The microstrain in the nano-compo-
Sample Weight % of Element Atomic % of element sites can be evaluated using the relation [14]:

Ni Sn O Ni Sn O
β
ε=
4tanθ (2)
K Series L Series K Series L Series
The interplanar spacing, crystallite size and micro strain of the
C1 24.66 54.05 21.29 19.04 20.64 60.32 nano-composites corresponding to the hkl planes (111), (200) and
C2 31.85 46.84 21.31 23.91 17.39 58.7
(110), (101) of NiO and SnO2 nanoparticles, respectively, are tabulated
C5 49.04 29.61 21.35 34.53 10.31 55.16
in Table 1. The results are in agreement with the earlier reports that the
strain increases with reduction in the crystalite size due to the segre-
gation of the ions at the interface [15]. Absence of any peaks of im-
purity phases in the XRD pattern confirms the purity of the prepared

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samples. Fig. 2(b) shows the variation of particle size measured by

Debye – Scherrer relation for the prominent diffraction planes of NiO
and SnO2 for each sample. The average crystallite size of C1, C2 and C5
calculated from the prominent peaks of XRD are 17 nm, 19 nm and
20 nm, respectively. Eventhough the average crystallite size of C1 is less
than C5, the variation in the crystallite size calculated from all the peaks
is least for C5 (Fig. 2(b)). Also the peaks of NiO and SnO2 are showing
relatively equal intensity and hence the sample C5 is used for further
study.

3.3. UV-VIS analysis

The optical properties of the semiconducting nano-composite are

studied using the powerful nondestructive technique, optical absorption
spectral analysis. The UV-VIS absorbance and reflectance spectra of C1
and C5 are shown in Fig. 3(a and b), respectively. A blue shift in the
absorption edge can be seen with increase in the nickel ion con-
centration. From the diffuse reflectance spectra shown in Fig. 3(b), a
poor reflectance is observed up to 300 nm where the absorbance is
maximum. Thereafter, a rapid increase in the reflectance can be ob-
served and is more for C5 than sample C1. Kubelka – Munk relation is
used to calculate the direct band gap energy of the nano-composite
materials [16]. According to the relation, the K-M function is:

(1 − R)2
f (R) =
2R (3)

where R is the reflectance. A graph is plotted between (f (R) hν )2

versus
hv and the bandgap energy is determined by extrapolating the linear
portion of the plot to zero. As indicated in Fig. 3(c), the bandgap energy
of C1 is obtained as 3.16 eV and that for C5 is 3.46 eV and is even less
than that of the bulk NiO and SnO2 nanoparticles [10], which reveals
their photo catalytic potential [17].

3.4. HRTEM and EDX studies

Fig. 6. a) XPS survey spectrum of C5, S6 and N6 samples b) High resolution Sn
3d core – level spectrum of C5 and S6.
The morphology of the annealed samples C1 and C5 was investigated
by HRTEM and is shown in Fig. 4. The HRTEM images at various re-
solutions for the samples C1 and C5 is shown in Fig. 4(a and b) and
Fig. 4(d and e), respectively. The particles are almost spherical and are

Fig. 7. High resolution Ni 2P core – level spectrum of a) N6b) C5.

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Fig. 8. High resolution O 1S core – level spectrum of a) S6b) N6 and c) C5.

Fig. 9. Room temperature M − H curves of the samples a) S6 and N6b) C1c)C5.

Table 3 0.20 nm (Fig. 4(e)), respectively, could be associated with the (111)
Coercive magnetic Field (BC), Remanent Magnetization (MR) and Saturation plane and (200) plane of the cubic structured NiO nanoparticles and is
Magnetization (MS) of the nano-composites. in good agreement with the results obtained from XRD. This confirms
Sample BC (G) MR (emu/g) MS(emu/g) the formation of SnO2/NiO nano-composites. The size distribution of
the C1 and C5 nanoparticles is determined from HRTEM images. From
N6 160 1.57 9.06 the histogram shown in Fig. 4(c and f), the particle size ranges from 9 to
C1 435 0.14 0.44
20 nm for C1 and 9–26 nm for C5. Most of the particles in C1 are having
C5 433 0.77 2.41
a particle size of 17–18 nm and that for C5 is 20–21 nm which agrees
with the XRD results.
uniformly distributed. According to the high resolution TEM images From the EDX spectrum the phase purity of the nano-composites is
shown in Fig. 4(b, e), the inter-planar spacing of 0.33 nm is associated obtained and the elemental composition of the samples C1, C2 and C5
to the (111) plane of the tetragonal tin oxide nanoparticles (JCPDS no. are shown in Fig. 5 and its quantitative analysis done is listed in
00-041-1445). The inter-planar distance of 0.24 nm (Fig. 4(b)) and Table 2. An increase in the intensity of the peaks of NiO can be seen

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Fig. 10. UV–Vis absorption spectra (a) reduction of MB by NaBH4 unassisted by
nanocatalyst (inset shows the linear plot of ln (a/a0) with time) b)reduction of
EY by NaBH4 unassisted by nanocatalyst (inset shows the linear plot of ln (a/a0)
with time).
with increase in the molar ratio of the Nickel ion consistent with the
results obtained from the XRD and HRTEM.
3.5. X-ray photoelectron spectra
X-ray photoelectron spectroscopy (XPS) measurements have been
performed to illuminate the elemental surface composition, the oxida-
tion state and the chemical state of the elements, in the as prepared
nano-composites as well as in the pure SnO2 and NiO nanoparticles.
Fig. 6(a) shows the XPS survey scan spectrum of N6, S6 and C5 samples
and it confirms the presence of Sn, Ni, O and C peaks. The peak at
285 eV is attributed to the adventitious carbon based contaminant ad-
sorbed on the samples. The absence of any other peaks of impurities
confirms the high chemical purity of the samples [18].
The Sn 3d high resolution XPS spectra of S6 and C5 are shown in
Fig. 6(b). The doublet spectral lines of S6, centered at 495.4 eV and
486.9 eV corresponds to the Sn 3d3/2 and Sn 3d5/2 lines, respectively. A
spin – orbital splitting of 8.5 eV is observed between the peaks which
are due to the +4 oxidation of Sn in S6 sample [19,20]. However, a
remarkable red shift in the peaks of Sn 3d for the nano-composite
sample C5 can be observed. This shift towards the lower binding energy
side is associated with the reduction in the oxidation state from Sn4+ to
Sn2+ due to the presence of Ni ions.
The high resolution Ni 2P XPS spectra of N6 and C5 is shown in
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Ceramics International 46 (2020) 786–794
Fig. 7(a and b), respectively. Both the XPS spectra can be deconvoluted
into eight peaks. In Fig. 7(a), the binding energy at 853.6 eV and 856 eV
corresponds to Ni 2P3/2 peaks and the energies at 871.3 eV and
873.8 eV is attributed to Ni 2P1/2 peaks. The corresponding binding
energies of Ni 2P3/2 and Ni 2P1/2 peaks for the nano-composite C5
(Fig. 7(b)) is 852 eV, 853.7 eV and 869.3 eV, 870.9 eV, respectively. The
spin – orbital splitting for N6 is obtained as 17.7 eV and that associated
with C5 is observed as 17.3 eV. In metals having high electron density
near to the Fermi edge exhibits satellite peaks due to the interaction of
the leaving electrons with the valence electrons. When the core elec-
tron, removed by photo ionization, interacts with valence electrons
excites to the higher energy level. Hence the energy of the core electron
is reduced and satellite structures having higher binding energy are
formed. Such satellite peaks of Ni 2P3/2 and Ni 2P1/2 can be clearly seen
in Fig. 7. The red shift in the binding energy of Ni 2P XPS spectra of the
nano-composite is evident from the figure, similar to the case of Sn 3d
spectra. This shift in the binding energy may arise due to the different
electronegativity values of the metal ions which causes electron transfer
occurring between NiO and SnO2 particles thereby reducing the oxi-
dation state of the element. The value of the spin – orbital splitting and
the red shift in the binding energy indicates Ni is having a +2 oxidation
state [21].
The previous reports suggest that the O 1S core level peaks for
oxides lie between 529 eV and 532 eV. Fig. 8(a and b) gives the XPS
spectra of O 1S core level peaks for the samples S6 and N6 and can be
deconvoluted into two peaks. The binding energies at 531.8 eV and
530.9 eV (Fig. 8(a)) are attributed to the chemisorbed oxygen and the
O−2 ions in the lattice of SnO2. This result confirms the +4 oxidation
state of Sn in S6 [22]. In the O 1S spectrum of N6, as shown in Fig. 8(b),
the peak having binding energy 532.1 eV is associated with the defec-
tive sites within the oxides [23] and the peak at 529.3 eV corresponds
to the lattice oxygen [24]. As shown in Fig. 8(c), the O 1S peak of C5 can
be Gaussian divided into three peaks. The peak at 531.7 eV corresponds
to the deficient oxygen in NiO, the one at 530.8 eV corresponds to
O–Sn4+ bond and the peak at 529.9 eV is associated with Ni–O–Sn bond
[25]. All these results suggest the existence of pure NiO, SnO2 nano-
particle and also the formation of SnO2/NiOnano-composites.
3.6. Vibrating sample magnetometer study
The dependency of magnetization with the applied magnetic field
for the nano-composites is unveiled from the hysteresis curve. The room
temperature magnetic response of the nano-oxides and nano-compo-
sites is shown in Fig. 9. The coercive magnetic field, remanent mag-
netization and the saturation magnetization of N6, C1 and C5 are given
in Table 3. The M − H curve clearly reveals that N6 shows ferro-
magnetism while S6 exhibits diamagnetic property with negative
magnetic susceptibility (Fig. 9(a)). Fe, Co and Ni doped SnO2 nano-
particles have been reported to show ferromagnetic behavior at room
temperature [26,27]. The diamagnetic behavior of S6 is mainly due to
the lack of unpaired d electrons for any ferromagnetic ordering in the
4+ valence state which favors 4d10 electronic configuration of Sn in
SnO2 [28]. The ferromagnetic behavior of FCC structured N6 nano-
particle may be mainly due to the presence of Ni clusters [29]. But for
the samples C1 and C5 (Fig. 9(b and c)), the diamagnetic property of
SnO2 vanishes and becomes ferromagnetic due to the presence of NiO.
The saturation magnetization (Ms) and remanent magnetization (MR) of
the nano-composites increases with increase in the Ni concentration.
The mechanism for the ferromagnetic behavior of the SnO2/NiO nano-
composites may be stated as follows: the substitution of Ni2+ ion for
Sn4+ ions creates oxygen vacancies by escaping O2− to maintain charge
neutrality. These oxygen vacancies located near the Ni ions trap the
unpaired electrons and results in magnetic polarization. Hence these
oxygen vacancies play the vital role in enriching ferromagnetism in the
nano-composites [21].
V.S. Suvith, et al. Ceramics International 46 (2020) 786–794

Fig. 11. UV–Vis absorption spectra (a) reduction of MB by NaBH4 in the presence of C5 (inset shows the plot of % degradation with reaction time) b) the linear plot of
ln (a/a0) with time c) reduction of EY by NaBH4 in the presence of C5 (inset shows the plot of % degradation with reaction time) d)the linear plot of ln (a/a0) with
time.

Table 4 colorless leucomethylene blue (LMB) [33], which is a slow process.

The percentage of degradation of the dye (%D), reaction rate constant (k) and However, the addition of nano-composites enhances the rate of de-
time for the degradation of MB and EY in the presence and absence of C5. gradation of MB and is indicated by the reduction in intensity of ab-
Pollutant Nano-Catalyst Degradation time (min) K (min−1) %D sorption bands. The degradation of MB unassisted by nano-composites
over a period of 20 min is shown in Fig. 10(a). As the figure depicts, a
MB Nil – 0.006 – little degradation of MB has occurred during this time and the rate
C5 14 0.2227 98.4
constant of the reaction calculated from the slope of the plot between ln
EY Nil – 0.004 –
C5 20 0.2153 97.3 (A/A0) against reaction time is obtained as 0.006 min−1 (inset of
Fig. 10(a)). A rapid fall in the intensity of the absorption band is ob-
served upon the incorporation of the nano-composite C5 and the de-
3.7. Catalytic degradation of organic dyes gradation is completed in 14 min as shown in Fig. 11(a). The percentage
degradation of the reaction is calculated using the relation:
Environmental pollution due to various causes is a major threat to
A − A⎞
the living organisms. The non-degradable organic pollutants discharged %D = ⎛ 0
⎜ X 100
⎟

from various industries, holds a major share in polluting land as well as
water. In this scenario, photo-catalytic degradation using nanoparticles
plays a crucial role in the treatment of these environmental pollutants.
Enhanced photocatalytic activity of nano-composites due to better
electron hole pair transfer has been reported earlier [30,31]. The pre-
sent work is slated to accomplish the chemo-catalytic potential of as
prepared SnO2/NiO nanoparticles in the degradation of certain organic
dyes. Here, the degradation of MB and EY in the presence of excess
NaBH4 is used as the probe reaction. UV–Vis spectrophotometer is used
to monitor the degradation of the probe reaction in the presence and
absence of the nano-catalyst.
3.7.1. Degradation of MB
MB is an aromatic dye with a blue coloration in oxidized state and is
commonly used in textile industry. Aqueous MB shows a sharp ab-
sorption band at 664 nm which arises due to n-π* transitions with a
shoulder band at 614 nm. These major absorption peaks of MB are
associated with monomer and dimer form, respectively, in its oxidized
state [32]. The addition of NaBH4, reduces the blue colored dye to
⎝ A0 ⎠ (4)
Using this relation, the % D of MB in the presence of C5 is computed
as 98.4% and the corresponding plot is shown in the inset of Fig. 11(a).
The reaction rate constant for the chemocatalytic degradation of MB is
obtained as 0.2227 min−1 and the corresponding plot is shown in
Fig. 11(b).
3.7.2. Degradation of EY
EY, a water soluble fluorescein dye has diverse applications and it is
used in textile and paper industries [34]. The direct release of this
heterocyclic dye by the industrial sources is a major threat to the en-
vironment. The chromophore in the EY is responsible for its red color
which shows a strong absorption band at 517 nm. The shoulder band at
490 nm is attributed to its dimeric form [35]. The degradation of EY in
the presence of excess NaBH4 unassisted by nano-composite catalyst
over a period of 12 min is shown in Fig. 10(b). From the inset of the
figure a poor reaction rate constant of 0.004 min−1 can be observed. A
faster degradation of EY with the addition of nano-composites is evi-
dent from the decrease in the absorption at 517 nm as shown in

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Fig. 11(c). After a time period of 20 min the absorption band vanishes
and the rate constant of the reaction obtained from the slope of ln (A/
A0) against reaction time (Fig. 11(d)) is 0.2153 min−1. A percentage of
degradation of 97.3% is achieved using the nano-composite sample, C5,
as catalyst and is depicted in the inset of Fig. 11(c).
The catalytic potential of the synthesized nano-composites have
been depicted by the already described probe reaction. The reaction
rate constant (k) and percentage of degradation (% D) for each linear fit
are detailed in Table 4. The degradation of the MB and EY by NaBH4
can be explained by means of the redox reaction between the electron
provided by the nucleophilic BH4− and the electrophilic acceptor dye.
However, in the absence of the catalyst, the rate of reaction slows down
due to their large kinetic barrier. But the nano-composite particles re-
duces the time for reduction by adsorbing the reactant molecules
through electrostatic force and thereby initiating the electron transfer
by creating an intermediate potential level [36].
4. Conclusion
In the present study, a two-step tannic acid mediated synthesis of
SnO2/NiO nano-composite by wet chemical method is reported. An
optimized annealing temperature of 500 °C is obtained from the
thermal analysis. The structural and morphological characterization has
been done by XRD, HRTEM and EDX analyses and the results are in
good agreement with each other. The elemental composition, the oxi-
dation state and the chemical state of the elements in the nano-com-
posites analysed using XPS analysis technique. The optical bandgap
energy of the nano-composite obtained from the analysis of UV–Visible
measurements is 3.16 and 3.46 eV, respectively, for the sample C1 and
C5. Even though SnO2 is exhibiting diamagnetic property, the SnO2/
NiO nano-composite shows ferromagnetic behavior at room tempera-
ture. The catalytic activity of SnO2/NiO nano-composite is elucidated
through the degradation of MB and EY. The enhanced catalytic per-
formance of the synthesized nano-composites may find applications in
industrial waste water treatment thereby eliminating the hazardous
environmental pollutants while its ferromagnetic property may be
useful in magnetic sensors and memory devices.
Declarations of interest
None.
Acknowledgment
The authors thankfully acknowledge Sophisticated Analytical
Instrument Facility centres in STIC Cochin, National Centre for Earth
Science Studies (NCESS) Thiruvananthapuram, and SICC, Kerala
University, Thiruvananthapuram for technical support.
References
[1] M.L. di lorenzo, M. Frigione, Compatibilization criteria and procedures for binary
blends: a review, J. Polym. Eng. 17 (1997) 429.
[2] C. Corcione, M. Frigione, Characterization of nanocomposites by thermal analysis,
Materials 5 (12) (2012) 2960–2980.
[3] A.I. Aparnev, A.A. Golubchuk, I.S. Chukanov, N.F. Uvarov, Synthesis of nano-
composite materials in the SnO2-NiO system, Glass Phys. Chem. 38 (2012)
131–136.
[4] T. Pagnier, M. Boulova, A. Galerie, A. Gaskov, G. Lucazeau, Reactivity of SnO2-CuO
nanocrystalline materials with H2S: a coupled electrical and Raman spectroscopic
study, Sens. Actuators B 171 (2000) 134–139.
[5] I.S. Hwang, J.K. Choi, S.J. Kim, et al., Enhanced H2S sensing characteristics of Sno2
nanowires functionalized with cuo, Sens. Actuators B 142 (2009) 105–110.
[6] X.L. Wang, Z.X. Dai, Z. Zeng, Search for ferromagnetism in Sno2 doped with
transition metals (V, Mn, Fe, and Co), J. Phys. Condens. Matter 20 (2008) 045214.
[7] W. Cui, M. Shao, L. Liu, Y. Liang, D. Rana, Enhanced visible-light-responsive pho-
tocatalytic property of PbS-sensitized K4Nb6O17 nanocomposite photocatalysts,
Appl. Surf. Sci. 276 (2013) 823–831.
794
Ceramics International 46 (2020) 786–794
[8] W. Cui, D. Guo, L. Liu, J. Hu, D. Rana, Y. Liang, Preparation of ZnIn2S4/
K2La2Ti3O10 composites and their photocatalytic H2 evolution from aqueous
Na2S/Na2SO3 under visible light irradiation, Catal. Commun. 48 (2014) 55–59.
[9] W. Cui, Y. Qi, L. Liu, D. Rana, J. Hu, Y. Liang, Synthesis of PbS-K2La2Ti3O10 com-
posite and its photocatalytic activity for hydrogen production, Progr. Nat. Sci.: Mat.
Int. 22 (2012) 120–125.
[10] R.M. Mohamedand, E.S. Aazam, Photocatalytic oxidation of carbon monoxide over
NiO/SnO2 nanocomposites under UV irradiation, J. Nanotechnol. 2012 (2012)
794874.
[11] H.K. Schmidt, E. Geiter, M. Mennig, H. Krug, C. Becker, R.P. Winkler, The sol-gel
process for nano-technologies: new nanocomposites with interesting optical and
mechanical properties, J. Sol. Gel Sci. Technol. 13 (1998) 397–404.
[12] R.H.R. Castro, P. Hidalgo, J.A.H. Coaquira, J. Bettini, D. Zanchet, D. Gouvea,
Surface segregation in SnO2- Fe2O3 nanopowders and effects in mossbauer spec-
troscopy, Eur. J. Inorg. Chem. 11 (2005) 2134.
[13] M. Ashraf, S.M.J. Akhtar, A.F. Khan, Z. Ali, A. Qayyum, Effect of annealing on
structural and optoelectronic properties of nanostructured ZnSe thin films, J. Alloy.
Comp. 509 (2011) 2414–2419.
[14] P. Pascariu, A. Airinei, N. Olaru, I. Petrila, V. Nica, L. Sacarescu, F. Tudorache,
Microstructure, electrical and humidity sensor properties of electrospun nio-sno2
nanofibers, Sens. Actuators, B 222 (2016) 1024–1031.
[15] P. Hidalgo, R.H.R. Castro, A.C.V. Coelho, D. Gouvêa, Surface segregation and
consequent SO2 sensor response in SnO2-NiO, Chem. Mater. 17 (2005) 4149–4153.
[16] V.D. Malčić, Ž.B. Mikočević, K. Itrić, Kubelka-munk theory in describing optical
properties of paper (I), Tech. Gaz. 18 (2011) 117–124.
[17] F. Motahari, M.R. Mozdianfard, F. Soofivand, M. Salavati-Niasari, NiO nanos-
tructures: synthesis, characterization and photocatalyst application in dye pollution
wastewater treatment, RSC Adv. 4 (2014) 27654–27660.
[18] G. Zorn, L. Li-Hong, L. Árnadóttir, H. Wang, L.J. Gamble, D.G. Castner, M. Yan, X-
ray photoelectron spectroscopy investigation of the nitrogen species in photoactive
perfluorophenylazide-modified surfaces, J. Phys. Chem. C 118 (2014) 376–383.
[19] C. Gu, Y. Cui, L. Wang, E. Sheng, S. Jae-Jin, J. Huang, Synthesis of the porous NiO/
SnO2 microspheres and microcubes and their enhanced formaldehyde gas sensing
performance, Sens. Actuators, B 241 (2017) 298–307.
[20] N. Jayababu, M. Poloju, J. Shruthi, M.V.R. Reddy, Semi shield driven P-N hetero-
structures and their role in enhancing the room temperature ethanol gas sensing
performance of nio/sno2 nanocomposites, Ceram. Int. 45 (2019) 15134–15142.
[21] A. Ahmed, T. Ali, M.N. Siddique, A. Ahmad, P. Tripathi, Enhanced room tem-
perature ferromagnetism in Ni doped SnO2 nanoparticles: a comprehensive study,
J. Appl. Phys. 122 (2017) 083906.
[22] X.Q. Pan, L. Fu, Oxidation and phase transitions of epitaxial tin oxide thin films on
(1012) sapphire, J. Appl. Phys. 89 (2001) 6048.
[23] L. Marchetti, F. Miserque, S. Perrin, M. Pijolat, XPS study of Ni-base alloys oxide
films formed in primary water conditions of pressurized water reactor, Surf.
Interface Anal. 47 (2015) 632–642.
[24] M.A. Peck, M.A. Langell, Comparison of nanoscaled and bulk NiO structural and
environmental characteristics by XRD, XAFS, and XPS, Chem. Mater. 24 (2012)
4483–4490.
[25] J. Zhang, D. Zeng, Q. Zhu, J. Wu, Q. Huang, W. Zhang, C. Xie, Enhanced room-
temperature NO2 response of NiO-SnO2 nanocomposites induced by interface
bonds at p-n heterojunction, Phys. Chem. Chem. Phys. 18 (2016) 5386–5396.
[26] S. Mehraj, M.S. Ansari, Alimuddin, Structural, electrical and magnetic properties of
(Fe,Co) Co-doped Sno2 diluted magnetic semiconductor nanostructures, Physica E
65 (2015) 84–92.
[27] F.H. Aragón, J.A.H. Coaquira, P. Hidalgo, S.L.M. Brito, D. Gouvêa, R.H.R. Castro,
Experimental study of the structural, microscopy and magnetic properties of Ni
doped Sno2 nanoparticles, J. Non Cryst. Sol. 356 (2010) 2960–2964.
[28] F.H. Araǵon, J.A.H. Coaquira, P. Hidalgo, S.L.M. Brito, D. Gouvêa, R.H.R. Castro,
Structural and magnetic properties of pure and nickel doped Sno2 nanoparticles, J.
Phys. Condens. Matter 22 (2010) 496003.
[29] Z.N. Kayani, M.Z. Butt, S. Riaz, S. Naseem, Synthesis of nio nanoparticles by sol-gel
technique, Mater. Sci. 36 (2018) 547–552.
[30] S. Asaithambi, R. Murugan, P. Sakthivel, M. Karuppaiah, S. Rajendran, G. Ravi,
Influence of Ni doping in SnO2 nanoparticles with enhanced visible light photo-
catalytic activity for degradation of Methylene blue dye, J. Nano Sci. Nanotechnol.
19 (2019) 4438–4446.
[31] R. Saravanan, S. Karthikeyan, V.K. Gupta, G. Sekaran, V. Narayanan, A. Stephen,
Enhanced photocatalytic activity of Zno/CuoNanocomposite for the degradation of
textile dye on visible light illumination, Mater. Sci. Eng. C 33 (2013) 91–98.
[32] U.P. Azad, V. Ganesan, M. Pal, Catalytic reduction of organic dyes at gold nano-
particles impregnated silica materials: influence of functional groups and surfac-
tants, J. Nano Res. 13 (2011) 3951–3959.
[33] V.S. Suvith, D. Philip, Catalytic degradation of Methylene blue using biosynthesized
gold and silver nanoparticles, Spectrochim. Acta 118 (2014) 526–532.
[34] S. Acharya, B. Rebery, Fluorescence spectrometric study of eosin yellow dye–-
surfactant interactions, Arab. J. Chem. 2 (2009) 7–12.
[35] V.R. Batistela, D.S. Pellosi, F.D. de Souza, W.F. da Costa, S.M.O. Santin, V.R. de
Souza, W. Caetano, H.P.M. de Oliveira, I.S. Scarminio, N. Hioka, pKa determina-
tions of xanthene derivates in aqueous solutions by multivariate analysis applied to
UV–vis spectrophotometric data, spectrochim, Acta A 79 (2011) 889–897.
[36] K. Mallick, M. Witcomb, M. Scurrell, Silver nanoparticle catalysed redox reaction:
an electron relay effect, Mater. Chem. Phys. 97 (2006) 283–287.