Vacuum 175 (2020) 109255

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Vacuum
journal homepage: http://www.elsevier.com/locate/vacuum

Synthesis of Gd2O3/CdO composite by sol-gel method: Structural,

morphological, optical, electrochemical and magnetic studies
Ramesh Sivasamy a, c, *, Potu Venugopal b, Edgar Mosquera d, e
a
Department of Chemical Engineering, Biotechnology and Materials, University of Chile, Beauchef 851, Santiago, Chile
b
Department of Chemistry, Pondicherry University, Pondicherry, 605014, India
c
Saveetha School of Engineering, Saveetha University, Chennai, Tamilnadu, 602105, India
d
Departamento de Física, Universidad Del Valle, A.A, 25360, Cali, Colombia
e
Centro de Excelencia en Nuevos Materiales, Universidad Del Valle, A.A, 25360, Cali, Colombia

A R T I C L E I N F O A B S T R A C T

Keywords: Metal-oxide based hybrid composite materials have broad applications in optical and electrochemical applica­
Composite tions. Hence, in this present work fabrication of multifunctional Gd2O3/CdO composite using the facile sol-gel
Sol-gel synthesis method. The crystalline structure, surface morphology, optical, electrochemical and magnetic behavior were
Rietveld refinement
studied. The composite formation, phase identification and crystalline structures of the cubic crystalline Gd2O3
Optical energy band gap
and CdO particles of the composite were confirmed by the X-ray diffraction. Surface morphology and chemical
Cyclic voltammetry
Paramagnetic behavior composition analysis were examined using scanning electron microscopy with energy dispersive X-ray analysis.
The optical energy band-gap of the composite from the diffuse reflectance spectra is found to be 1.27 eV and
2.76 eV. The electrochemical performance was estimated from the cyclic voltammetry analysis. The symmetric
nature of the voltammetry curve shows that this composite is a promising entrant for fast redox reactions with
enhanced specific capacitance. The magnetization curve explores the sample behaves as paramagnetic at room
temperature.

1. Introduction applications such as magnetic resonance imaging, catalytic, luminescent

devices and magnetocaloric materials [9,10]. Besides, the gadolinium
Transition metal oxide multifunctional hybrid composite materials element with a half-filled 4f-shell and 5d orbitals which offers to inter
have attracted much attention due to their interesting properties such as (4f-5d), intra (5d-5d) interaction through charge carriers and the empty
electrical, catalytic, magnetic, optical, and structural stability [1–3]. The 5d shell behave as a trapping center to prevent the recombination of
multifunctional composites were desired because of their integrated carriers for the visible light photocatalytic activities [11,12].
properties in a single material which often suitable for the futuristic However, using a single metal oxide may not be more effective
development in device miniaturization in several industrial applications because of their poor visual light absorption and the rapid recombina­
[4,5]. At present, energy storage and conversion are the great challenges tion process affects their properties. The low light harvesting, and
to advanced technology due to their high energy-consuming ability [6]. charge recombination process are the main issues to affect the photo­
Henceforth, the researchers have concentrated on a wide range of electrode, photovoltaic and catalytic applications of the nanoparticles.
multifunctional high-efficiency, environment-friendly and cost-effective To overcome these issues, two or more materials combined to pro­
composite materials for the photocatalytic and electrochemical appli­ duce a composite material with new properties for multifunctional ap­
cations [7,8]. plications [13,14]. The hybrid metal oxide composite materials can alter
Rare earth compounds with elements such as Nd, Gd, Eu, and Er are the band-gap and enhancing the visible light absorption. There are
characterized by multiple absorption energy levels in the ultraviolet several reports are presented to enhance the properties of the material
(UV) and visible range. The gadolinium oxide (Gd2O3) shows an inter­ by making composites with different materials [15–19].
esting optical and magnetic property that is used in several industrial Among the several transition metal oxide semiconductors, cadmium

* Corresponding author. Nanoscale Functional Materials Laboratory, Department of Chemical Engineering, Biotechnology and Materials, University of Chile, Floor
5, Office 533, Beauchef 851, Santiago, Chile.
E-mail addresses: rsivasamy@ing.uchile.cl, rameshsiva_chem@yahoo.com (R. Sivasamy).

https://doi.org/10.1016/j.vacuum.2020.109255
Received 28 November 2019; Received in revised form 5 February 2020; Accepted 10 February 2020
Available online 12 February 2020
0042-207X/© 2020 Elsevier Ltd. All rights reserved.
R. Sivasamy et al. Vacuum 175 (2020) 109255

transparency, chemical stability, and low-cost material [20,21].

Thus, in this work, we synthesize a Gd2O3/CdO hybrid composite by
a facile sol-gel method and studied their structure, morphology, optical,
electrochemical, and magnetic properties.

2. Experimental

2.1. Synthesis of Gd2O3/CdO composite

The Gd2O3/CdO composite was synthesized using a simple sol-gel

method via the nitrate-citrate route. Calculated amounts of reagent
grade solutions of cadmium nitrate tetrahydrate (CdN2O6⋅4H2O; 99.9%;
Himedia) and gadolinium nitrate (Gd(NO3)3) were kept stirring sepa­
rately. The Gd(NO3)3 was prepared using the gadolinium oxide (Gd2O3;
99.90%; Himedia) mixed with nitric acid (2 M) and stirred well for 15
min followed by 50 ml of 2 M citric acid solution (C6H8O7; 99.7%
Fig. 1. Powder X-ray diffraction patterns of Gd2O3/CdO composite. Himedia) was added. Then the pH of the solution was adjusted to ~7
using the liquid ammonia. The resultant solution was kept stirring for
oxide (CdO) is a n-type (II-VI) semiconductor with the band-gap value of 160 h, at ~45 � C to form a gel, then the gel was decomposed at ~100 � C
2.5 eV have been used for photovoltaic cells, transparent electrodes, to get the powder and finally, it was sintered at 600 � C for 6 h to achieve
photodiodes, phototransistors, IR detectors, liquid crystal displays, and polycrystalline Gd2O3/CdO composite. The systematic preparation is
sensors because of their properties such as low resistivity, optimum presented with supporting information (Fig. S1).
refractive index, suitable band-gap, high carrier mobility, optical

Fig. 2. SEM images (up), EDX profile (middle) and X-ray mapping (down) of Gd2O3/CdO composite.

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R. Sivasamy et al. Vacuum 175 (2020) 109255

Fig. 3. (a) UV–Vis DRS spectra, and (b) Tauc plot of Gd2O3/CdO composite.

2.2. Characterizations fitting. The structural refinement converged for two-phase system of
CdO and Gd2O3 cubic lattice type. The crystal structures of the two
Phase identification and the structural information of the composite phases are shown in Supplementary Information Fig. S3. In CdO crystal
were revealed using room temperature powder X’Pert PRO PANalytical structure (phase-1), the Cd atoms are placed in the Wyckoff positions of
diffractometer with CuKα as a source which was operated at 40 kV/30 4b, and the O atoms at the 4a position. In Gd2O3 structure (phase-2), Gd
mA power. The surface morphology and the chemical composition was atoms are occupied in 12b and 8a positions and the O atoms at the 24c
examined using the Hitachi-S3000H scanning electron microscopy with position. Rietveld refinement, XRD profile fit, and crystal information
energy-dispersive X-ray spectroscopy (SEM-EDX). Electrochemical were listed in supporting information (Fig. S3, Tables T1, T2 and T3).
behavior was observed from the cyclic voltammetry (CV) curve using a
three-electrode system. In the three-electrode system, the Pt wire and 3.2. Electron microscopy
KCl-saturated Ag/AgCl are used as a counter and reference electrodes.
The working electrode was prepared using a mixture of the Gd2O3/CdO The SEM-EDX was used to get the surface morphology and compo­
composite, carbon powders and polyvinylidene fluoride (PVDF) with the sition of the Gd2O3/CdO composite. Fig. 2 shows the SEM micrographs
ratio of 85:5:5 to confirm the conductivity. The 1 M aq. KOH was used as and EDX-profile of the sample. The composite shows agglomeration and
an electrolyte in the measurements. Magnetic behavior was identified the morphology was found to be irregular with rough surface. The EDX-
using a LAKESHORE VSM 7404 vibrating sample magnetometer (VSM). profile and X-Ray mapping of the composite show that the constituent
elements are present without impurities and distributed throughout the
3. Results and discussions surfaces.

3.1. X-ray diffraction studies

3.3. Optical absorbance studies
The phase identity, crystallite structure, and sizes of the synthesized
Gd2O3/CdO composite were investigated by XRD. Fig. 1 shows the XRD The optical absorbance spectrum of the Gd2O3/CdO composite is
pattern of Gd2O3/CdO composite compared with the simulated XRD shown in Fig. 3 (a). Here, we considered all transitions of the Gd2O3/
patterns of CdO and Gd2O3 structures. The predominant peaks in the CdO sample. Therefore, in the nanocomposite, the Gd2O3 nanoparticles
experimental pattern are in good agreement with the simulated CdO and show an indirect transition while CdO nanoparticles exhibit both, an
Gd2O3 patterns. The diffraction peaks at 32.81, 38.13, 54.87, 65.51, indirect transition and direct transition. Thus, Fig. 3(a) shows a strong
68.86, and 81.46 correspond to 111, 200, 220, 311, 222, and 400 planes photon absorption around 300 nm (4.13 eV) and 453 nm (2.74 eV),
which belong to a cubic lattice with Fm-3m (225) space group of CdO respectively. The absorbance band at 300 nm (4.13 eV) is attributed to
8
(Phase-1). The rest of the diffraction peaks at 20.21, 28.48, 33.21, 42.66 S7/2 → 6IJ (f-f) transitions of Gd3þ ions in Gd2O3 (Gd3þ; 4f7 electrons).
47.59, 56.65, 69.65 and 82.65 corresponds to the lattice planes of 211, This transition shows redshift (Δ ¼ 0.97 eV) with respect to reported
222, 400, 341, 440, 622, 800, 662, and 671 which corresponds to a cubic Gd2O3 (5.1 eV) [19]. Instead, the absorbance band at 453 nm (2.74 eV)
lattice type with I213 (199) space group of Gd2O3 (Phase-2). The XRD corresponds to the direct transition of CdO crystallites present in the
pattern of the as-synthesized sample reveals the existence of both phases nanocomposite and which is slightly show a blueshift (Δ ¼ 0.23 eV).
and the peaks do not affect each other which confirms the formation of On the other hand, the Tauc’s plot [6] have been used to verify the
Gd2O3/CdO composite. The phase-1 and phase-2 are present in the nature of the optical transition of the sample. The relation is written as
composite of 45.81% and 54.19% respectively. Eq. (2):
The average crystallite size of the composite from XRD peaks was αhυ ¼ A(hυ-Eg)n (2)
obtained using the Debye-Scherrer formula (Eq. (1)) [17,22].
where Eg-energy band gap, α-absorption coefficient, hυ-photon energy,
D ¼ Kλ/βcosθ (1) A-constant, and n is the transition types. Here, the direct transition (n ¼
where D stands for crystallite size, K denotes Scherrer constant, λ meant 1/2) has been considered and two energy band gaps at 1.27 eV and 2.76
for CuKα radiation, β is full width half maximum of the peak, and θ eV are observed in the composite, Fig. 3 (b). The calculated energy band
represents Bragg angle. The calculated average crystallite sizes of the gap of the composite is found to be 1.27 eV which is narrower than the
phase-1 are found to be 386 nm and the phase-2 is 257 nm. constituent oxides such as Gd2O3 (5.1 eV) [24] and CdO (1.98 eV, 2.51
Rietveld analysis for structural refinement was carried out using the eV) [20]. Therefore, the energy band gap of 1.27 eV (Δ ¼ 0.71 eV) and
FullProf package [23]. The pseudo-Voigt function was used for profile 2.76 eV (Δ ¼ 0.25 eV) could be related to the indirect and direct tran­
sition of CdO nanocrystals in the composite. Additionally, it was

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R. Sivasamy et al. Vacuum 175 (2020) 109255

Fig. 4. (a) Cyclic voltammetry at different scanning rates, and (b) specific capacitance plot of Gd2O3/CdO composite.

where Cs denotes specific capacitance (Cs, Fg 1), v signifies scan rate

(mVs 1), ω indicates sample weight (g), and ΔV represents applied po­
tential range (Va to Vc). The specific capacitance of as-synthesized of
Gd2O3/CdO composite is 521 Fg 1 at a scan rate of 5 mVs 1 is shown in
Fig. 4 (b). The reported specific capacitance of the CdO and Gd2O3
nanoparticles are 380 Fg 1 and 580 Fg 1 respectively [29,30]. Hence
the synthesized Gd2O3/CdO composite is higher than recently reported
constituent nanoparticles. The synergetic effects of the composite for­
mation enable the enhanced specific capacity of the sample.

3.5. Magnetic studies

Fig. 5 illustrates the magnetization curve of Gd2O3/CdO composite

was recorded in the range of �12000 G at 300 K. The magnetization
versus magnetic field curve indicates that the composite is para­
magnetic. Magnetic susceptibility, (χ) of the sample was calculated ac­
cording to the relation below (Eq. (4)) [4].
Fig. 5. Magnetization (M H) plots of Gd2O3/CdO composite.
M ​ ¼ χH (4)
observed that the composite presents an indirect transition with redshift where M denotes magnetization (emu g 1) and H is applied magnetic
compared to that of CdO and Gd2O3 reported. In a previous report, field. The calculated magnetic susceptibility of the composite is 1.857
Mosquera et al. studied the energy band gap in CdO/ZnO composites x10 6 emu/g which further confirms the paramagnetic behavior at 300
and found a slight redshift with the CdO content [20]. These results K.
confirm that CdO may have an indirect optical transition at lower the
direct absorption edge of 2.20 eV, thus the redshift can be attributed to 4. Conclusion
the indirect optical transition. Concerning the above, the variation in the
energy band gap suggests that this like composite-type can be used as In summary, the multifunctional cubic lattice Gd2O3/CdO composite
catalysts in oxygen and hydrogen evolution electrochemical reactions. was successfully synthesized by the sol-gel method. The calculated op­
tical energy band-gap energy is 1.27 eV which shows a strong redshift in
3.4. Electrochemical studies the energy band-gap with respect to the CdO and Gd2O3 reported. The
CV curves indicate that the reversible redox process implicate in the
Electrochemical properties were examined using cyclic voltammetry system. The specific capacitance of the composite is found to be 521
(CV) experiments. The CV curves of Gd2O3/CdO composite was Fg 1 at a scan rate of 5 mVs 1 which is higher than the reported CdO
observed in the potential range from 0.61 V to 0.61 V at various and Gd2O3 oxides. The shape of the magnetization curve reveals that the
scanning rate. The CV curves of the sample are shown in Fig. 4 (a). The composite is paramagnetic at 300 K. The estimated narrow optical en­
separate anodic and cathodic peaks about 0.342 V and 0.124 V are due ergy band-gap, specific capacitance and the magnetic properties of the
to the Cd2þ/Gd3þ to Cd/Gd0 reversible conversion. Throughout the scan composite can offer this material as a magnetically mediated electro-
rate increases, it also increases the current density. The current density photo catalyst under visible light region which can be explored in future.
increases and the quasi-rectangular shape CV curves indicate that the
composite has the pseudocapacitive behavior with the high surface area. Declaration of competing interest
The composite favorable for the fast-redox reactions [25–27].
The specific capacitance (Cs, F g 1) of the composite was estimated The authors declare that they have no known competing financial
from the CV curves using the following relation given below in Eq. (3) interests or personal relationships that could have appeared to influence
[28]. the work reported in this paper.
� Z Vc
Cs ¼ 1 ðνωðΔVÞ iVdV (3) Acknowledgment
Va

The author Ramesh Sivasamy is thankful to the National Fund for

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R. Sivasamy et al. Vacuum 175 (2020) 109255

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