Microstructural,Optical properties and Photocatalytic performance of Cobalt doped Cerium

Oxide nanocrystals
G.Killivalavana, B. Sathyaseelan 1*, I.Baskarann2, K.Senthilnathan3, E.Manikandan4,5
aResearch
Scholar, Department of Physics, Bharathiar University, Coimbatore-641046, Tamil Nadu, India.
1 Dept of Physics, University College of Engineering Arni , Anna University Chennai, Arni 632326, Tamil Nadu, India.
2Department of Physics, Arignar Anna Govt. Arts College, Cheyyar-604407, Tamil Nadu, India.
3Photonics Division, School of Advanced Sciences, VIT University, Vellore, 632014, Tamil Nadu, India
4Dept. of Physics, Thiruvalluvar University, TVUCAS Campus, Thennangur, 604408, Tamil Nadu, India
5UNESCO UNISA Africa Chair in Nanosciences & Nanotechnology, College of Graduate Studies, University of South Africa, Muckleneuk Ridge, Pretoria, South Africa.

ABSTRACT SEM and EDS analysis

Nanostructured materials have variety of potential uses in optical, electronic and
biomedical applications. The potential reason of their different applications can be The SEM image of Co-doped CeO2 nanoparticles the sample is observed to be irregular and
structural types lies from atomic size to bulk materials. On the nanometric scale, physical agglomerated. No other elements were detected, indicating that Co doped CeO2
and chemical properties of the materials are relatively different from those of bulk microspheres were free of impurity.
materials. The microstructural, optical and photocatalytic properties of undoped and Co
doped CeO2 nanocrystals (NCs) have been explored through several analytical methods,
viz. powder x-ray diffraction (PXRD), transmission electron microscopy (TEM), UV-visible
spectroscopy. XRD data analysis revealed face centred cubic (FCC) crystal symmetry of
the samples with average crystallite size in the range of 10–20 nm. Internal structure and
morphology observed by TEM exhibited almost identical cubical shape of the particles of
average size 20–26 nm. The effect of bandgap fine-tuning was observed in UV-visible
absorption spectra of CeO2 NCs with Co incorporation. Improvement in the photocatalytic
activity was observed for Co incorporated sample attributed to the degradation of TEM IMAGES
methylene blue dye under visible light absorption or/and fall in charge recombination rate
The particle size and morphology of the sample with is shown in the TEM image. The
between CeO2 and Co.
average particle size is around 18 nm. TEM analysis reveals that the particles are
INTRODUCTION nearly spherical in shape. The particle size determined through TEM was found to be
Doped cerium oxides have been intensively studied over the past years because in close agreement with the observed values from powder XRD studies.
of their high thermal stability, oxygen storage capacity and catalytic activity. The
properties of doped cerium oxides are closely related to their defect chemistry [1],
which is mainly determined by the size, charge and concentration of the dopant cations.
Doped cerium oxides have been reported for many applications such as photocatalysis
[2], fuel cell [3], CO preferential oxidation [4], water gas shift reaction [5], partial
oxidation of methane , and many others. Among these, cobalt can greatly increase the
oxygen interchange capacity compared with other metal elements, because of the
synergistic fenton and other reactions between the redox couple of the cerium
(Ce4+/Ce3+) and cobalt (Co2+) cations. In this work, Co-doped CeO2 with high specific Photocatalytic activity
surface area and good thermal stability were prepared by a simple co-precipitation
method . The photocatalytic performance was tested by measuring the enhancement To evaluate the influence of cobalt particles in modifying the dye degradation
mechanism was proposed as well. properties of methylene blue. Due to the reduction in the band-gap of Cerium oxide
nanoparticles after binding with Cobalt particles, it shows a higher photocatalytic activity in
PREPARATION TECHNIQUE the preferred visible light region, when compared with virgin CeO2 samples. With the
Mixed salt solution Ce(NO3)3 6H2O and Co(NO3)3 9H2O was added to the above assistance of Cobalt particles, nearly 95 % of the MB solution was degraded by 5% Co
solution under stirring and kept stirring for one hour. Then, a solution NaOH in 10 mL doped CeO2 Np’s under UV-visible light within the same reaction time of 6 hours (h). It has
distilled water was added drop wise to the mixture under further stirring for 1 h. The been indicated in Fig. This may be due to the fact that the recombination rate of the charge
mixture was aged at ambient temperature for 12 h. The precipitate was collected by carriers decreases exponentially with the increase in composite concentration, consequent
centrifugation, and washed twice with distilled water and once with ethanol. Then, the to the average distance between trap sites increase with an increase of binder restricted
precipitate was dried at 100◦C for 6 h.The dried powder was grounded thoroughly in a within a particle.
clean agate mortar and taken to further analysis. The crystalline quality and the grain
size of the samples were evaluated using X-ray diffraction (XRD) measurements. Powder
X-ray diffraction (XRD) technique (Rich Siefert, Model 3000) using CuKα1 (λ = 1.5406 Å)
radiation. The average crystallite size was calculated using Debye – Scherrer formula.
The morphological feature of the prepared samples was observed by scanning electron
microscope (SEM; Hitachi S-3000N).
RESULTS AND DISCUSSION
POWDER X – RAY DIFFRACTION STUDIES
The XRD patterns show that all diffraction peaks of the as-prepared samples
matched well with the powder diffraction data for CeO2 (JCPDS card No. 34-0394),
no extra XRD peaks arising from the cobalt oxide or other impurities are observed. CONCLUSION
The broadness of the diffraction peaks relates to a decrease in the crystallite size,
the crystallite size of as-prepared samples is estimated by Scherrer formula. The In summary, undoped and Co doped CeO2 NCs have been studied to explore their
values of crystallite size for the samples varied between 20 nm. structural, optical and photocatalytic properties through various techniques like XRD, TEM
and UV-visible spectroscopy. Average grain size estimated from the Debye–Scherrer
equation and TEM image analysis are very close to each other. The analysis of XRD data
established highly pure, single phase and cubic fluorite structure of the samples, and slightly
increase in latticeparameter was also observed with the reduction in crystallite size. The
effect of bandgap tuning was observed in UV-visible absorption spectra of CeO2 NCs with Co
incorporation. A blue shift in the absorption was observedin CeO2 NCs compared to its bulk
counterpart, as well as for Co doped CeO2 sample. It was also demonstratedthat the
crystallinity and luminescence properties of the nanocomposite increased significantly after
Co doping.Finally, Co doped CeO2 NCs exhibit superior photocatalytic performance
compared to undoped NCs for thedegradation of methylene blue dye under visible light.

UV–Vis diffuse reflectance spectra analysis

CeO2 is a direct band gap semiconductor , decrease in particle size should be REFERENCES
manifested a blueshift of absorption edge. The band gap undoped CeO2 is 2.91 eV and
for 1%,3% and 5% Co doped CeO2 is 2.8 eV, 2.62 eV and 2.51 eV respectively and it
shows band gap decreasing upon increasing dopant percentage and the reduction in
[1].W. Yu, J. Zhu, L. Qi, C. Sun, F. Gao, L. Dong, Y. Chen, J. Colloid Interface Sci. 364
the band gap leads higher absorption in visible region.
(2011) 435–442.
[2]. N. Chubar, V. Gerda, D. Banerjee, G. Yablokova, J. Colloid Interface Sci. 487
(2016) 388–400.
[3]. B. Liang, T. Suzuki, K. Hamamoto, T. Yamaguchi, H. Sumi, Y. Fujishiro, B.J.
Ingram, J.D. Carter, J. Power Sources 202 (2012) 225–229.
[4]. K. Sirichaiprasert, A. Luengnaruemitchai, S. Pongstabodee, Int. J. Hydrogen
Energy 32 (2007) 915–926.
[5].G.K. Reddy, P. Boolchand, P.G. Smirniotis, J. Catal. 282 (2011) 258–269. 7.A. Hornés, M.J.
Escudero, L. Daza, A. Martínez-Arias, J. Power Sources 249
(2014) 520–526.

POSTER PRESENTATION: International Conference on “Advanced Nanomaterials for Energy, Environment and Healthcare Applications” (ANEH-2018) , 31 AUG –01ST SEP 2018,
ORGANIZED BY K.S.R. College of Arts and Science for Women, Tiruchengode, Tamilnadu, India & Swansea University, United Kingdom.