Home / Advanced Science Letters, Volume 24, Number 8
Development
and
Catalytic
Application of Palladium Doped
Titania (Ti0.98Pd0.02O2) Through Low
Temperature Solution Combustion
Method
/content/asp/asl/
1
Authors: Obaiah, G. O1; Shivaprasad, K. H1; Bhat, K. Srikanth1; Hegde, M. S1; Mylarappa, M2
Source: Advanced Science Letters, Volume 24, Number 8, August 2018, pp. 6004-6007(4)
Publisher: American Scientific Publishers
DOI: https://doi.org/10.1166/asl.2018.12235
Abstract
The objective of the research was mainly focused on development of TiO 2 and Palladium doped TiO2 by low
temperature solution combustion method using Glycine as fuel. Palladium substituted Titania (Ti0.98Pd0.02O2)
was prepared by taking stoichiometric amounts of titanyl nitrate, palladium chloride and Glycine by solution
combustion method. The accurate size and morphology of the doped metal oxide was studied Scanning
electron microscope (SEM). The phase composition of the palladium substituted Titania (Ti 0.98Pd0.02O2) was
confirmed from powder X-ray Diffractometer (PXRD). The functional groups are analyzed by Fourier
transfer infrared spectroscopy. The doped metal oxide shows superior catalytic performance.
Keywords: Catalytic Application; PdCl2; Ti(OC3H7)4; Ti0.98Pd0.02O2; TiO2
Document Type: Research Article
Affiliations: 1: Department of Chemistry, Vijayanagara Sri Krishna Devaraya University, Bellary 583104,
Karnataka, India 2: Research Centre, Department of Chemistry, AMC Engineering College, Bengaluru
560083, Karnataka, India
Publication date: August 1, 2018
Development and Catalytic Application of Palladium Doped Titania
1
(Ti 0.98 Pd 0.02 O2) through low temperature Solution Combustion Method
G.O. Obaiah1, a, K.H. Shivaprasad*1, K. Srikanth bhat1, M.Mylarappa2
1
Department of chemistry, Vijayanagara Sri Krishna Devaraya University, Bellary.
a
2
Research center, Talent development center, IISC, Kudhapur, Chitradurga.
Research Centre, Department of Chemistry, AMC Engineering College, Bannerghatta
Road Bengaluru-560083, and India (Affiliated to Tumkur University)
Corresponding Author
E-mail: 1*khsprasad60@gmail.com
Abstract
The objective of the research was mainly focused on development of TiO2 and Palladium
doped TiO2 by low temperature solution combustion method using glycine as fuel.
Palladium substituted Titania (Ti
0.98
Pd
0.02
O2) was prepared by taking stoichiometric
amounts of titanyl nitrate, palladium chloride and Glycine by solution combustion method.
The accurate size and morphology of the doped metal oxide was studied Scanning electron
microscope (SEM). The phase composition of the palladium substituted Titania
(Ti
0.98
Pd
0.02
O2) was confirmed from powder X-ray Diffractometer (PXRD). The
functional groups are analyzed by Fourier transfer infrared spectroscopy. The doped metal
oxide shows superior catalytic performance
Keywords: TiO2, Ti (OC3H7)4, Pdcl2, Ti 0.98 Pd 0.02 O2, catalytic application
2
1. Introduction
In current study we can develop a uniform solid catalyst where the catalyst is a
single phase solid having, definite structure and it is possible to identify active sites
for catalysis. The palladium is the cheapest and most commonly used metal.
Palladium based catalysts particularly nanoscale palladium particles have recently
drawn enormous attention due to their versatile role in organic synthesis [1, 3]. The
use of palladium nanoparticles in catalysis is not only industrially important [4-6],
but also scientifically interesting as a result of the sensitive relationship between
catalytic activity, nanoparticle size and shape as well as the nature of the
surrounding media [7].
Newly, it has received extensive attention utilizing support interactions to
increase the electro catalytic activity and stability of supported metal catalysts
[8-10]. Also confirmed that the interactions can change the electronic structure of
the metal catalyst, which in go changes its catalytic activity. The durability of the
support materials could also influence the durability of the resultant catalyst [11].
At low-temperature treating, denote a favourable application and TiO2-based
catalyst
[12-14].
The synthesis of palladium doped Titania is most useful for the high oxygen
storage capacity. The synthesized doped metal oxides will be characterized by
powdered-XRD, SEM and FTIR. The main applications of this catalyst is used as
high rates of H2+O2 recombination, solvent-free reduction of aromatic nitro
compounds to amines as high with olefins prepared. TiO2 is a nontoxic reducible
oxide and noble metal ions can be substituted in TiO2. In Ti1-xPdxO2-x (x=0.01 0.02
and 0.03) where Pd is in +2 oxidation state showed high rates of NOx reduction by
CO, high rates of hydrogen-oxygen recombination and good photo catalytic activity
for CO oxidation. Smaller the metal particle, large is the surface area, higher is the
amount of CO absorption and higher is the catalytic conversion. Highly distributed
nanoparticles of noble metals (Pt., Pd, Rh, Ru and Au), in mesoporous supports
such as Titania, alumina, silica are broadly used as catalysts in organic synthesis,
petro chemistry.
3
Pd doped electrons can easily flow to the metal sites on TiO2 and the role of the
metal is to act as an electron sink and thus to enhance the activity. [15-16].
This paper reports the development and catalytic application of Pd doped
Titania through low temperature solution combustion method. The activity of Pd on
TiO2 for both un-doped and doped materials was analysed in terms of lattice
parameters, average crystalline size and internal micro strains.
2. Experimental methods
2.1. Materials
Tetraethyl ortho titanate (Ti (OC3H7)4), TiO (NO3), PdCl2 and Glycine were purchased
from Merck.
2.2. Development of Palladium doped Titania (Ti 0.98 Pd 0.02 O2)
Both un-doped and Pd-doped TiO2 catalysts were synthesized using solution
combustion method. The compound Ti0.97Pd0.03O2 can be prepared from solution
combustion method. The starting materials are Ti (OC3H7)4, PdCl2, and Glycine as
fuel. For the synthesis of Ti0.97Pd0.03O2, the stoichiometric ratio of starting materials
were to be taken as 9.89 mmol of TiO (NO3)2 which is prepared from Ti(OC3H7)4,
0.31 mmol of PdCl2 and 10.99 mmol of Glycine in a 300 ml capacity crystallizing
dish. The compounds were fully dissolved in 15 ml of H2O. The solution was kept in
preheated furnace at 350° C. The combustion takes place after dehydration and the
solid product is left behind.
3. Results and discussion
3.1. X-Ray diffraction analysis
The XRD pattern of undoped and palladium doped TiO2 was obtained using a X-ray
Diffractometer Schimadzu model: XRD 6000 with CuKα radiation in the range of
20-70o (λ=0.154nm). The XRD patterns of the undoped and palladium doped TiO2
nanoparticles obtained by solution combustion method was shown in Fig. 1 a) and 1
b) respectively. All the peaks in the XRD patterns can be indexed as anatase phases
of TiO2 and the diffraction data were in good agreement with JCPDS No: 21-1272.
4
Crystallite size was obtained by Debye-Scherrer’s formula given by equation
D=K λ/ (β cos θ)………… (1)
Where D is the crystal size; λ is the wavelength of the X-ray radiation (λ=0.15406
nm) for CuKα; K is usually taken as 0.89 and β is the line width at half-maximum
height. The crystallite size obtained using this formula is 6.24 nm for undoped and
7.8 nm palladium doped TiO2. This reveals that Pd ions are uniformly doped in TiO2
matrix. In the region of 2θ˚=10˚-85˚, the shape of diffraction peaks of the crystal
planes of pure TiO2 is moderately analogous to those of Pd/TiO2. The average crystal
sizes of TiO2 and Pd doped TiO2 nanoparticles were calculated and also the average
crystal size was not significantly altered due to the addition of the Pd+2
The Rietveld refined XRD profiles of undoped and palladium doped TiO2 are shown
in Figure.2. The pattern are indexed to anatase TiO2 (tetragonal) one to two atomic
percent Pd metal can be detected by slow scan in the XRD. If Pd ion was substituted
for Ti4+ ion in six coordination, there should have been a measurable increase in
lattice parameters and if at all, a slight decrease in cell volume from135.6 to135.2A
as indicated in Table 1. Therefore, Pd ion in these oxides is not in octahedral
coordination. Ionic radius of Pd2+ ion in a square planar coordination is 0.64 A,
which is close to Ti4+ ion in octahedral coordination. Because for every Pd2+ ion
substitution one oxide ion vacancy needs to be created for charge balance, Pd is
likely to be in square planar coordination.
Table 1. Rietveld refined lattice parameters of TiO2 and Ti0.98Pd0.02 O2
(0, 0.01, 0.02 and 0.03)
Catalysts
a
c
Cell volume
Rf
RB
TiO2
3.779(1)
9.497(1)
153.62
2.8
2.6
Ti0.98Pd0.02 O2
3.779(0)
9.491(1)
153.54
3.8
2.8
Ti0.98Pd0.02 O2
3.779(0)
9.487(0)
153.48
3.9
3.1
Ti0.98Pd0.02 O2
3.778(1)
9.473(0)
153.21
2.7
2.5
5
Fig 1. XRD Pattern of a) TiO2
and b) Palladium doped TiO
Fig 2. Rietveld refined XRD of Palladium doped TiO2
6
3.2. Scanning Electron microscope analysis
SEM images of the palladium doped TiO2 prepared are shown in Fig. 3 a) and Fig 3 b).
In Fig.3 a), the clear nanostructures can be seen having grain size of ~ 1µm and the
tetragonal morphology with uniform particle distribution. In Fig 3 b), demonstrating the
particles are in little accumulation and tetragonal morphology. The SEM analysis showed
that the doped palladium on TiO2 does not affect the morphology and structure of the TiO2
nano particle.
b)
a)
Fig 3. SEM image of Palladium doped TiO2
7
3.3. Fourier Infrared spectroscopy analysis
FT-IR spectra of un-doped and Pd-doped TiO2 are shown in Fig. 4 a) and b). Both FT-IR
spectra from Fig. 4 point out four-fold Ti coordination in vitreous matrix.
In Fig. 4 a) show the following vibration bands: 1630 cm-1 (dHOH), 683.5 cm-1
corresponds to Ti-O bond vibration. With the increase of the temperature, the intensity of
the vibration bands due to Ti-O bonds increases and they are better defined. At the same
time, the vibration bands due to the presence of molecular water and structural OH
diminish. A similar profile is obtained for palladium doped TiO2 as shown in the Fig. 4 b).
8
42
a)
40
35
30
%T
25
20
15
10
5
1630.88cm-1, 0.24%T
3290.00cm-1, 0.01%T
2938.50cm-1, 0.10%T
-0
-1
4000
3500
3000
431.00cm-1, 0.07%T
683.50cm-1, 0.01%T
2500
2000
1500
1000
500 400
cm-1
Name
TiO2..NEW
Description
Sample 135 By Administrator Date Wednesday, October 05 2016
0.32
b)
0.30
0.28
0.26
0.24
0.22
0.20
%T
0.18
0.16
0.14
0.12
0.10
406.00cm-1, 0.10%T
0.08
0.06
0.04
0.02
433.50cm-1, 0.02%T
766.50cm-1, 0.01%T
2518.50cm-1, 0.01%T
-0.00
-0.01
4000
419.50cm-1, 0.01%T
3500
3000
2500
2000
cm-1
Name
3% TiPdO...2
Description
Sample 131 By Administrator Date Wednesday, October 05 2016
9
1500
1000
500 400
Fig 4. FTIR Spectra of undoped and Palladium doped TiO2
3. Conclusion
From X-ray diffraction studies revealed that the average crystalline size of undoped and
Palladium doped TiO2 were found to be 6.24 nm and 7.8 nm. The synthesized particles are
in tetragonal structure and showed that doped palladium on TiO2 doesn’t change
morphology of material.
Tetragonal morphology with uniform particle distribution. In Fig 3 b), demonstrating the
particles are in little accumulation and tetragonal morphology. The SEM analysis showed
that the doped palladium on TiO2 does not affect the morphology and arrangement of the
TiO2 nano particle. This reveals the Ti
0.98
Pd
0.02
O2 was vital applications for oxygen
storage capacity and H2 reduction catalyst in coupling reactions.
Acknowledgments
The one of the author (G.O. Obaiah) thank to the Research center, Talent development
center, IISC, Kudhapur, Chitradurga, providing the lab facilities for completion of the
work.
References
1. E. Negishi, Wiley, Chichester, UK, 2000.
2. J. Tsuji, John Wiley & Sons, Ltd, Chichester, UK, 2004.
3. K. Esumi, R. Isono, T. Yoshimura, Langmuir. 2004, 20, 237.
4. N. Toshima, Y. Wang, Adv. Mater. 1994, 6, 245.
5. A.J. Bard, Science 207. 1980, 139.
6. Willner, R. Maidan, D. Mandler, H. Durr, G. Dorr, K. Zengerle, J. Am. Chem. Soc.
1987, 109, 6080.
10
7. Y. Mizukoshi, K. Okitsu, Y. Maeda, T.A. Yamamoto, R. Oshima, Y. Nagata,
J.
Phys. Chem. B. 1997, 101,7033.
8. Y.H. Qin, H.H. Yang, X.S. Zhang, P. Li, C.A. Ma, Int. J. Hydrog. Energy. 2010, 35,
7667-7674.
9. Z. Zhang, J. Liu, J. Gu, L. Su, L. Cheng, Energy Environ. Sci. 2014, 7 2535-2558.
10. C. Zhang, L. Xu, N. Shan, T. Sun, J. Chen, Y. Yan, ACS Catal. 2014, 1926-1930.
11. Y. Shao, J. Sui, G. Yin, Y. Gao, Appl. Catal. B-Environ. 2008, 79, 89-99.
12. H. Dislich, E. Hussmann, Thin Solid Films. 1981, 771, 29-139.
13. H. Dislich, J. Non-Cryst. Solids. 1984, 63, 237-241.
14. B.E. Yoldas, T.W. O’Keeffe, Appl. Opt. 1979, 18, 3133-3138.
15. K.T. Ranjit, T.K. Varadarajan, B. Viswanathan, J. Photochem. Photobiol. A Chem.
1996, 96A 18-185.
16. S. Yuan, Q. Sheng, J. Zhang, F. Chen, M. Anpo, W. Dai, Catal. Lett. 2006, 107,
19-24.
11