Radiation Physics and Chemistry 88 (2013) 5659

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Radiation Physics and Chemistry

journal homepage: www.elsevier.com/locate/radphyschem

Effect of -ray irradiation on the properties of nanostructured oxovanadate

based oxidative dehydrogenation catalysts
M. Ishaque Khan a,n, Kadir Aydemir a, M. Raq H. Siddiqui b, Abdulrahman A. Alwarthan b,
James A. Kaduk a, Christopher L. Marshall c
a

Department of Biological and Chemical Sciences, Illinois Institute of Technology, Chicago, IL 60616, USA
Chemistry Department, Science College, King Saud University, Riyadh 11451, Saudi Arabia
c
Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA
b

art ic l e i nf o

a b s t r a c t

Article history:
Received 14 February 2013
Accepted 28 February 2013
Available online 15 March 2013

Effect of varying doses of -ray irradiation on the catalytic oxidative dehydrogenation properties of a
nanostructured oxovanadate based material is described for the rst time. -ray irradiation enhanced
catalysts' selectivity to propylene during the oxidative dehydrogenation of propane.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
Oxidative dehydrogenation
Catalysis
Propylene
Framework-materials
Polyoxovanadates
-Ray irradiation

1. Introduction
Oxidative dehydrogenation (ODH) of propane offers a promising approach for the synthesis of propylene. Consequently, there is
an intense current interest in the oxidative dehydrogenation of
propane (Boucetta et al., 2009; Cherian et al., 2002; Dai et al.,
2004; Klisinska et al., 2004, 2006; Liu et al., 2006; Lucarelli et al.,
2007; Pless et al., 2004; Rao et al., 2004; Shee et al., 2006).
Polyoxovanadates (POVs) offer potentially promising ODH
catalysts due to rich redox chemistry owing to a variety of
oxidation states (2, 3, 4 and 5) and coordination geometry
(tetrahedral, octahedral and square pyramidal) exhibited by vanadium. During the course of our work on the design, synthesis and
properties of polyoxometalate based framework materials, we
have prepared and studied a series of materials composed of
polyoxovanadate motifs and nanoclusters (Khan et al., 1999a;
Khan, 2000; Khan et al., 1999b, 2003, 2007). Besides their novel
structural, electronic and magnetic properties, these systems also
exhibit interesting catalytic properties for ODH of propane to
propylene (Khan et al., 2011, 2010, 2009).

Gamma ray irradiation of metal oxides causes structural

modication that inuences their catalytic properties (which has
been documented for reactions other than ODH) (AbdelDayem and
Sadek, 2008; El-Shobaky et al., 2006; El-Shobaky and Shaheen,
2003; Jin et al., 2007; Mucka, 1993; Mucka et al., 2002). Gamma
ray irradiation changes the concentration of catalytically active
sites and alters the reducibility of the catalysts. Effect of such
irradiations on the catalytic properties of NiMoO4 has recently
been described for the ODH of cyclohexane (AbdelDayem and
Sadek, 2008). Gamma ray irradiation increased the catalyst selectivity for cyclohexene by lowering - to -phase transition
temperature for NiMoO4 and stabilizing the more selective
-NiMoO4 phase.
Here we describe the effect of varying doses of Gamma ray
irradiation of a novel polyoxovanadate based open-framework
material[Co3V18O42(H2O)12(XO4)]  24H2O (X V, S in 1:1 ratio)
(Co-POV) on its catalytic performance for the oxidative dehydrogenation of propane. To our knowledge, this is the rst report
describing the effect of Gamma ray irradiation on the catalytic
oxidative dehydrogenation properties in this class of materials.
2. Experimental

Correspondence to: Department of Biological and Chemical Sciences, Illinois

Institute of Technology, 3101 S Dearborn Street, Life Sciences Building, Room 178,
Chicago, IL 60616, USA. Tel.: 1 312 567 3431; fax: 1 312 567 3494.
E-mail address: khan@iit.edu (M.I. Khan).
0969-806X/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.radphyschem.2013.02.040

Co-POV was prepared by employing bottom up synthetic

approach from an aqueous reaction mixture. Further details of
the synthesis are given elsewhere (Khan et al., 1999b).

M.I. Khan et al. / Radiation Physics and Chemistry 88 (2013) 5659

Powder X-ray Diffraction (XRD) data was collected as follows:

samples were ground in a mortar and pestle, and mounted in zerobackground cells using double-sided adhesive tape. The X-ray
powder patterns were measured (5100 deg 2, 0.0202144 deg
steps, 8 s/step, 0.6 mm divergence slit, 2.5 deg Soller slits, 3 mm
scatter screen height) on a Bruker D2 Phaser diffractometer
equipped with a LynxEye position-sensitive detector. Quantitative
phase analysis of the crystalline phases was carried out by the
Rietveld method using GSAS (Larson and Von Dreele, 2004).
Catalyst samples were irradiated with gamma-ray as follows:
three identical samples, each one weighing 450 mg, were placed in
sealed glass vials and irradiated in air in a 60Co- cell for different
durations at a constant rate. The Gamma source was calibrated
against a Fricke ferrous sulfate dosimeter and the dose rates in the
irradiated samples were calculated by applying corrections based
on the average massenergy absorption coefcient for the sample
and the dosimeter solution, respectively. The absorbed doses
investigated in the present work are 8, 10 and 12 kGy.
All catalytic activity measurement of the samples was carried
out at atmospheric pressure in a xed bed tubular quartz reactor.
The reaction products were analyzed by online SRI 8610C Gas
Chromatograph equipped with thermal conductivity detector.
For analysis of hydrocarbons, silica gel column was employed,
and for CO, CO2 and O2, molecular sieve packed column was used.
Details of the reactor system are given elsewhere (Khan et al.,
2010, 2009). Catalysts were grinded and mixed with equal
amounts of SiC to produce uniform mixtures. Tests were performed at 350 and 400 1C. The gas hourly space velocity (GHSV) of
9786 h-1 and propane to oxygen ratio (1:1) were kept constant in
all runs. Nevertheless, iso-conversion ODH data was obtained with
varying ow rate of the reactants. The catalyst pretreatment was
performed at 400 1C under the ow of 20% O2/Ar (50 ml/min) for
1 h. Average values of several runs performed at each temperature
were reported. Carbon balance, dened as percentage of moles of
output carbon in products to moles of input carbon reactants, was
greater than 99% in all tests.

3. Results and discussion

Co-POV structure (Fig. 1) consists of three-dimensional arrays
of {V18O42(XO4)} nanoclusters interconnected via {OCoO}
bridging groups. We investigated the effect of Gamma-ray irradiation on the Co-POV based catalyst in terms of the structure and
ODH of propane performance. Fig. 2 shows the SEM micrographs
of the crystals of Co-POV before and after irradiation with -rays.
Degree of softening and deformation of crystals increases as
irradiation dose is increased.
Surface areas of non-irradiated and irradiated samples of
Co-POV were less than 1 m2/g. Hence, BET surface area could not

57

be determined even with krypton gas sorption measurements.

Powder diffraction patterns of irradiated samples (Fig. 3) revealed
loss of crystallinity of the irradiated samples regardless of irradiation dose. The XRD patterns resembled oxovanadate phases
V5O12  6H2O (PDF#00-045-1401) and HNaV6O16  6H2O (PDF#00049-0996), indicating that the irradiated samples consist of
hydrated reduced vanadates. However, to our knowledge, no exact
structural information has been reported for these phases. There
are sharp peaks in these samples, which are indicative of the
presence of small concentrations of shcherbinaite, V2O5.
The relative concentrations of this phase in the 8/10/12 kGy
samples are 1.00/0.89/0.10, respectively. There was no evidence
for the presence of CoO phase.
Gamma ray irradiation of Co-POV resulted into the formation of
nanocrystallites. The size of the nanocrystallites (derived from the
widths of the 26.3 deg peaks (Fig. 3) using the Scherrer equation)
varied from 6.38.2 nm, and decreased linearly with increasing
radiation dose.
We did a comparative study of the catalytic performance of
three identical samples of Co-POV (which were exposed to varying
doses of Gamma radiation) for the ODH of propane. Table 1
summarizes the results of this investigation. Overall, the catalytic
performance was notably altered upon irradiation of catalysts with
Gamma rays. The effect on the activity and selectivity of the
irradiated catalysts varies with the dosages of the irradiation.
In general, Gamma ray irradiated catalysts gave less total conversion of propane at both temperatures (350 and 400 1C) studied in
this work. As seen in Table 1, the propylene yields (conversion x
selectivity) for irradiated catalysts were comparable to nonirradiated catalyst. The effect of irradiation was especially notable
at high temperature, where catalytic performance increased with
increasing irradiation doses. Selectivity to propylene increased,
especially at 400 1C, and the production of undesired COx gases
decreased. At this temperature catalyst irradiated with the highest
dose (12 kGy) of Gamma rays gave the highest selectivity (54.3%)
to propylene. The lowest selectivity (25.9%) was observed for nonirradiated catalyst. A similar increase in selectivity with radiation
dose is also observed in iso-conversion tests (Table 2).
It is reported that Gamma radiation doses higher than 10 kGy
cause observable atom displacement in the crystal lattice (Kostova
and Spojakina, 2005; Zacheis et al., 1999). In addition, Gamma
irradiation affects the phase transition temperatures of metal
oxides resulting in enhanced catalytic performances for exposure
to different doses of radiation (AbdelDayem and Sadek, 2008).
Crystalline V2O5 phases are known to have catalytic activity
toward ODH of propane with a low selectivity (Schwarz et al.,
2008). Powder XRD results indicate the presence of similar
amounts of V2O5 phase in Co-POV samples irradiated with 8 kGy
and 10 kGy doses. On the other hand, Co-POV sample irradiated
with 12 kGy dose contains 90% less V2O5 phase as compared to the

Fig. 1. A view of the framework structure (right) of [Co3V18O42(H2O)12(XO4)] (X V, S) in Co-POV showing arrays of constituent nanoclusters[V18O42(XO4)] (left)
interconnected by {OCoO} bridges.

58

M.I. Khan et al. / Radiation Physics and Chemistry 88 (2013) 5659

Fig. 2. SEM micrographs of Co-POV crystals (a) before, and after irradiation with (b) 8 kGy, (c) 10 kGy and (d) 12 kGy radiation doses.

Table 2
Selectivity of irradiated catalysts at constant propane conversion
(1.5%).
Catalyst

Temperature
(oC)

Selectivity (%)

C3H6
yield

CO CO2 C3H6

Fig. 3. XRD patterns of irradiated catalysts and comparison to non-irradiated

Co-POV.

Table 1
Conversion, selectivity and propylene yield of non-irradiated Co-POV and
gamma ray irradiated Co-POV samples.
Catalyst

Co-POV
8 kGy
irradiated
10 kGy
irradiated
12 kGy
irradiated

Temperature
(oC)

350
400
350
400
350
400
350
400

Conversion
(%)

Selectivity
(%)

C3H8

CO CO2 C3H6

1.3
2.3
0.7
1.8
0.5
1.5
0.6
1.1

26
27
47
45
38
53
37
46

37
47
23
14
30
12
26
0

37
26
30
41
32
35
37
54

C3H6
yield

0.5
0.6
0.2
0.7
0.2
0.5
0.2
0.6

Co-POV samples irradiated with 8 kGy and 10 kGy radiation doses.

Hence, the sample treated at 12 kGy has the highest propylene
selectivity. The promoted selectivity of irradiated Co-POV samples
as compared to non-irradiated catalyst can be attributed to the
new reduced oxovanadate phases.

Co-POV

400

53 24

23

0.35

8 kGy
irradiated
Co-POV

400

44 29

27

0.40

10 kGy
irradiated
Co-POV

400

31 42

27

0.40

12 kGy
irradiated
Co-POV

400

40 21

39

0.59

4. Conclusions
Gamma irradiation of Co-POV enhanced its catalytic ODH performance with higher selectivity to propylene, albeit at the cost of
substrate conversion. The effect of irradiation was especially notable
at high temperature, with increased selectivity to propylene, where
catalytic performance increased with increasing irradiation doses.
Structural analysis by powder XRD indicated loss of crystallinity and
the presence of several hydrated reduced oxovanadate systems
together with a V2O5 phase, depending upon the irradiation dose.
The present work is the rst study exploring the effect of Gamma ray
irradiation on the ODH catalytic performance of a polyoxovanadate
based open-framework material with well-dened structure. It has
potential for opening door to newer and efcient ODH catalysts.
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