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Chemical degradation of trimethyl phosphate as surrogate for organophosporus pesticides on nanostructured metal oxides
Vclav tengl *, Jir Henych, Tom Grygar, Ral Prez
Materials Chemistry Department, Institute of Inorganic Chemistry AS CR v.v.i., Re,
250 68, Czech Republic
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 27 December 2013
Received in revised form 26 September 2014
Accepted 6 October 2014
Available online 12 October 2014
Nanostructured TiO2 and mixed oxides of Ti and Fe, Hf, In, Mn or Zr -were prepared by homogeneous
hydrolysis of aqueous solution of metal sulphates with urea. The oxides were characterised by X-ray
powder diffraction (XRD), scanning electron microscopy, particle size distribution, surface area and
porosity. The oxide materials consists of a few nanometre primary crystals (mainly anatase) arranged in a
few micrometre regular spherical agglomerates with specic surface area 133511 m2 g1. The FTIR
diffuse spectroscopy was used for monitoring chemical degradation of trimethylphosphate (TMP) as a
surrogate for organo-phosphorus pesticides under ambient and higher temperatures. Undoped TiO2 and
Ti,Mn-mixed oxide were most active in cleavage (hydrolysis) of CH3O from TMP at room temperature and
100 C. Cleavage of CH3O in the other studied mixed oxides was not complete until temperature exceeds
the boiling point of TMP.
2014 Elsevier Ltd. All rights reserved.
Keywords:
Nanostructured oxides
Stoichiometric degradation
Trimethyl phosphate
1. Introduction
Laboratory research on degradation of chemical warfare agents
(CWAs) as sarin and soman or organophosphate-based pesticides
as malathion is complicated by their high toxicity. Therefore, their
surrogates, containing similar functional groups, are used [1].
Dimethylmethyl phosphate (DMMP) and trimethyl phosphate
(TMP) are the most common surrogates used in this eld [2].
Interactions between DMMP and metal oxides, which includes
chemisorption and surface chemical decay, have been studied
thoroughly, especially between DMMP and TiO2 [211]. Other
studies were dedicated to interactions of DMMP and aluminium
oxides [12], as well as TMP sorption and decomposition on
hematite, maghemite and goethite nanoparticles [13,14] and
zeolites [15]. Also a computational research was conducted on
DMMP and TMP interactions with CaO [16]. Apart from adsorption
process, many of mentioned studies were focused on successive
decomposition processes, both stoichiometric [314] and photocatalytic [2,9,10,14,17]. It should be mentioned, that most of the
studies used a procedure with solid oxide exposed to gaseous
phosphates, while liquid-phase TMP was employed in this work.
Photocatalytic decomposition enhancement by TiO2 doping
was studied already in two last decades of the 20th century [18].
Positive effect of Au-doped TiO2 on DMP decomposition have been
* Corresponding author. Tel.: +420 2 6617 2193; fax: +420 2 2094 0157.
E-mail addresses: stengl@iic.cas.cz, stengl@me.com (V. tengl).
http://dx.doi.org/10.1016/j.materresbull.2014.10.030
0025-5408/ 2014 Elsevier Ltd. All rights reserved.
proven later [5]. With regard to CWAs, TiO2 doping by Zn, Mn, In
and Ge also resulted in better decomposition rates of sulphur
mustard [1923] and soman [1,19,21,23]. Zirconium doped titania
resulted in increased specic surface area, decreased particle size
and enhanced surface hydroxylation leading to better sorption and
decomposition of toxic compounds (or their surrogates) [19,22].
Hirakawa et al. [11] observed that decomposition rate of sarin on
TiO2 was 3.3 times higher than the DMMP. Still, bonding energies of
DMMP sorbed on CaO showed to be closer to the values of
adsorbed tabun bonds, that those in case of TMP [16].
1.1. TMP/DMMP adsorption on TiO2
DMMP adsorption on TiO2 (and iron oxides and hydroxides
[13]) surface can have both molecular and reactive form. While the
rst mentioned occurs mainly by hydrogen bonding between
oxygen atom in phosphoryl group (PO) and surface hydroxyl
group [3,4], the latter takes place on Lewis acid sites (Ti4+) and
active oxygen species of initial surface [3]. Higher surface
concentration of OH group lead to lower TMP stability compared
to dehydroxylated surface [16]. DMMP decomposition on dehydroxylated TiO2 surface seems unlikely [7].
1.2. TMP/DMMP decomposition on TiO2
The decomposition itself is mostly considered as a CH3O group
cleavage from DMMP/TMP molecule at low temperature such as
214 K (59 C) [8], room temperature [4], or after heating at 200 C
260
2. Experimental
2.3. Stoichiometric degradation of methyl phosphate
2.1. Preparation of nanostructured metal oxides
All used chemicals, titanium oxo-sulphate, indium(III) sulphate,
zirconium chloride, iron(III) sulphate, hafnium chloride, potassium
permanganate, urea and trimethylphosphate (>99,5% purity) were
supplied by Aldrich. ZrOSO4 and HfSO4 were prepared by a reaction
of stoichiometric mount of ZrCl4 or HfCl4 and sulphuric acid.
Chlorides were dissolved in a 98% sulphuric acid solution in a
porcelain crystallization dish, heated at 100 C until HCl escaped
from the reaction mixture. Then, the solution was heated to
crystallization.
Stoichiometric degradation experiments were run on ve
different mixed oxides based on titania, included non doped
TiO2 and mixed oxides of Ti with In, Zr, Fe/Zr, Mn and Hf. All studied
oxides were prepared by homogeneous hydrolysis of TiOSO4 in
aqueous solutions using urea as the precipitation agent as
described in previous studies [20,23,25,26]. The process consisted
Table 1
Properties of the prepared samples.
Sample
Total pore
Cryst. Specic
surface area volume
size
2 1
[nm] [m g ]
[cm3 g1]
Average
agglomerate
size
[nm]
TiO2
TiIn
TiZr
TiFeZr
TiMn
TiHf
3.9
8.9
5.6
7.7
5.5
2188
1501
1497
1218
689
660
73.7
64.2
47.6
44.2
86.3
72,5
1,071
1,229
1,658
1,785
0,914
1,088
8,051
4,680
3,246
4,756
4,065
3,050
133.1
262.6
510.7
375.4
224.9
356,8
0.0834
0.2343
0.2908
0.3558
0.3005
0,2555
9.8
16.86
24.31
16.59
19.41
25,868
specic surface area 340 m2/g) can be hydrolysed stoichiometrically [6]. It would mean over-dosage in our case (Table 1).
Prior to the FTIR measurements all samples were annealed in
the cell for 30 min at 300 C in order to remove most of the
humidity and organic species adsorbed on the oxide surface. Before
TMP was dosed onto the oxide surface, all samples were allowed to
cool to room temperature. Consequent measurements were
carried out at ambient temperature, or using temperature
programme shown in Fig. 1.
3. Results and discussion
3.1. Structure and texture of prepared oxides
The identity of synthesized ZrOSO4 and HfSO4 was veried by
XRD (it corresponded to ICDD PDF 01-0366 and HfSO4 to ICDD PDF
24-0467, respectively).
The powder XRD patterns of the prepared TiO2 and mixed
oxides of Ti and Zr, Hf, Fe/Zr, Mn and In are shown in Fig. 2. From
the XRD patterns and the corresponding characteristic 2u values of
the diffraction lines, it can be conrmed that TiO2 has anatase
structure (ICDD PDF 21-1272), no other polymorphs of titania were
formed. The broadening of diffraction lines indicates a small size of
primary titania crystals. The average size t of primary crystals was
calculated from the peakwidth at half maximum B (FWHM), using
the Scherrer equation [30],
t
kl
Bcosu
(1)
261
262
Fig. 2. XRD patterns of prepared oxides: (a) TiO2, Ti,Zr-, Ti,Hf-, Ti,In-mixed oxides, (b)Ti,Mn mixed oxide, (c) and Ti,Fe,Zr-mixed oxide.
263
264
Fig. 4. SEM images of the studied oxide samples. (a) TiO2, (b) Zr-doped, (c) In-doped, (d) Fe/Zr doped, (e) Mn-doped and f) Hf-doped Ti oxides.
265
Fig. 5. Position of bands in CH region (left), differences in spectra intensities (right) (TMP measurement with oxide as a background).
CH3O groups were still present on the solid. The most visible
change in the spectra was the disappearance of n(PO) band at
1280 cm1. Despite n(PO) band increase has not been so
signicant, we suppose that PO bond were converted into P
O bonds. Small intensity change of this band could be masked by a
cleavage of methoxy-groups from the molecule. Simultaneously,
many bands appeared in the region centred at 1120 cm1. We
associate them to some decomposition products strongly bonded
to the oxide surface, as they do not disappear even at higher
temperatures (see below). Note, that boiling point temperature of
TMP is 197 C, DMP 174 C and MMP 250 C. When temperature
was increased to 200 C, remaining bands in CH region on TiO2
sample can be attributed to decomposition products of CH3O
groups, which are not present in the sample anymore, as conrmed
by disappearance of the band at 1452 cm1. On the contrary, CH
vibrations bands in Ti,In- and Ti,Zr increased and decreased in Ti,
Mn- and Ti,Fe,Zr-mixed oxides. As d(CH3O) band in these samples
almost disappeared, we can assume that the part of the CH3O
groups not escaped as gaseous products as was transformed into
some other, non-volatile CH species. In Ti,Hf-oxide blue shift of
bands in CH region is clearly visible, thus, in conjunction with n(P
O) band we can assume, that both changes are interrelated and
refer to methoxy group cleavage. Moreover, decrease of the n(PO)
band intensity was observed in mixed oxides of Ti with In, Zr and
Fe,Zr only at that increased temperature (not at room temperature).
The intensity of the broad band between 1170 cm1 and
1000 cm1 further increased on heating (except for Ti,Mn-oxide),
but rather due to the oxide structural rearrangement and not as a
consequence of TMP reactions, because these bands signicantly
weaken when the oxides were cooled to room temperature. The
decomposition of CH3O group further continues at 200 C. This
temperatures is sufcient for TMP destruction on non-doped
titania or TMP evaporation (TMP boiling point is 197 C). If any CH
groups are present in a sample at 200 C, those cannot be
associated to free TMP molecules, but to either chemisorbed TMP
or to some of its decomposition products. On the contrary, decrease
of CH bands in the spectra at temperatures below 200 C should
indicate chemical, not thermal decomposition of the molecule.
At 300 C, the CH bands are still present in the spectra of Ti,In-, Ti,
Zr-, Ti,Fe,Zr- and Ti,Hf-oxides. Small frequency shifts have been
observed indicating some transformation of sorbed species. Broad
band with a centre at 1340 cm1 observed only in TiO2 and Ti,Mnmixed oxide (the wavenumber of the band is lower than on TiO2)
continued to rise. We can say, that 300 C is a sufcient temperature
for TMP destruction or desorption from Mn doped titania. At 400 C,
the CH vibrational bands can be seen only in Ti,Fe,Zr-mixed oxide
(Fig. 8) and Ti,Hf mixed oxide spectra (Fig. 7). Despite very signicant
intensity decrease, the presence of these bands denotes, that
decomposition products are different (and more stable) from those
in other oxides. The rest of the spectra just replicates the progress
observed at 300 C. At the temperature 500 C and higher, no CH
species can be seen in the spectra of any oxide. This temperature is
sufcient for destruction of all organic residues irrespective of their
form. There were only phosphorous species located on the oxide
surface, probably forming Ti-O-P-O-Ti network [4], with some
adsorbed simple CO species. TiO2 and Ti,Mn-oxide spectra show
increase of the broad band at 1360 cm1, respectively 1300 cm1
under heating up to 600 C. As stressed before, this is probably
related to the heating as there were no remaining species which
could be transformed into products with vibrations in this region.
Some changes in TiO2 and Ti,Mn-oxide specic band mentioned
above occurred, but their origin remains unclear for us.
After 30 min at 600 C, all samples were cooled to a room
temperature and then the spectra were acquired again. Surface rehydroxylation is clearly visible as broad OH negative bands
disappeared. Simultaneously, all bands in 13001000 cm1 region
decreased signicantly in intensity. As mentioned above, unidentied wide bands at 1360 cm1 in TiO2 and 1320 cm1 in Ti,Mnmixed oxide nearly disappeared (Fig. 9).
Previous studies performed on chemical warfare agents revealed,
that Zr-doped titania increased the removal of CWA [26], while Mndoped titania had only half such activity towards soman as compared
to non-doped titania [1]. Based on our different conclusions we must
assume, that chemical interactions between titania and TMP (or
organophosphorus CWAs) that we must distinguish removal of those
agents (deactivation, decontamination) and chemical decomposition, as mentioned before [11].
266
Fig. 6. CH and ngerprint region of IR spectra of TiO2, Ti,In- and Ti,Zr-mixed oxides at different temperatures (TMP measurement with oxide as a background).
Fig. 7. CH and ngerprint region of the IR spectra of TiO2, Ti,Zr-and and Ti,Hf-mixed oxides (TMP measurement with oxide as a background).
267
268
Fig. 8. CH and ngerprint region of IR spectra of Ti,In-, Ti,Fe,Zr- and Ti,Mn-mixed oxides at different temperatures (TMP measurement with oxide as a background).
269
References
Fig. 9. Effect of cooling in the spectra of non-doped TiO2 spectrum after interaction
with TMP and heating according to programme in Fig. 1 (TMP measurement with
oxide as a background).