DOI 10.

1007/s10812-018-0658-9
Journal of Applied Spectroscopy, Vol. 85, No. 2, May, 2018 (Russian Original Vol. 85, No. 2, March–April, 2018)

FOURIER TRANSFORM IR SPECTROSCOPIC STUDY

OF NANO-ZrO2 + NANO-SiO2 + NANO-H2O SYSTEMS UPON
THE ACTION OF GAMMA RADIATION

T. N. Agayev*, N. N. Gadzhieva, and S. Z. Melikova UDC 620.3;539.166.2

The radiation decomposition of water in a nano-ZrO2 + nano-SiO2 + H2O system at 300 K by the action of gamma
radiation has been studied by Fourier transform IR spectroscopy. Water adsorption in the zirconium and silicon
nanooxides is attributed to molecular and dissociative mechanisms. Active intermediates in this radiation-induced
heterogeneous decomposition of water were detected including zirconium and silicon hydrides and hydroxyl groups.
Variation in the ratio of ZrO2 and SiO2 nanopowders was shown to lead to change in their radiation catalytic activity
compared to initial ZrO2.

Keywords: zirconium and silicon nanooxides, water, radiation decomposition, gquanta, Fourier transform IR
spectroscopy, radiation chemical yield G(H2).
Studies of the radiolysis of water using disperse metal oxides by the action of gradiation have shown that the use
of oxide nanopowders such as ZrO2, SiO2, TiO2, and Al2O3 as catalysts significantly enhances the rate of accumulation of
molecular hydrogen [1–4] with much greater radiation chemical yields of H2 in comparison with both homogeneous and
heterogeneous water decomposition processes, in which microsized oxides are used [5–7]. Zirconium and silicon dioxides are
the most promising among these nanooxides since they are selective catalysts for radiation-induced heterogeneous processes
[6, 7]. Various methods including spectroscopy have been employed to elucidate the mechanism of the radiation-induced
catalytic action of oxide catalysts in the radiolysis of water [8, 9]. In particular, Fourier transform IR spectroscopy has been
used to study the radiation-induced thermal decomposition of water in nano-ZrO2 in the range 300–673 K [9]. Detected
intermediates in the radiation-induced heterogeneous decomposition of water include radicalions of molecular oxygen and
hydrogen peroxide as well as zirconium hydride and hydroxyl groups. IR spectroscopy has also shown a hydroxyl coating
and electron-accepting properties of nano-ZrO2 itself [4]. Perez-Luna et al. [10] have examined the effect of γ-radiation on
nano-SiO2 and the change in the absorption bands of the OH groups and water molecules at room temperature and radiation
dose 25–200 kGy. However, there are virtually no spectroscopic data in the literature on the radiation decomposition of water
in a mixture of nano-ZrO2 + nano-SiO2 + H2O.
In the present work, we present the results of an FTIR spectroscopic study of the radiation decomposition of water in
the heterogeneous nano-ZrO2 + nano-SiO2 + H2O system at 300 K upon γ-irradiation in order establish the role of the active
intermediate species (radicalion groups) in these processes. The ratio of the nano-ZrO2 + nano-SiO2 nanopowders was varied:
0.1 g + 0.1 g, 0.05 g + 0.15 g, and 0.15 g + 0.05 g.
There are only limited data on the effect of the second component on the surface physicochemical and radiation
catalytic properties of the nano-ZrO2 + nano-SiO2 binary system. Thus, we studied the kinetics of hydrogen formation in the
heterogeneous radiolysis of water relative to the component ratio in the nano-ZrO2 + nano-SiO2 in order to elucidate the effect
of the interaction between the components of this mixture on its radiation catalytic properties.
We used nanopowders of 99.9%pure ZrO2 and SiO2 from Sky Spring Nanomaterials with particle diameter d = 20–30
and 20–60 nm. X-ray phase analysis showed that the ZrO2 sample had monoclinic centro-symmetric crystal structure [2].
Prior to adsorption, the zirconium dioxide and silicon dioxide samples were heated in vacuum at 673 K and 10–3 Pa for 8 h in
_____________________
*
To whom correspondence should be addressed.
Institute of Radiation Problems, National Academy of Sciences of Azerbaijan, 9 B. Vahabzade Str., AZ1143, Baku,
Azerbaijan; email: agaevteymur@rambler.ru. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 85, No. 2, pp. 351–354,
March–April, 2018. Original article submitted April 3, 2017.

0021-9037/18/8502-0365 ©2018 Springer Science+Business Media, LLC 365

 Fig. 1. FTIR spectra of nano-ZrO2 (1), nano-SiO2 (2), and the system with (0.1 g nano-
ZrO2) + (0.1 g nano-SiO2) + H2O before (3) and after γ-irradiation (4).

order to remove organic impurities and dehydroxylate the surface. The surface purity was monitored relative to the intensity
of the bands due to water and hydrocarbon impurities.
The FTIR spectra were taken on a Varian 640IR spectrometer at 4000–400 cm–1 at room temperature. Pellets with
thickness 50–100 μm were pressed from ZrO2 and SiO2 nanopowders. The IR spectra of these samples were measured in a
special quartz cell with CaF2 windows, which permit us to obtain the spectra of adsorbed water dissociated by the action of
γ-radiation [2]. In the case of the overlap of bands related to different forms of adsorbed water, the total contour was resolved
into individual components according to Miyata et al. [1].
Doubly distilled water, from which extraneous gases were removed by repeated freezing in a liquid nitrogen trap
with subsequent pumping, was used as the adsorbate. The adsorption of water vapor was carried out according to our previous
procedure [2]. The radiolysis of water in the nano-ZrO2 + nano-SiO2 + H2O system was carried out at 300 K. The samples
were irradiated with 60Co; the dose magnitude was dDγ/dt = 0.20 Gy/s. The dosimetry of the source was carried out by
ferrosulfate and methane dosimetry [4]. The absorbed radiation in these systems was measured by comparison of the electron
densities. The radiation time τ = 15 h (Dγ = 10.8 kGy).
The IR spectra of nano-ZrO2, nano-SiO2, and the system with (0.1 g nano-ZrO2) + (0.1 g nano-SiO2) + H2O before
and after water adsorption upon γ-irradiation are given in Fig. 1. The γ-irradiation of this system was carried out with a dose
of 10.8 kGy at 300 K. Curves 1 and 2 in Fig. 1 show that the surfaces of nano-ZrO2 and nano-SiO2 after heat treatment with
evacuation are clean since their spectra lack absorption bands due to water and hydrocarbon impurities [3]. The spectra in
the region of lattice vibrations of nano-ZrO2 (800–400 cm–1) show bands with a maximum at 745 cm–1 and a doublet at 490
and 410 cm–1 (curve 1). The bands at 745 and 490 cm–1 are assigned to asymmetric Zr–O2–Zr vibrations and ZrO stretching
vibrations [5]. The region of lattice vibrations of nano-SiO2 (1400–400 cm–1) show bands with maxima at 472, 798, and
1095 cm–1 (curve 2), which are assigned to symmetrical and asymmetrical Si–O and SiO2–Si stretching vibrations. Change in
the ratio of the ZrO2 and SiO2 nanopowders is accompanied by redistribution of band intensities of the Zr–O and Si–O bands.
Bands appear in the unirradiated heterosystem after water adsorption on the surface of zirconium and silicon dioxides in the
region of OH group stretching vibrations indicating adsorption of the molecular form (strong broad bands with maxima at
3240 and 3280 cm–1 in the region 3500–3000 cm–1) and dissociative chemisorption (relatively narrow bands with maxima
at 3450, 3475, 3520, and 3580 cm–1 (curve 3). The adsorption of two species is also suggested by the finding of bands in the
region of OH deformation vibrations with maxima at 1610, 1630, 1640, and 1680 cm–1.
Gamma irradiation of the heterosystem (0.1 g nano-ZrO2) + (0.1 g nano-SiO2) + H2O at 300 K leads to radiation
decomposition of water and formation of decomposition intermediates (curve 4), of which surface zirconium and silicon
hydrides are the most interesting. Thus, the frequency region 2000–1700 cm–1 shows bands with maxima at 2100, 2000,
1995, and 1880 cm–1 assigned to Zr–H (1995, 1880 cm–1) and Si–H stretching vibrations (2100, 2000 cm–1), which indicate
the formation of zirconium and silicon hydrides such as ZrH, ZrH2, SiH, and SiH2 [6]. ZrH2 and SiH2 are the most stable
among these forms. Unfortunately, we were unable to detect absorption bands of oxygen-containing water decomposition
surface species since the corresponding bands overlap with SiO stretching bands (1200–900 cm–1).

366