Journal of Organometallic Chemistry 830 (2017) 146e149

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Journal of Organometallic Chemistry

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

Communication

Facile preparation of nanosized yttrium oxide by the thermal

decomposition of amorphous Schiff base yttrium complex precursor
Martin Pi
zl a, Ondrej Jankovský a, Pavel Ulbrich b, Norbert Szabo
 a, Irena Hoskovcova
 a,
David Sedmidubský a, Vile m Bartunek a, *
a  5, 166 28 Prague 6, Czech
Department of Inorganic Chemistry, Faculty of Chemical Technology, University of Chemistry and Technology Prague, Technicka
Republic
b
Department of Biochemistry and Microbiology, Faculty of Food and Biochemical Technology, University of Chemistry and Technology Prague, Technicka  3,
166 28 Prague 6, Czech Republic

a r t i c l e i n f o a b s t r a c t

Article history: Nanoparticles of yttrium (III) oxide were synthetized by thermal combustion of previously prepared
Received 12 June 2016 yttrium complex of pyridoxylidenealanine under air atmosphere at 750
C. Amorphous complex was
Received in revised form characterized by XRD and IR and NMR spectroscopy. The prepared nanoparticles were characterized by
13 December 2016
XRD and TEM revealing the size of the vast majority of particles ranging from 10 to 30 nm. The synthesis
Accepted 16 December 2016
Available online 18 December 2016
method can be modified by addition of any RE and can be used for many applications especially in the
field of non-linear optics or in biomedical applications where use of more fine nanoparticles may be
problematic or even dangerous.
Keywords:
Non-linear optics
© 2016 Elsevier B.V. All rights reserved.
Nanoparticles
Y2O3
Schiff base
Thermal decomposition
Rare earths

1. Introduction Y2O3 nanoparticles have been prepared by various ways

Yttrium is one of the rare earths (RE) elements group which,
unlike many of RE elements, does not exhibit luminescence because
it has no accessible f orbitals. Still its chemical behaviour is similar
to lanthanides. Alongside with its relative abundance and afford-
ability in comparison with for example lutetium, these properties
make yttrium excellently suitable for the function of a host material
in RE optical materials such as white LED phosphors, scintillation
phosphors, up-conversion and down-conversion phosphors, and
lasers medium [1]. Among the applications taking use of these
optical properties are such as up-conversion for utilizing the
infrared region of solar radiation to improve solar cell performance
[2] or for photodynamic therapy application in cancer treatment
[3]. Alongside with yttrium fluoride [3,4], Y2O3 is due its stability
and insolubility the most usable material for these purposes
especially in the form on nanoobjects.
including methods based on thermal decomposition of an yttrium
alginate gel [5] microemulsion method [6], laser ablation in liquid
[7], hydrolysis and oxidation [8] or an electrodeposition from
chloride bath [9,10].
RE complexes containing a Schiff base ligand are currently
widely studied [11e14]. Schiff bases are formed by condensation of
aromatic aldehydes with primary amines. This reaction is impor-
tant in living systems, in particular in course of deamination. In this
work pyridoxal (PL), a form of vitamin B6, was used as aldehyde and
an aminoacid alanine (Ala) as amine. In our paper we are pre-
senting a simple preparation technique of yttrium oxide nano-
particles of previously prepared Y-PL-Ala complex by thermal
decomposition in air.
2. Material and methods

Yttrium chloride hexahydrate and pyridoxal hydrochloride

* Corresponding author. Faculty of Chemical Technology, University of Chemistry
and Technology Prague, Technicka 5, 166 28 Prague 6, Czech Republic.
E-mail address: vilem.bartunek@vscht.cz (V. Bart
unek).
(PL$HCl) were purchased from Sigma-Aldrich. L-Alanine (Ala) was
purchased from Acros Organics and potassium bicarbonate and
diethylether from Penta.

http://dx.doi.org/10.1016/j.jorganchem.2016.12.018
0022-328X/© 2016 Elsevier B.V. All rights reserved.
 M. Pizl et al. / Journal of Organometallic Chemistry 830 (2017) 146e149 147

Potassium salt of the ligand, pyridoxylidenealanine (PL-AlaK)

was prepared by modified method [15]. The free base of pyridoxal
(PL) was separated out from the aqueous solution of pyridoxal
hydrochloride (PL.HCl) by addition of equimolar amount of KHCO3.
Ligand was prepared by the reaction of pyridoxal (vitamin B6) free
base with equimolar amounts of Ala and KHCO3. Subsequently,
6.25 mmol of PL (1.045 g), Ala (0.557 g) and KHCO3 (0.626 g) which
served as a weak base were added to 100 ml of dry methanol
(molecular sieves No. 3). The mixture was heated to 50e55
C for
five hours under permanent stirring until all starting material was
dissolved and a yellow solution was formed. The volume of the
solution was reduced to 1/3 at 40
C under vacuum.
Yttrium complex (Y-PL-Ala) was prepared by the modified
method [13]: Ligand (1.23 mmol) was freshly prepared in solution
by dissolving PL$HCl and Ala in 20 ml methanol (1 h). An amount of
93.2 mg of YCl3$6H2O (0.31 mmol) was added to the yellow solution
of the ligand and the mixture was refluxed for 16 h. After this time,
40 ml of diethylether was added and the solid precipitate was Fig. 1. Structure of PL-Ala.
isolated by filtration.
Combustible elemental analysis (CHNS-O) was performed using
a PE 2400 Series II CHNS/O Analyzer (Perkin Elmer, USA). The in- elemental combustion analysis and NMR. The obtained results,
strument was used in CHN operating mode (the most robust and 44.9 wt% of C, 5.5 wt% of H and 9.0 wt% of N, are in very good
interference-free mode) to convert the sample elements to simple agreement with the calculated composition of C11H13N2O4K$H2O
gases (CO2, H2O and N2). The PE 2400 analyzer automatically per- corresponding to 44.9 wt% of N, 5.1 wt% of H, and 9.5 wt% of N.
formed combustion, reduction, homogenization of product gases, As a result of hydrogen signals shifts in the 1HNMR spectrum,
separation and detection. An MX5 microbalance (Mettler Toledo) we can determine the structure of the ligand. The signal shifts
was used for precise weighing of the samples (1.5e2.5 mg per clearly correspond to our ligand structure in Fig. 1. (d (ppm)
single sample analysis). Using this procedure, the accuracy of CHN 1.57 d,CH3-Ala; 2.42 s,CH3-Aromatic; 4.16 q, H-Ala; 4.75 d,CH2-
determination is better than 0.30% abs. The internal calibration was Arromatic; 7.69 s, H-Aromatic; 8,87 s, H-azomethine). This results
performed using an N-fenyl urea. are in good agreement with [15].
Fourier transform infrared spectroscopy (FTIR) measurements Subsequently, the yttrium complex (Y-PL-Ala) was also analysed
were performed on a NICOLET is 50R FTIR spectrometer (Thermo by elemental combustion analysis. Also in this case the obtained
Scientific, USA). A Diamond ATR crystal and DTGS detector were results (34.7 wt% of C, 5.0 wt% of H and 7.6 wt% of N) are in good
used for all measurements, which were carried out in the range agreement with the calculated composition, C22H35N4O11Cl4Y. For
4000e400 cm1. C22H35N4O11Cl4Y the expected values are 34.7 wt% of C, 4.6 wt% of H
Thermal combustion of Y-PL-Ala was performed in a tube and 7.4 wt% of N.
furnace at 750
C in air atmosphere for 30 min with the heating and The Y-PL-Ala complex was also analysed using XRD. Results
cooling rate was 10
C.min1. confirmed completely amorphous nature of Y-PL-Ala. The XRD
NMR spectra were collected on Varian MercuryPlus at the pattern of Y-PL-Ala is not shown, since no reflection corresponding
operating frequency 299.97 MHz for 1H NMR in CD3OD. Signals are to this pattern was found within the sample.
marked as s e singlet, d e doublet, t e triplet and q equartet. The ligand donor groups of Y-PL-Ala were compared to PL-AlaK
X-ray powder diffraction data were collected at room temper- by FT-IR spectroscopy. We selected only those vibrations, which
ature on Philips X'Pert PRO diffractometer using CoKa radiation determine the donor atoms of the ligand. Their typical peaks (Fig. 2)
(l ¼ 1.5418 Å). X'Pert HighScore Plus program was used for XRD [11] show characteristic changes in vibration energy: vibrations of
data processing and calculations of nanoparticles sizes were eval-
uated using Scherrer formula.
The samples for transmission electron microscopy were pre-
pared by the deposition of a 6 ml drop of the studied solution onto
carbon coated copper grid, the excess solution was removed and
the grids were dried by Whatman filtration paper. The samples
were observed by transmission electron microscope JEOL JEM-
1010 at accelerating voltage of 80 kV. Pictures were taken by SIS
MegaView III digital camera (Soft Imaging Systems) and analysed
by AnalySIS v. 2.0 software.
Thermal behaviour was probed by simultaneous thermal anal-
ysis (STA). The DTA and TG curves were recorded simultaneously on
a Linseis STA PT1600 apparatus at a heating rate of 10 K min1 in
dynamic air with a flow rate of 50 ml min1 to imitate the real
conditions during the thermal decomposition of Y-PL-Ala in the
tube furnace.

3. Results and discussion

Fig. 2. FT-IR spectra of PL-AlaK (red) and Y-PL-Ala (black). (For interpretation of the
Firstly, yellow fine needle-like crystals of the potassium salt of references to colour in this figure legend, the reader is referred to the web version of
the ligand, pyridoxylidenealanine (PL-AlaK) was analysed by this article.)
148 M. Pizl et al. / Journal of Organometallic Chemistry 830 (2017) 146e149

COO group shifted from 1412 to 1431 cm1, azomethine C]N group
from 1638 to 1618 cm1 and the vibration of phenolic CeO group
changed from 1189 to 1210 cm1. Other vibrations are those cor-
responding to the remaining organic ligands.
The thermal decomposition in air atmosphere of Y-PL-Ala
complex was investigated by STA analysis in dynamic air atmo-
sphere to reproduce the synthesis procedure (Fig. 3). The first
exothermic effect at 256
C is associated to the oxidation of the
complex forming a black powder. This powder has an amorphous
nature which was confirmed by XRD measurement. This effect was
accompanied by the weight loss ~50 wt%. In the temperature range
500e700
C the sample continuously releases some components
losing additional ~7 wt%. The second exothermic effect at 722
C
was caused by the decomposition of black amorphous powder
forming white Y2O3 nanocrystals. Also this effect was accompanied
by a weight loss ~3 wt%.
Fig. 3. DTA-TGA curves of thermal decomposition of Y-PL-Ala complex.
The prepared precursor Y-PL-Ala was decomposed in tube
furnace at 750
C in air and the obtained white powder was char-
acterized by XRD. The XRD patterns confirmed the presence of
single phase Y2O3 nanoparticles (Fig. 4). Scherrer formula was used
to evaluate the average sizes of the obtained nanocrystals yielding
the average size was 30 nm. This is in good agreement with the
image analysis of TEM micrographs (Fig. 5). Nanocrystals with
relatively homogenous size distributions were found on TEM im-
ages. The majority of nanocrystals were in range of sizes between
10 and 30 nm and no particles larger than 50 nm were present. The
size range of the prepared nanoparticles manifests their suitability
for biomedical applications because the mid-size nanoparticles are
easier to fabricate, better for surface processing and are consider-
Fig. 4. XRD patterns of prepared nanosized Y2O3.
ably less dangerous than ultrafine nanoparticles [16].

Fig. 5. TEM images of the prepared Y2O3 nanoparticles and their size distribution.
 M. Pizl et al. / Journal of Organometallic Chemistry 830 (2017) 146e149 149

4. Conclusions (2011) 2675e2680.

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