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OPEN A comparative study of ZnAl2O4

nanoparticles synthesized from
different aluminum salts for use as
received: 21 January 2015
accepted: 08 July 2015
Published: 04 August 2015
fluorescence materials
Shi-FaWang1,2, Guang-ZhuangSun1,2, Lei-MingFang2, LiLei3, XiaXiang1 & Xiao-TaoZu1

Three ZnAl2O4 samples were prepared via a modified polyacrylamide gel method using a citric acid
solution with different aluminum salt starting materials, including AlCl36H2O, Al2(SO4)318H2O,
and Al(NO3)39H2O under identical conditions. The influence of different aluminum salts on the
morphologies, phase purity, and optical and fluorescence properties of the as-prepared ZnAl2O4
nanoparticles were studied. The experimental results demonstrate that the phase purity, particle
size, morphology, and optical and fluorescence properties of ZnAl2O4 nanoparticles can be
manipulated by the use of different aluminum salts as starting materials. The energy bandgap (Eg)
values of ZnAl2O4 nanoparticles increase with a decrease in particle size. The fluorescence spectra
show that a major blue emission band around 400nm and two weaker side bands located at 410 and
445nm are observed when the excitation wavelength is 325nm. The ZnAl2O4 nanoparticles prepared
from Al(NO3)39H2O exhibit the largest emission intensity among the three ZnAl2O4 samples,
followed in turn by the ZnAl2O4 nanoparticles prepared from Al2(SO4)318H2O and AlCl36H2O. These
differences are attributed to combinational changes in Eg and the defect types of the ZnAl2O4
nanoparticles.

Spinel ZnAl2O4 is known to have a wide energy bandgap (Eg), high mechanical resistance, high fluores-
cence efficiency, high chemical and thermal stability, high photocatalytic activity, and low surface acidity,
all of which make it a suitable material for a wide range of applications, including use in photoelectronic
devices, catalysts, electroluminesence displays, stress imaging devices, optical coatings, and highly effi-
cient phosphors13. Based on the above mentioned applications, various morphologies of spinel ZnAl2O4
have been prepared, including one-dimensional microfibers, porous structures, nanoparticles, nanorods,
nanotubes, and so on48. It has been noted that the optical properties of these materials are strongly
dependent on their morphologies and preparation methods. In particular, ZnAl2O4 nanostructures
are expected to exhibit enhanced optical and fluorescence properties usually absent in bulk ZnAl2O4.
Therefore, the preparation and study of the optical and fluorescence properties of ZnAl2O4 nanostructure
powder is of great interest.
Spinel ZnAl2O4 semiconductors have been synthesized using a variety of different methods, such as
the solid-state reaction method9,10, a self-generated template pathway9, the combustion synthesis route11,
the solgel method12, a co-precipitation approach6, the polymeric precursor method13, the citrate pre-
cursor method4, a hydrothermal process7, a solvothermal approach14, and the microwave-hydrothermal
route15. The particle size of ZnAl2O4 has a large effect on its optical and fluorescence properties. Generally,

1
School of Physical Electronics and Institute of Fundamental and Frontier Sciences, University of Electronic Science
and Technology of China, Sichuan, Chengdu, 610054, China. 2Institute of Nuclear Physics and Chemistry, China
Academy of Engineering Physics, Sichuan, Mianyang, 621900, China. 3Institute of Atomic and Molecular Physics,
Sichuan University, 610065, Chengdu, China. Correspondence and requests for materials should be addressed to
X.T.Z. (email: xtzu@uestc.edu.cn)

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Figure 1. XRD patterns of ZnAl2O4 nanoparticles prepared from (S1) Al2(SO4)318H2O, (S2)
AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 600C.

smaller particles have a relatively larger specific surface area, and therefore have a larger amount of dan-
gling and unsaturated bonds on the particle surface. This in turn affects the defect levels and fluores-
cence properties of the powder16. However, the main disadvantage of preparing spinel ZnAl2O4 by the
traditional synthesis routes, such as the co-precipitation approach, the solid-state reaction method, and
others, is the large particle size of the product.
The polyacrylamide gel route is a very good sol-gel method for the preparation of superfine nanopar-
ticles17. Appropriate selection of a chelating agent, monomer systems, initiator, pH value, and sintering
temperature can significantly improve the quality of the prepared nanoparticles17. In addition, different
aluminum salts, i.e. different anionic species in the precursor solutions, can greatly influence the mor-
phology, phase purity, and optical and fluorescence properties of the ZnAl2O4. However, most previously
reported studies have only used a single aluminum salt as a starting material and have not investigated
the influences of different aluminum salts on the morphology, structure, and optical and fluorescence
properties of the obtained ZnAl2O4.
In this study, three different aluminum salts are used as starting materials to synthesize three ZnAl2O4
gels via a polyacrylamide gel route, specifically aqueous solutions of citric acid with Al2(SO4)318H2O,
AlCl36H2O, or Al(NO3)39H2O were used under identical conditions. In order to obtain superfine nan-
oparticles, N,N-methylene-bisacrylamide was used as a cross-linking agent, and glucose was used to
prevent gel collapse. After sintering these xerogels, three ZnAl2O4 nanostructure samples were obtained.
Their phase purity, morphologies, and optical and fluorescence properties were then characterized and
compared. The objective of the present work is to investigate the influence of different aluminum salt start-
ing materials on the resulting ZnAl2O4 nanostructures and on their optical and fluorescence properties.

Results
The obtained ZnAl2O4 xerogels decomposed into products after being sintered at 600C for 5h in air.
Figure 1 shows the XRD patterns of ZnAl2O4 nanoparticles prepared from (S1) Al2(SO4)318H2O, (S2)
AlCl36H2O, and (S3) Al(NO3)39H2O. It can be seen that samples S1 and S2 have crystallized in a sin-
gle phase with a spinel structure and with space group O7h, but sample S3 contains small amounts of
ZnO (JCPDS card No. 361451) impurities in addition to the major phase of spinel ZnAl2O4 structure
(JCPDS card No. 050669). According to the literature2,18, the relevant reactions can be described by the
following equations:

4Zn (NO3 )2 6H 2O + 4Al 2 (SO 4 )3 18H 2 O + 4C 6 H8 O7 + 4C6 H12 O6 + 4C3 H5 ON

600 C
+ 4C7 H10 N 2 O 2 + 4NH3 H 2 O + 75O 2
4ZnAl 2O 4 + 10N 2 + 88CO 2 + 170H 2 O
+ 12SO 2 + 4NH3 ( 1)

4Zn (NO3 )2 6H 2O + 8AlCl 3 6H 2O + 4C 6H8O7 + 4C 6H12O6 + 4C 3H5ON + 4C 7H10N 2O 2

600 C
+ 24NH3 H 2O + 81O 2
4ZnAl 2O 4 + 10N 2 + 88CO 2 + 154H 2 O + 24NH3
+ 24HCl (2)

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Figure 2. FT-IR spectrum of ZnAl2O4 nanoparticles prepared from (S1) Al2(SO4)318H2O, (S2)
AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 600C.

8Zn (NO3 )2 6H 2O + 8Al (NO3 )3 9H 2O + 4C 6H8O7 + 4C 6H12O6 + 4C 3H5ON

+ 4C 7H10N 2O 2 + 4NH3
600 C
H 2O + 41O 2
4ZnO + 4ZnAl 2O 4 + 26N 2 + 88CO 2 + 194H 2O + 4NH3 (3)
For samples S1 and S2, the observed diffraction peaks at 2 are 31.22, 36.77, 44.69, 48.98, 55.52, 59.27,
65.06, 73.97, and 77.12 and can be ascribed, respectively, to the (220), (311), (400), (331), (422), (511),
(440), (620), and (533) planes of ZnAl2O4. The mean grain size of samples S1, S2, and S3 were quan-
titatively evaluated based on the line broadening of the (220), (311), (511), and (440) peaks using the
Scherrer formula, to be 13, 16, and 24nm, respectively. XRD results indicate that the choice of the
aluminum salts also has an influence on the phase purity of the final product. A possible reason for the
formation of impurity phases when using citric acid as a chelating agent is that citric acid has a relatively
weak coordinating capacity toward the metal ion of Al(NO3)39H2O, and hence the formed metal com-
plexonate is not expected to be highly stable.
Fourier transform infrared (FT-IR) spectra of the ZnAl2O4 nanoparticles prepared from (S1)
Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O are shown in Fig.2. The FT-IR spectra show
a series of absorption peaks in the range of 4002000cm1. According to the specific frequencies of the
absorption peaks, the functional groups existing in the samples can be deduced. Peaks at 1633, 656, 552,
and 493cm1 are present in all samples, and are assigned to the H-O-H bending vibration of adsorbed
water19, Al-O symmetric stretching vibration (1)1922, Al-O symmetric bending vibration (2)1922, and
Al-O asymmetric stretching vibration (3)21,22, respectively. For sample S2, the peaks located at 1186 and
1117cm1 are attributed to the S=O asymmetric stretching vibration23 and the S-O symmetric stretching
vibration23,24, respectively.
Figure 3 shows the TG/DTA curves of the ZnAl2O4 xerogels obtained from (S1) Al2(SO4)318H2O,
(S2) AlCl36H2O, and (S3) Al(NO3)39H2O. There are four weight loss stages observed for each sample.
The first weight loss stage is seen at a low temperature range (before 200C) and corresponds to the
evaporation of surface water in the ZnAl2O4 xerogel precursors25,26. The second weight loss stage (around
200250C) is due to the evaporation of structural water25,26. The third weight loss stage (between 250
400C) is due to the decomposition of small molecular organic compounds. The largest and final weight
loss stage (around 400620C) is due to decomposition of complexes, glucose, and the polyacrylamide
side-chain, as well as combustion of the polyacrylamide backbone and other residues27,28. The total
weight loss measured for the ZnAl2O4 xerogel precursors were 97.31% for (S1) Al2(SO4)318H2O, 95.201%
for (S2) AlCl36H2O, and 98.234% for (S3) Al(NO3)39H2O. In Fig. 3 (S1), the main endothermic peak
appeared at around 535 C and corresponds to the thermal decomposition of the complexes, polyacryla-
mide backbone, and other residues originating from Al2(SO4)3 18H2O. Meanwhile, the main endother-
mic peaks appeared at 557C (Fig.3(S2)) for the ZnAl2O4 xerogel precursor obtained from AlCl36H2O,
and at 528C (Fig.3(S3)) for (S3) Al(NO3)39H2O. The slightly different decomposition temperatures of
the three ZnAl2O4 xerogels may be related to differences in the microstructures caused by the presence
of different anionic species (Cl, SO42, and NO3) in the synthesis process. The chemical reaction is
complete at ~600/620C and results in the formation of ZnAl2O4 nanoparticles. However, for ZnAl2O4

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Figure 3. TG/DTA curves of ZnAl2O4 xerogel prepared from (S1)Al2(SO4)318H2O, (S2) AlCl36H2O, and
(S3) Al(NO3)39H2O.

nanoparticles prepared from Al2(SO4)318H2O, a higher heat treatment temperature is usually needed to
improve the phase purity.
To confirm whether the formation of ZnAl2O4 nanoparticles prepared from Al2(SO4)318H2O needed
a higher heat treatment temperature, FT-IR measurements were carried out using a Bruker IFS 66v/S
spectrometer. The FT-IR spectra of the ZnAl2O4 xerogel prepared form Al2(SO4)318H2O and sintered at
different temperatures are presented in Fig.4. Here is can be seen that the S=O asymmetric stretching
vibration (1186cm1) and S-O symmetric stretching vibration (1117cm1) peak intensities decrease with
the increase of sintering temperature. This result indicates that the SO42 anion coordinates to Zn and
Al cations and forms a bridged bidentate structure23,29,30.
In the case of the sample obtained by sintering the xerogel at 900C, all of the organic peaks disappear
except for the HOH peak (1633cm 1). These results indicate that the effects of aluminum salts and
sintering temperature on the phase purity of ZnAl2O4 cannot be neglected. Based on the subtle infor-
mation gathered from the XRD and FT-IR results, the relevant reactions can be described as follows:

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Figure 4. FT-IR spectrum of ZnAl2O4 xerogel prepared from Al2(SO4)318H2O and sintered at 700, 800,
and 900C.

4Zn (NO3 )2 6H 2O + 4Al 2 (SO 4 )3 18H 2 O + 4C 6 H8 O7 + 4C6 H12 O6 + 4C3 H5 ON

+ 4C7 H10 N 2 O 2 + 4NH3
600 800 C
HO 2 + 79O 2 4SO 4 2 / ZnAl 2O 4 + 10N 2 + 88CO 2 + 170H 2O + 8SO 2 + 4NH3 ( 4)

900 C
SO 4 2/ ZnAl 2O 4
ZnAl 2O 4 + SO 2 + O 2 (5)
The results indicate that the reaction (1) cannot occur at 600C, and that a higher sintering temper-
ature is needed for the formation of pure ZnAl2O4 nanoparticles.
In order to investigate the effects of different aluminum salts on the formation of ZnAl2O4, including
the particle size and surface morphology, SEM and TEM images were collected of the ZnAl2O4 samples
prepared using different aluminum salts and sintered at 700C, and are shown in Fig.5 and Fig.6. The
SEM images of the ZnAl2O4 samples reveal that the particles are almost spherical in shape and have a
narrow particle size distribution (Fig.5(S1S3)). When AlCl36H2O is added into the ZnAl2O4 precursor,
large particles form, however, if Al2(SO4)318H2O is added into the precursor, small particles with little
adhesion are observed, as shown in Fig.5(S1-S2).
Figure 6 shows (S1S3) TEM image, (SH1- SH3) HRTEM image, and (SP1SP3) the particle size
distribution of ZnAl2O4 nanoparticles prepared from (S1) Al2(SO4)318H2O, (S2) AlCl36H2O, and
Al(NO3)39H2O. The ZnAl2O4 nanoparticles are spherical in shape with a narrow particle size distribu-
tion, as shown in Fig. 6(S1S3). The corresponding particle size distribution patterns are given in the
Fig. 6 (SP1SP3). The average particle sizes of samples S1, S2, and S3 are around 12, 18, and 24nm,
respectively. TEM results show that the particle size variation tendencies for samples S1, S2, and S3 are
consistent with those calculated from XRD patterns (Fig. 1). In addition, the BET surface area of the
sample decreases with the increase of particle size as shown in Table1. Compared with sample S2, the
average particle size and BET surface area of sample S1 is significantly reduced, an effect which may
be due to the SO42 anion forming a bridged bidentate structure31. Fig.6(S2) inset presents the SAED
pattern taken from a portion of the ZnAl2O4 nanoparticles shown in Fig.6(S2). The associated electron
diffraction pattern is consistent with that of pure ZnAl2O4 crystals of a spinel structure, indexed as shown
in Fig. 1(a). The SAED pattern revealed that the ZnAl2O4 nanoparticles possess interplanar spacings
of 2.8235, 2.4156, 2.0205, 1.6328, 1.5531, and 1.4203 corresponding to the (220), (311), (400), (422),
(511), and (440) planes, respectively.
Figure 6 (SH1)-(SH3) shows the HRTEM image of ZnAl2O4 nanoparticles prepared from (S1)
Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O. For these samples, the lattice planes of
ZnAl2O4 nanoparticles were (111) with a lattice space of 4.6687, (220) with a lattice space of 2.8437,
(222) with a lattice space of 2.3345, (400) with a lattice space of 2.0210, (331) with a lattice space
of 1.8550, and (440) with a lattice space of 1.4356. It has been noted that (111), (220), (222), (400),
(331) and (440) planes can be attributed to spinel ZnAl2O4 structure corresponding to JCPDS card No.
050669.
Figure 7(a) shows the UV-Vis diffuse reflectance spectra of ZnAl2O4 samples prepared from (S1)
Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O. Considering that ZnAl2O4 is a direct band-
gap semiconductor32, the Eg of the ZnAl2O4 samples can be estimated from plots of (h)2 versus h

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Figure 5. SEM images and particle size distribution of ZnAl2O4 xerogel prepared from (S1)
Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 700C.

using the Tauc relation33. This is shown in Fig.7(b), where h is the Planck constant, is the Kubelka
Munk (KM) absorption coefficient, and is the frequency. The linear portions of the plots are extrap-
olated to the h axis to give the values of Eg. The calculated Eg values of samples S1, S2, and S3 are
3.980.01, 3.920.01 and 3.220.01eV, respectively. Generally, the Eg values of nano-sized semicon-
ductors increase with a decrease in particle size. In this case, the observed phenomenon is consistent
with what has been previously reported.

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Figure 6. (S1S3) TEM image, (SH1- SH3) HRTEM image, and (SP1SP3) Particle size distribution of
ZnAl2O4 nanoparticles prepared from (S1) Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O
and sintered at 700C. The inset presents the SAED pattern taken from a portion of the ZnAl2O4
nanoparticles shown in Fig.6(S2).

BET specific
Crystallite Particle Eg surface area
Sample size (nm) size (nm) (eV) (m2/g)
S1 13 12 3.98 40.13
S2 16 18 3.92 27.75
S3 24 24 3.22 19.38

Table 1. Crystallite size, particle size, Eg and BET specific surface area of samples S1, S2 and S3.

Figure8(a) show the fluorescence spectra of ZnAl2O4 samples prepared from (S1) Al2(SO4)318H2O,
(S2) AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 700C. The fluorescence spectra with a wave-
length range of 385~445nm for all samples are presented after excitation with light, exc=325nm. The
fluorescence spectrum of the ZnAl2O4 sample is wide and can be resolved using three Gaussian peaks
at 400, 410, and 445nm (Fig.8b). The three emission peaks at 400, 410, and 445nm can be ascribed to
intra band gap defects such as oxygen vacancies34. It has been noted that there is an obvious increase in
the fluorescence intensity of the peak located at 400nm when the Eg value decreases (see Fig.8(a) inset).

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Figure 7.(a) UV-Vis diffuse reflectance spectra and (b) Eg values of ZnAl2O4 samples prepared from (S1)
Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 700C.

Compared with the ZnAl2O4 nanoparticles prepared from Al2(SO4)318H2O, the ZnAl2O4 nanoparticles
obtained from AlCl36H2O have a smaller Eg value, however, their fluorescence intensity is also smaller.
Therefore, in this case we cannot simply attribute the differences in the fluorescence intensity for the
three ZnAl2O4 samples only to the differences in their Eg values. The difference in the fluorescence inten-
sity of the two ZnAl2O4 samples may also be related to the different phase purities of ZnAl2O4 samples
prepared from (S1) Al2(SO4)318H2O and (S2) AlCl36H2O. In the case of the ZnAl2O4 sample prepared
from Al2(SO4)318H2O, traces of the S=O and S-O are visible in the FT-IR spectrum after sintering at
700C.

Discussion
In order to understand the fluorescence mechanism of the prepared ZnAl2O4 samples, it is necessary to
propose a schematic band diagram to illustrate the process of excitation and emission for the system.
Figure9 shows a schematic band diagram for the fluorescence mechanism of ZnAl2O4 samples obtained
from (S1) Al2(SO4)318H2O, (S2) AlCl36H2O, and (S3) Al(NO3)39H2O. It is known that Al3+ 2p orbitals
and s orbitals located at the upper part of the Al3+ 2p orbitals make up the major conduction band (CB)
edge of ZnAl2O4, and the hybridization band composed of O2 2p and Zn2+ 3d orbitals makes up the
upper valence band (VB)35. When the Eg value >exc, (3.82eV vs. 325nm) it can be seen that one elec-
tron transition occurs from VB onto the intra band gap defects (IBGD) energy level (Fig.9(S1) and (S2)).
After that, the electron will be driven by continued transition from IBGD to CB. Then, the electron on
the CB drops down to the low energy level through loss of energy by vibration relaxation (VR). Finally,
the electron on the low energy level undergoes a radiative recombination with a hole in the valence band,
accompanied by three blue-light emissions. For sample S1, the impurity (SO42) plays a crucial role to

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Figure 8. Fluorescence spectra of ZnAl2O4 samples prepared from (S1)Al2(SO4)318H2O, (S2)

AlCl36H2O, and (S3) Al(NO3)39H2O and sintered at 700C.

promote the electron transition from IL (impurity level) to CB and improve the fluorescence properties.
When Eg<exc, one electron transition occurs from the VB to the high energy level (Fig.9(S3)). Then,
the electron on the high energy level drops down to the CB by internal conversion. At the same time,
the electron on the CB by VR drops down to the low energy level with an accompanying loss of energy.
Finally, the electron on the low energy level undergoes a radiative recombination with a hole in the
valence band, accompanied by a series of blue-light emissions.
Figure10 shows the Commission International De IEclairage (CIE) diagram of a ZnAl2O4 phosphor
under 325nm laser excitations. The CIE color coordinates (x, y) of the ZnAl2O4 phosphor was calculated
using the fluorescence spectra. A typical CIE color coordinate of a ZnAl2O4 phosphor was found to be
x, y equals 0.1729, 0.0048 respectively under 325nm laser excitations.
According to equation (7)36, the fluorescence quantum efficiency of the ZnAl2O4 phosphor can be
calculated from the experimental data.

Is As s
QE s = QE s s
Is s As ( 7)
Where QEs and QEs-s are the fluorescence quantum efficiencies of the prepared sample and standard
sample, respectively, under an excitation wavelength of 325nm. Is and Is-s are the integrated emission
intensities of the prepared sample and standard sample under an excitation wavelength of 325nm. As and
As-s are the absorbance of the prepared sample and standard sample under an excitation wavelength of
325nm. The standard sample is 5-sulfosalicylic acid, which has a quantum efficiency of about 58% under
an excitation wavelength of 325nm. The fluorescence quantum efficiencies of samples S1, S2, and S3 were
calculated to be 6.38%, 4.24%, and 10.11%, respectively. Observations made during these experiments
show that the spinel ZnAl2O4 phosphor could be useful for blue light-emitting materials.
In summary, ZnAl2O4 nanoparticles with different particle sizes were prepared using a modified pol-
yacrylamide gel route from different aluminum salt starting materials: Al2(SO4)318H2O, AlCl36H2O,
and Al(NO3)39H2O. The type of aluminum salt used can markedly influence the phase purity, particle

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Figure 9. Fluorescence mechanism of ZnAl2O4 samples prepared from (S1) Al2(SO4)318H2O, (S2)
AlCl36H2O, and (S3) Al(NO3)39H2O.

Figure 10. CIE diagram of ZnAl2O4 phosphor under 325nm laser excitations.

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Al(NO3)3 Zn(NO3)2 citric

Sample Al2(SO4)318H2O AlCl36H2O 9H2O 6H2O acid glucose acrylamide Bis-acrylamide
S1 6.6644g / / 1.4875g 4.7282g 20g 9.5958g 1.9192g
S2 / 2.4143g / 1.4875g 4.7282g 20g 9.5958g 1.9192g
S3 / / 3.7513g 1.4875g 4.7282g 20g 9.5958g 1.9192g

Table 2. Starting compositions of samples S1, S2 and S3.

size, and optical and fluorescence properties of the final product. Under 325nm excitation, samples of
ZnAl2O4 phosphor show blue emissions and the CIE colour coordinate was found to be (0.1729, 0.0048).
The fluorescence mechanisms of the ZnAl2O4 phosphor have been discussed based on the experimental
results. The fluorescence experiments revealed that the as-prepared ZnAl2O4 phosphor exhibits interest-
ing abilities for application in blue light-emitting materials. Interestingly, similar preparation methods
may be employed for the synthesis of other metal oxides nanoparticles, including fluorescence materi-
als, multiferroic materials, oxide thermoelectric materials, photocatalytic materials, solid oxide fuel cell
materials, and high-temperature superconducting materials.

Methods
Materials. Zn(NO3)26H2O, AlCl36H2O, Al2(SO4)318H2O, and Al(NO3)39H2O were purchased
from DaMao Chem. Ltd., Tianjing. Citric acid (C6H8O7, AR), glucose (C6H12O6.H2O, 99%), acrylamide
(C3H5NO, AR), and N, N-methylene-bisacrylamide (C7H10N2O2, 99%) were purchased from Kemiou
Chem. Ltd., Tianjing and used without further purification.

Synthesis. A certain stoichiometric amounts of Zn(NO3)26H2O and different aluminum salts

(Al2(SO4)318H2O, AlCl36H2O, and Al(NO3)39H2O are labeled sample S1, S2 and S3, respectively) were
dissolved in the deionized water to obtain a final solution of 0.015mol/L with the total cations. Starting
compositions of samples S1, S2 and S3 are given in Table2. After the solution was transparent, a stoichi-
ometric amount of chelating agent (citric acid) was added into the solution in the mole ratio 1.5:1 with
respect to the total cations (Zn2+ and Al3+) to complex the cations. After that, 20g glucose was dissolved
into the solution. Finally, the acrylamide and N, N-methylene-bisacrylamide monomers were added
into the solution. The resultant solution was heated to 90C on a hot plate to initiate the polymerization
reaction, and a few minutes later a polyacrylamide gel was formed. The gel was dried at 120C for 24h
in a thermostat drier. The obtained xerogel precursor was ground into powder and some powder was
sintered at 600, 700, 800, and 900C for 5h in air to prepare the objective products.

Sample characterization. The ZnAl2O4 xerogel precursor sintered at 600 and 700C were analyzed
by X-ray diffractometer (DX-2700) with Cu K radiation. Fourier transform infrared (FTIR) spectra
in the range 4002000cm1 were recorded using a Bruker IFS 66 v/S spectrometer. Thermogravimetric
(TG) and differential thermal analysis (DTA) analyses were performed in a SDT Q600 (TA instruments,
Inc. USA) simultaneous thermal analyzer at a heating rate of 10C/min. The surface morphology of the
synthesized ZnAl2O4 sample was characterized by scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). The surface area of the samples were characterized by a 3H-2000BET-M
instrument. The absorption spectra of the samples were examined on a Shimadzu UV-2500 UV-Visible
spectrophotometer. The fluorescence spectra were collected at room temperature in a confocal Raman
system using a He-Cd laser (325nm, RGB laser system, NovaPro 30mW, Germany).

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Acknowledgements
This work was supported by the NSAF joint Foundation of China (U1330103) and by Outstanding
Doctoral Student Support Plan (A1098524023901001074).

Author Contributions
S.W. and G.S. contributed to the preparation and characterization of the nanoparticles. L.L. measured
the fluorescence spectra. S.W., G.S., L.F. and X.X. analyzed data from experiments and wrote the main
manuscript. X.Z. led the project.

Additional Information
Competing financial interests: The authors declare no competing financial interests.
How to cite this article: Wang, S.-F. et al. A comparative study of ZnAl2O4 nanoparticles synthesized
from different aluminum salts for use as fluorescence materials. Sci. Rep. 5, 12849; doi: 10.1038/
srep12849 (2015).
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Scientific Reports | 5:12849 | DOI: 10.1038/srep12849 12