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Simple preparation of potassium sulfate

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Cite this: CrystEngComm, 2018, 20,

nanoparticles
7713
Yan Dong, *a Xian Bian,a Yibing Fu,b Qiyue Shao a
and Jianqing Jiangac

Received 15th August 2018,
Accepted 12th November 2018
DOI: 10.1039/c8ce01373j
rsc.li/crystengcomm
Water-soluble salts are widely used in the synthesis of porous materials, hollow materials, and nanostruc-
tured materials as templates or isolation media. However, there are some restrictions on their application,
as it is difficult to prepare nanoscale water-soluble salt particles. In this study, potassium sulfate nano-
particles were prepared by anti-solvent precipitation, and the effects of parameters such as the initial con-
centration, mixing order, and surfactant addition on the particle size were investigated. Polyacrylic acid was
found to promote nucleation, and the size of the particles obtained in its presence was reduced signifi-
cantly. As the amount of polyacrylic acid increased, the particle size decreased, such that the average parti-
cle size could be controlled within the range of 10–100 nm by adjusting the amount of additive. This
method can be used to prepare potassium sulfate nanoparticles on a large scale; further, the obtained
nanoparticles should be suitable as sacrificial template materials for preparing nanoporous materials, hol-
low nanomaterials, and other nanoparticles.

Introduction soluble salts because of their high hygroscopicity and ag-

Water-soluble salts have been used as hard templates in the
preparation of porous materials, hollow materials, and nano-
structured materials1–11 because they can be easily removed
and have good chemical stability and high temperature resis-
tance when compared to other sacrificial template materials
such as SiO2 and zeolites.12–14 However, the particle size of
existing water-soluble salts for hard templates is generally on
the scale of a few micrometers, which severely limits their ap-
plication. For example, when micrometer-sized salts are used
to prepare porous materials, only micrometer-sized pores are
obtained.2–6 When they are used as isolation media for the
preparation of nanoparticles like FePt, large quantities are re-
quired, usually hundreds or thousands of times the weight of
the raw materials, owing to the large size of the salt
particles.8–11
It is more difficult to prepare water-soluble salt nano-
particles than water-insoluble nanoparticles such as metallic
oxides, metal sulfides, and metal powders. Water-insoluble
nanoparticles can be prepared by methods like grinding,15,16
chemical precipitation,17–21 or sol–gel synthesis,22,23 but none
of these processes are suitable for the preparation of water-
a
School of Material Science and Engineering, SouthEast University, 2 Sipailou,
Nanjing 210096, China. E-mail: dongyan@seu.edu.cn; Tel: +86 25 52090634
b
Jiangsu Bree Optronics Co., Ltd., Nanjing, China
c
Nanjing Forestry University, Nanjing 210037, China
glomeration tendencies.24–26
Currently, a limited number of methods are available for
the preparation of nanoscale water-soluble salts. A small
amount of water-soluble salt nanoparticles can be prepared
by steam quenching,27,28 but the yield is very low. Andrews
et al.29 used spray drying to prepare NaCl particles, but the
size of the obtained particles was still in the micrometer
range. Malonic ester synthesis was used by Annen et al.30 to
prepare 100–300 nm-sized NaCl nanoparticles, but the raw
materials were expensive, and all operations were carried out
strictly in the absence of water. Ravi Kumar et al.31 prepared
CaCl2 nanoparticles by combining a water-in-oil micro-
emulsion system with vacuum evaporation, and Zhang
et al.32 improved this method by adding cyclohexane. How-
ever, the method was rather complicated, and the cost was
high. Therefore, it remains a challenge to prepare water-
soluble nanoparticles in a simple manner.
Here, we introduce a facile method for preparing water-
soluble potassium sulfate nanoparticles. We performed anti-
solvent precipitation, by mixing an aqueous solution of K2SO4
with ethanol. Because the solubility of K2SO4 in the aqueous-
ethanol solvent system is lower than that in the aqueous system,
the K2SO4 particles precipitate. Anti-solvent precipitation is a
relatively rapid and simple method for recovering water-soluble
materials; however, typically, only particles with micrometer or
submicrometer dimensions can be obtained.33–45 Polyacrylic
acid was introduced to promote particle nucleation and de-
crease the particle size of K2SO4. By varying the amount of

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Paper
polyacrylic acid, K2SO4 particles with dimensions in the range
of 10–100 nm could be obtained.
Experimental procedure
Materials
Raw potassium sulfate (K2SO4, analytical reagent (AR)-grade)
was purchased from Sinopharm Chemical Reagent Co. Ltd.,
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China. Polyacrylic acid (average molecular weight ∼3000) was
obtained from Shanghai Macklin Biochemical Co. Ltd.,
China. Ethyl alcohol (AR-grade) was supplied by Sinopharm.
Ultrapure water was used in the experiments.
Preparation of submicrometer- and nanometer-sized K2SO4
particles
Submicrometer- and nanometer-sized K2SO4 nanoparticles
were prepared by anti-solvent precipitation (Fig. 1). First, an
aqueous solution of K2SO4 (5 mL, 0.1 g mL−1) was mixed with
ethanol (50 mL) as an anti-solvent with stirring or sonication
to obtain white precipitates. The precipitates were then
washed twice with ethanol and dried to obtain K2SO4 parti-
cles. The size of the K2SO4 particles could be controlled by
adjusting parameters like the initial concentration of the
aqueous K2SO4 solution and the mixing order. If a certain
proportion of polyacrylic acid was added to the aqueous
K2SO4 solution, K2SO4 nanoparticles of a specific size could
be obtained.
Fig. 1 Procedure for the preparation of submicrometer-
nanometer-sized K2SO4 particles.
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Characterization
The morphology of the produced particles was inspected
using a field-emission scanning electron microscope (FE-
SEM; Sirion, FEI, USA) and a transmission electron micro-
scope (Tecnai G2 20, FEI, USA). An X-ray diffractometer (XRD;
D8-Discover, Bruker, Germany) and a Fourier-transform infra-
red (FT-IR) spectrometer (Nicolet iS10, Thermo Fisher Scien-
tific, USA) were utilized to characterize the crystal structure
of the precipitates.
Results
Preparation of submicrometer K2SO4 particles by anti-solvent
precipitation
Effect of initial K2SO4 concentration on particle size.
When the aqueous salt solution was mixed with the anti-
solvent (ethanol), the decreased solubility induced the nucle-
ation and growth of K2SO4 particles.46,47 The initial concen-
tration of the solution not only affects the formation of the
nuclei, but also the growth of the grains. We counted the par-
ticles and measured their size in the SEM images. The size of
each rectangular particle was calculated according to the ar-
ithmetic mean of its length and width. We compared the
maximum, minimum, and average sizes of the particles to
distinguish particle size trends as a function of preparation
conditions. As shown in Fig. 2, for an aqueous K2SO4 solution
concentration of 0.1 g mL−1, the average particle size is
∼300–400 nm, and as the concentration decreases, this value
declines. The average size of the obtained particles could be
reduced to 100–200 nm when the concentration of the
aqueous K2SO4 solution was 0.01 g mL−1.
On the one hand, a higher initial concentration could re-
sult in a larger degree of supersaturation, and a mass of seed
particles could grow to form stable nuclei or re-dissolve and
disappear.48 On the other hand, a higher initial concentra-
tion could lead to an increase in the density of crystal nuclei
per unit volume, and the probability that these nuclei would
collide, aggregate, and grow to form larger particles would
or Fig. 2 Effect of initial K2SO4 concentration on particle size: (a) 0.1 g
mL−1; (b) 0.05 g mL−1; (c) 0.01 g mL−1.
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also increase. Therefore, there is a tendency to form large,
non-uniform particles when the initial concentration is high.
Effect of mixing order on particle size and morphology. A
series of comparative experiments were conducted to confirm
that the mixing order could affect the particle size and mor-
phology. There are two ways to carry out anti-solvent precipi-
tation: positive precipitation, in which the ethanol is gradu-
ally added to the K2SO4 solution; or reverse precipitation, in
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which the mixing order is inverted. As shown in Fig. 3, the
particle sizes obtained by positive precipitation are much
higher and the uniformity is lower.
In our opinion, the precipitation process for a water-
soluble salt differs significantly from that of water-insoluble
particles. The water-insoluble particles have very extremely
low solubility, and the precipitate particles will hardly be
redissolved. However, the water-soluble salt has considerable
solubility in the aqueous-ethanol solvent system, such that
the precipitated crystalline nuclei can potentially dissolve
and ripen, which may lead to larger and uneven particle
sizes. In the reverse precipitation process, we used excess eth-
anol (equivalent to 10 times the volume of the K2SO4 aqueous
solution); hence, the solubility of the K2SO4 would be very
low. When the K2SO4 solution was added to ethanol, precipi-
tation occurred immediately, and growth of the precipitated
salt particles through dissolution was difficult because of
their low solubility. In contrast, with positive precipitation,
precipitation does not occur when ethanol is initially added
because the K2SO4 is not supersaturated. The solubility of
K2SO4 decreases with the increase in ethanol content, and
precipitation begins when supersaturation is reached. How-
ever, the ratio of water to ethanol is still high, and K2SO4 still
has relatively high solubility in the system. The newly formed
K2SO4 particles will dissolve and ripen, leading to larger and
uneven particle sizes.
Nevertheless, the size of the K2SO4 particles could not be
reduced below 100 nm either by altering the initial concen-
tration or by changing the mixing order.
Fig. 3 Effect of mixing order on particle size and morphology: (a) 0.1
g mL−1; (b) 0.05 g mL−1; (c) 0.01 g mL−1. The data were obtained by
positive precipitation.
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Preparation and size control of K2SO4 nanoparticles
To obtain K2SO4 particles with smaller sizes, polyacrylic acid
(PAA) was introduced during the preparation process in this
experiment. The amount of added PAA was calculated as a
weight percentage of the K2SO4 solution.
As shown in Fig. 4a, the average size of the particles with
no added PAA is 300–400 nm. As the amount of added PAA
increases, the particles become smaller. When the concentra-
tion of added PAA is 1 wt%, the average particle size is less
than 100 nm; at 4 wt% PAA, the average K2SO4 particle size is
reduced to only 10 nm. At the same time, the shape of the
K2SO4 particles also changes from tetragonal flakes to near-
spherical particles.
The XRD patterns in Fig. 5 indicate that the particles
obtained by anti-solvent precipitation exhibit a pure K2SO4
phase, and the selected-area electron diffraction (SAED) anal-
ysis confirms the result. The broadening of the XRD diffrac-
tion peaks indicates that the particles are very small. For PAA
contents of 0%, 1%, 2%, 3%, and 4%, particle sizes of 305,
97, 36, 25, and 12 nm, respectively, were calculated via the
Debye-Scherrer formula, in agreement with the TEM results.
Fig. 4 Effect of the introduction of PAA on the particle size and
morphology: (a) no PAA; (b) 1 wt% PAA; (c) 2 wt% PAA; (d) 3 wt% PAA;
(e) 4 wt% PAA. The experiments were conducted by reverse
precipitation at an initial K2SO4 concentration of 0.1 g mL−1.
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Fig. 5 X-ray diffraction patterns of the K2SO4 nanoparticles as a
function of PAA content.
In addition, with the increase of PAA content, the XRD dif-
fraction peak shifts to smaller angles, indicating that the ad-
dition of PAA results in a slight distortion of the crystal lat-
tice of K2SO4.
Discussion
From the above results, the addition of PAA is pivotal for
reducing the K2SO4 particle size to the <100 nanometer
level. However, the role of PAA is not clear. One speculation
is that PAA functions as a surfactant that can prevent the
agglomeration of K2SO4 nanoparticles through a steric hin-
drance mechanism.49 However, our experiments with other
surfactants such as polyethylene glycol (PEG), polyvinyl
pyrrolidone (PVP), sodium dodecyl benzene sulfonate
(SDBS), and polysorbate exhibited none of the effects
shown by PAA. Moreover, other water-soluble salt nano-
particles such as NaCl or KCl could not be prepared with
the addition of PAA, which means that PAA may not have
acted as a conventional surfactant in the preparation of the
K2SO4 nanoparticles.
As shown in Fig. 6a, the infrared spectrum of the K2SO4
sample prepared without PAA is consistent with the standard
spectrum of K2SO4.50 Unlike these two spectra, a peak occurs
at 1720 cm−1 in the IR spectrum of the K2SO4 nanoparticles
prepared with added PAA; this peak corresponds to a
COIJCH2CH–COOH) functional group. Moreover, the
intensity of this peak showed almost no change after the
sample was washed several times. This indicates that PAA is
attached to the K2SO4 particles. Its effect may be similar to
the interaction between PAA and CaCO3 particles.51 PAA ion-
izes the COOH anion group, and attracts the positive charge
on the surface of the potassium sulfate particles. The
remaining parts of the PAA molecular chain extend into the
solution, preventing the agglomeration and growth of the
K2SO4 particles.
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Fig. 6 FT-IR spectra of K2SO4 particles prepared with and without the
addition of PAA.
There is another possible explanation for the effect of
PAA. In Fig. 5, the XRD diffraction peaks of potassium sulfate
nanoparticle samples are shifted to a smaller angle with in-
creasing PAA addition. This indicates that the functional
groups of PAA may be adsorbed and incorporated in the
K2SO4 lattice, resulting in a slight lattice distortion of the
microcrystals. A similar phenomenon was found in the effect
of a scale inhibitor on CaCO3 particles.52 The distortion of
the crystal lattice interferes with and destroys the normal
growth of the K2SO4 crystals. Moreover, the interaction be-
tween the K ions and COOH groups may result in the hetero-
geneous nucleation of K2SO4, thus significantly increasing
the salt's nucleation rate.
Based on the IR and XRD results, we speculate that the
presence of PAA affects the nucleation and growth of K2SO4
grains. More experimental evidence is required to verify the
interaction mechanism of PAA.
K2SO4 nanoparticles show promise for many prospective
applications because their melting point is as high as 1067
°C and they have high solubility in water and excellent
chemical stability. They react with difficulty with carbon
materials, metallic oxides (Al2O3, MgO, Fe3O4, NiO), and
metals and alloys (Ni, Co, Cu, FePt, CoPt). Therefore, K2SO4
nanoparticles are very suitable as sacrificial templates for
the preparation of nanoporous materials, hollow nano-
materials, and materials composed of nanoparticles. For ex-
ample, they can be used to prepare chemically ordered
FePt and CoPt nanoparticles,8–11 which can only be
obtained at a temperature above 600 °C. In these salt-
based annealing processes, the particle size of the salt was
20–30 μm, and weights of hundreds of times the weight of
the precursor were required because of the salt's small spe-
cific surface area. If K2SO4 nanoparticles were used, the
amount of salt used can be expected to be reduced by two
orders of magnitude.
Finally, as a further attractive feature, the cost of this anti-
solvent precipitation method is quite low, as only inexpensive
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reagents (ethanol and PAA) are used. The process is also sim-
ple and easily realized on large scale.
Conclusion
Our study shows that anti-solvent precipitation is a feasible
and efficient method for preparing K2SO4 nanoparticles. The
particle size was affected not only by the initial concentration
and mixing order, but also by the addition of PAA. As the
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amount of added PAA increased, the particle size decreased,
such that 10 nm particles could be readily achieved. This
anti-solvent precipitation method can be easily applied in
large-scale production because of its low cost and simplicity.
The obtained K2SO4 nanoparticles would be very suitable as a
sacrificial template material for the preparation of nano-
porous materials, hollow nanomaterials, and other
nanoparticles.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the Industry Foresight and Com-
mon Key Technology Project of Jiangsu Province (grant num-
ber BE2017036); and the Natural Science Foundation for Dis-
tinguished Young Scholar of Jiangsu Province (grant number
BK20160073).
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