Materials Letters 215 (2018) 137–139

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Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Water adsorption capacity enhancement of ferroaluminophosphate

(FAPO4-5) by impregnation of CaCl2
Bao Nguyen Truong a,b, Jeasung Park a, Oh Kyung Kwon b,c, In Park a,b,⇑
a
Intelligent & Sustainable Materials Group, Korea Institute of Industrial Technology, 89 Yangdaegiro-gil, Ipjang-myeon, Cheonan-si 31056, South Korea
b
Department of Green Process and System Engineering, University of Science and Technology (UST), 176 Gajeong-dong, Yuseong-gu, Daejeon 34113, South Korea
c
Thermal & Fluid System Group, Korea Institute of Industrial Technology, 89 Yangdaegiro-gil, Ipjang-myeon, Cheonan-si 31056, South Korea

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

Article history: New composite materials were prepared by impregnating CaCl2 into FAPO4-5 to enhance the water
Received 28 August 2017 adsorption capacity of the FAPO4-5 and limit the deliquescence of CaCl2. The structure of the FAPO4-5
Received in revised form 4 December 2017 was not changed after impregnation, as confirmed by the corresponding X-ray diffraction (XRD) patterns.
Accepted 17 December 2017
The composite materials exhibited enhanced water adsorption capacity (up to 08 g/g-sorbent at 50.0 wt%
Available online 18 December 2017
loading) within the working relative pressure range of water vapor of adsorption heat pump (AHP) sys-
tems (0.1–0.3 of water vapor relative pressure). The composite material with CaCl2 loading up to 15.9 wt
Keywords:
% can also minimizes deliquescence of the salt which is not preferable in AHP applications. Despite partial
Ferroaluminophosphate
CaCl2
pore filling of CaCl2 in the matrix, the adsorption capacities of the composites were comparable to the
Impregnation sum of the adsorption capacities of CaCl2 and FAPO4-5 without significantly affecting that of the pristine
Water adsorption FAPO4-5.
Ó 2017 Elsevier B.V. All rights reserved.

1. Introduction have been investigated as components of CSPMs such as CaCl2/sil-

In recent years, studies on adsorption heat pumps (AHP) are
attracting attention because of its ability to utilize low tempera-
ture heat source such as waste heat and solar heat. In addition,
their working fluids such as water and methanol have little harm-
ful effects on environment [1]. For an AHP system operated by
using water as a working fluid, the heat source temperature and
working temperature are 80 and 30 °C, respectively, corresponding
to the adsorption and desorption relative pressures of water vapor
(0.3 and 0.1, respectively) [2]. In other words, an S-shaped steep
uptake in the relative pressure range of 0.1–0.3 is preferable for
adsorbents used in the AHP systems.
Among research on the adsorbents for AHP application, com-
posites ‘‘salt inside porous matrix” (CSPM) [3] showed many
advantages benefiting from their components, inorganic salts and
porous materials. Thus, on one hand, the salts improve the sorption
capacity of the porous materials. On the other hand, the porous
material can overcome the disadvantages of salt using in AHP such
as deliquescence and swelling [4]. Many salts and porous materials
⇑ Corresponding author at: Intelligent & Sustainable Materials Group, Korea
Institute of Industrial Technology, 89 Yangdaegiro-gil, Ipjang-myeon, Cheonan-si
31056, South Korea.
E-mail address: inpark@kitech.re.kr (I. Park).
ica gel [5,6], CaCl2/MCM-41 [7], CaCl2/SBA-15 [8], and LiBr/silica
gel [9].
In this work, we report a new CSPM prepared from porous
matrix named AQSOA-Z01, a partially Fe-substituted material from
aluminophosphate AlPO4-5 (named FAPO4-5) [10,11], and CaCl2.
The study aims to combine the advantages of the host and the salt
which are the high water adsorption capacity in AHP working rel-
ative pressure and the stability in that condition.
2. Experimental
FAPO4-5, an iron-doped aluminophosphate zeolite with the AFI
structure which is a one-dimensional pore structure, and pore size
of 0.74 nm [11], was studied as the host matrix. It was synthesized
by following the recipe from literature [10] (see Supplementary
data for more detail).
The porous material then was applied as the matrix for prepa-
ration of CSPM where CaCl2 was impregnated into. FAPO4-5-
CSPM samples in different mass contents of CaCl2/FAPO4-5 were
prepared by following procedure: a solution of calcium chloride
dihydrate in deionized water was mixed with a mixture of FAPO4-
5 in deionized water in proper weight ratios of CaCl2 compared to
the composites. A small amount of deionized water was then

https://doi.org/10.1016/j.matlet.2017.12.073
0167-577X/Ó 2017 Elsevier B.V. All rights reserved.
138 B.N. Truong et al. / Materials Letters 215 (2018) 137–139
added to the new mixture for better disperse the solid phase. After
that, the mixture was stirred at ambient temperature during 30
min followed by drying at 200 °C in the spray dryer (DJE-MD-
011R, spray type: nozzle, inlet temp: 200 °C, outlet temp.: 100 °C,
feed rate ca. 50 mL/min). More detail in preparation of CSPM sam-
ples is shown in Table S1. For comparison, the physical mixtures of
CaCl2 and FAPO4-5 were also prepared.
The existence of CaCl2 and the remaining structure of FAPO4-5
were analyzed by powder X-ray diffraction (XRD), scanning elec-
tron microscopic (SEM), and energy dispersive X-ray spectra
(EDX). Porosity of the CSPM samples was studied by N2 and Ar
adsorption. The water adsorption was also evaluated to consider
the applicability of the composite to the AHP (See Supplementary
data).
3. Results and discussion
The XRD patterns of FAPO4-5, CaCl2, and CSPM samples are
shown in Fig. 1. The patterns from CSPM samples confirm that
the host phase was retained after the impregnation and drying pro-
cesses. Moreover, reflections corresponding to CaCl2 observed in
the XRD pattern of the CSPM sample containing 15.9 wt% of CaCl2
show the formation of CaCl2 crystalline phase in the composite
which cannot be seen at the lower loading samples. It is reasonable
to think that in low loading CSPM samples, Calcium chloride mole-
cules are confined inside the micropores of FAPO4-5 which are
unable to form a crystalline phase and therefore resulting in no sig-
nal of the salt phase in the XRD pattern. The existence of CaCl2 in
the CSPM samples at the low salt loading than 15.9% was con-
firmed by SEM-EDX (see Supplementary data).
Although the structure of the porous phase was remained, the
N2 adsorption/desorption of CSPM samples (Fig. S2) shows that
the impregnation of CaCl2 into the micropore resulted in the reduc-
tion of the pore volume of the sample even at 3.8 wt% CaCl2 to one-
tenth of the pristine FAPO4-5. The reduction of pore volume at the
very low loading of CaCl2 can be explained by the one-dimensional
pore structure of FAPO4-5; therefore, the impregnated CaCl2 in the
internal space of the pores might block the entry of the N2
molecules.
Fig. 1. XRD patterns of CSPM samples (a) dihydrated CaCl2, (b) anhydrous CaCl2,
and samples containing (c) 0 wt%, (d) 3.8 wt%, (e) 7.7 wt%, (f) 15.9 wt%, (g) 33.3 wt%,
and (h) 50.0 wt% of CaCl2.
Fig. 2. Water adsorption isotherms of (a) FAPO4-5, (b-f) CSPM samples containing
various amounts (0, 3.8, 7.7, 15.9, 33.3, 50 wt%, respectively) of CaCl2, and (g) bulk
CaCl2 obtained as a function of water vapor relative pressure at 25 °C.
Water vapor adsorption isotherms of the CSPM samples are
indicated in Fig. 2. It shows that the amount of water sorption
capacity is enhanced in correlating with CaCl2 loading. Moreover,
water vapor sorption isotherms of CSPM samples with 15.9 wt%
loading and above show clear steeps corresponding to the hydra-
tion of CaCl2 while the isotherms of lower loading samples (3.8
and 7.7 wt%) do not. Furthermore, the linear isotherm of the sam-
ple at 50 wt% salt loading (P/P0 > 0.22) results from the deliques-
cence property of CaCl2 which is not desirable for AHP
applications. The observed phenomena can be explained that at
the low loading, the limited pore space prevents the confined salt
from adsorbing high number of water molecules that could cause
swelling and deliquescence. However, at high loading, the pores
are completely filled which results in the deposition of salt on
the external surface area of the matrix and therefore, cannot pre-
vent the deliquescence. The role of CSPM samples in minimization
of deliquescence of the salt was also studied by performing water
sorption of the CSPM samples and physical mixtures (Fig. S4). The
results show that the low loading (15.9 wt%) CSPM samples can
limit the deliquescence which can damage the AHP systems while
the others cannot. At the higher loading (33.3%), the deliques-
cence becomes serious for both kinds of samples as no comparable
difference between them can be seen.
Fig. 3 shows a comparison between the experimental (a) and
calculated (b) water vapor adsorption values of the samples. In
the case of the calculated plot, the values corresponding to the
open circles in (b) were obtained by adding linearly the adsorption
capacity of CaCl2 in range of relative pressure from 0.1 to 0.3 to
that of pristine FAPO4-5. Although the nitrogen adsorption
(Fig. S2b) shows pore blocking by CaCl2, the experimental adsorp-
tion capacity (squares, (a)) is comparable to the values shown by
circles (b) in Fig. 3, without significant negative effect on the water
vapor adsorption capacity of the matrix except the sample of 33.3
wt% CaCl2 loading. It might be that the N2 molecules which are
inert to interaction with the salt cannot pass through the blockage
of salt to access the adsorption sites inside the pore. In contrast, the
water molecules can hydrate the salt and therefore penetrate for
the adsorption sites. These phenomena are illustrated in
Scheme S1.
 B.N. Truong et al. / Materials Letters 215 (2018) 137–139
Fig. 3. Water adsorption values of (a) experimental (squares) and (b) calculated of
the pristine FAPO4-5 and the CSPM samples (b, circles calculated by adding the
water adsorption values of bulk CaCl2 to that of pristine FAPO4-5).
4. Conclusion
FAPO4-5 CSPMs were successfully synthesized by impregnating
CaCl2 into the FAPO4-5 pores. The new materials showed enhanced
water adsorption compared to that of pristine FAPO4-5 in the rela-
tive pressure range from 0.1 to 0.3, corresponding to the working
condition of AHP. The main advantage of the FAPO4-5/CaCl2 com-
posites is that the water adsorption capacities can be obtained
without reducing the water adsorption capacity of the matrix.
Another advantage of the CSPMs is that they hinder the deliques-
cence of the salt in the confined micropores and textural pores of
the porous matrix. Since the deliquescence of the adsorbents
may damage the stability of the coating on the heat exchangers
in AHP systems, among experimental samples, the CSPM samples
with amount of CaCl2 up to 15.9 wt% which were proved for the
ability to minimize the deliquescence leakage are more proper to
apply into AHP system than the higher loading. In addition, we
139
require a more detailed study on the application of this material
in AHP.
Acknowledgement
This research was supported by a grant of the Korea Institute of
Industrial Technology funded by Ministry of Strategy and Finance
(Project number: EO170030) of South Korea.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.matlet.2017.12.073.
References
[1] H. Demir, M. Mobedib, S. Ülkü, A review on adsorption heat pump: Problems
and solutions, Renewable Sustainable Energy Rev. 12 (2008) 2381–2403.
[2] K. Okada, M. Nakanome, Y. Kameshima, T. Isobe, A. Nakajima, Water vapor
adsorption of CaCl2-impregnated activated carbon, Mater. Res. Bull. 45 (2010)
1549–1553.
[3] L.G. Gordeeva, Y.I. Aristow, Composites ‘salt inside porous matrix’ for
adsorption heat transformation: a current state-of-the-art and new trends,
Int. J. Low-Carbon Technol. 7 (2012) 288–302.
[4] N. Yu, R.Z. Wang, L.W. Wang, Sorption thermal storage for solar energy, Prog.
Energy Combust. Sci. 39 (2013) 489–514.
[5] Y.I. Aristov, M.M. Tokarev, G. Cacciola, G. Restuccia, Selective water sorbents
for multiple applications, 1. CaCl2 confined in mesopores of silica gel: Sorption
properties, React. Kinet. Catal. Lett. 59 (1996) 325–333.
[6] Y.I. Aristov, M.M. Tokarev, G. Restuccia, G. Cacciola, Selective water sorbents
for multiple applications, 2. CaCl2 confined in micropores of silica gel: Sorption
properties, React. Kinet. Catal. Lett. 59 (1996) 335–342.
[7] M. Tokarev, L. Gordeeva, V. Romannikov, I. Glaznev, Y. Aristov, New composite
sorbent CaCl2 in mesopores for sorption cooling/heating, Int. J. Therm. Sci. 41
(2002) 470–474.
[8] I.V. Ponomarenko, I.S. Glaznev, A.V. Gubar, Y.I. Aristov, S.D. Kirik, Synthesis and
water sorption properties of a new composite ‘‘CaCl2 confined into SBA-15
pores”, Microporous Mesoporous Mater. 129 (2010) 243–250.
[9] L.G. Gordeeva, G. Restuccia, G. Cacciola, Y.I. Aristov, Selective water sorbents
for multiple applications, 5. LiBr confined in mesopores of silica gel: Sorption
properties, React. Kinet. Catal. Lett. 63 (1998) 81–88.
[10] H. Kakiuchi, S. Shimooka, M. Iwade, K. Oshima, M. Yamazaki, S. Terada, H.
Watanabe, T. Takewaki, Novel water vapor adsorbent FAM-Z01 and its
applicability to an adsorption heat pump, Kagaku Kogaku Ronbunshu 31
(2005) 361–364.
[11] S. Shimooka, K. Oshima, H. Hidaka, T. Takewaki, H. Kakiuchi, A. Kodama, M.
Kubota, H. Matsuda, The evaluation of direct cooling and heating desiccant
device coated with FAM, J. Chem. Eng. Jpn. 40 (2007) 1330–1334.