Adsorption (2018) 24:345–355

https://doi.org/10.1007/s10450-018-9946-1

Confinement effect on enthalpy of fusion and melting point of organic

phase change materials in cylindrical nanospace of mesoporous silica
and carbon
Jihye Choi1 · Hirotaka Fujita1 · Masaru Ogura1 · Akiyoshi Sakoda1

Received: 8 December 2017 / Revised: 8 February 2018 / Accepted: 21 March 2018 / Published online: 26 March 2018
© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
Organic phase change materials (PCMs) were successfully confined into mesopores of host materials independently via vapor
transportation to precisely investigate the changes in the enthalpy of fusion and the melting point of such confined PCMs
under various conditions. Paraffins, fatty acids, and fatty alcohols with long hydrocarbon chains were employed as guest
PCMs. Mesoporous silica SBA-15s and soft-templated mesoporous carbons with cylindrical mesopores were employed as
host materials of the guest PCMs. It was elucidated that mesopore diameter, functional groups of both PCMs and functional
groups of host materials result in significant changes in the enthalpy of fusion and the melting point of confined PCMs. Fur-
thermore, it was concluded that the host materials with mesopores of diameter 10–20 nm and minimum interaction between
PCM molecules and the functional group on the wall of mesopores of host materials are required to obtain an enthalpy of
fusion of confined PCMs as much as 50% of that in its bulk phase.

Keywords  Confinement effect · Phase change material · Enthalpy of fusion · Melting point

1 Introduction solid–liquid phase change is most commonly used because

Owing to the depletion of fossil fuels and increased energy
consumption, it is important to not only develop new green
energies but also conserve energy. Specifically, efficient use
of energy such as heat recovery and thermal energy storage
are urgently required. Heat can be divided into three dif-
ferent types: sensible heat (Dincer et al. 1997), latent heat
(Kadoono and Ogura 2014), and heat generated during a
chemical reaction (Aihara et al. 2001). Among them, latent
heat enables us to store thermal energy at a high density level
within a narrow temperature range. In order to utilize the
merits of latent heat of phase change, a phase change mate-
rial (PCM) is employed in various heat storage applications
such as solar energy harvesting (Feng et al. 2011), building
materials (Zhou et al. 2012) and enhancement of perfor-
mance of the adsorption process (Horstmeier et al. 2016;
Li and Li 2015). Among various types of phase changes,
* Masaru Ogura
oguram@iis.u‑tokyo.ac.jp
1
Institute of Industrial Science, The University of Tokyo,
Komaba 4‑6‑1, Meguro, Tokyo 153‑8505, Japan
it is easier to confine solid–liquid PCMs due to small volume
change as compared to gas–liquid or gas–solid PCMs (Mon-
dal 2008). There are many types of PCMs such as organics,
inorganics, metals, and hydrates (Farid et al. 2004). For host
materials to confine solid–liquid PCMs in their structures,
polymer (Sari 2004), metallic voids (Li et al. 2015), and
micro-capsule (Sari et al. 2014), etc., were reported.
Recently, porous materials have newly been reported as a
novel host material owing to their high specific surface area,
high structural stability, and most importantly, less leakage
of liquefied PCMs owing to high surface tension derived
from nanopores (Kadoono and Ogura 2014; Mitran et al.
2015; Wang et al. 2016). In the past, melting and freezing
properties in a limited space such as a capillary have mainly
been researched using small model molecules such as water
(Morishige and Iwasaki 2003), methane (Miyahara and Gub-
bins 1997), and benzene (Jackson and Mckenna 1990). How-
ever, these molecules are not suitable for PCMs owing to
their high degree of super cooling and much lower or higher
melting point as compared to room temperature. Currently,
the phase change behaviors of confined, long-chain organic
PCM molecules with less degree of super cooling and
melting point near room temperature such as polyethylene

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346
glycol (Min et al. 2015), paraffin (Nomura et al. 2015), and
fatty acid (Kadoono and Ogura 2014) are under discussion.
Specifically, among the melting properties, decrease in the
melting point of these PCM molecules is being intensively
investigated. On the other hand, in addition to the melting
point, the enthalpy of fusion, which determines the amount
of stored heat, is an important property for the practical
application of PCMs in thermal energy storage. However,
only a few previous works dealt with the change of enthalpy
of fusion. To the best of our knowledge, almost all PCM-
confined materials were prepared using a liquid impregna-
tion method in the previous works (Mitran et al. 2015; Wang
et al. 2016; Jackson and Mckenna 1990). Liquid impregna-
tion is a method of confining PCM into mesopores of host
material via evaporation of volatile liquid solvent from a
mixture of dissolved PCM and host material by heating or
evacuation. During this liquid impregnation step, host mate-
rial comes into contact with the dissolved liquid phase PCM,
and this result in PCM exists not only inside mesopore, but
also outside mesopore, i.e., on the external surface and inter-
granular space. Consequently, the enthalpy of fusion of con-
fined PCM in mesopore was discussed in terms of the units
of J/g-sample or J/g-PCM approximately (Mitran et al. 2015;
Wang et al. 2016; Jackson and Mckenna 1990) because the
accurate amount of PCM existing inside the mesopore and
the exact pore filling ratio of PCM were unknown.
In this study, we confined PCMs using vapor transpor-
tation. With this method, PCMs can exist only inside the
mesopores and this enables us to calculate the exact value of
the pore filling ratio. Using the pore filling ratio, the change
of enthalpy of fusion could be accurately calculated with
the unit of J/g-PCM, and the adequate and effective condi-
tions for obtaining a high value of the latent heat of PCMs
were determined. Paraffin, fatty alcohol, and fatty acid were
selected as PCMs in this study. Mesoporous silica SBA-15
and soft-templated mesoporous carbon, which possesses a
structure analogous to SBA-15, were prepared as the host
materials for the PCMs. Various methods of confining
PCMs, pore diameters of the hosts, functional groups of
PCMs, and quantity of functional groups of host materials
are investigated as the key parameters toward achieving high
value of enthalpy of fusion.
2 Experimental
2.1 Preparation of mesoporous silica SBA‑15s
SBA-15 was synthesized using triblock copolymer
­E O 20PO 70EO 20 (pluronic P123, Sigma-Aldrich) as the
surfactant for cylindrical micelle to form a mesoporous
structure, with tetraethyl orthosilicate used as the silica
source. Each SBA-15 sample name was denoted by the pore
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Adsorption (2018) 24:345–355
diameter, e.g., SBA-15-7.6 nm. SBA-15-7.6 nm was syn-
thesized by following the procedure proposed by Zhao et al.
(1998). 4.0 g of pluronic P123 was added in 30 g of water
and 120 g of 2 M HCl aqueous solution. After P123 was
totally dissolved in solution, 8.50 g of TEOS was added,
and the mixture was stirred for 20 h at 35 °C. Subsequently,
the mixture was aged at 100 °C without stirring. Then, the
solid product was filtered, washed with DI water and dried
at 100 °C for 12 h. Then, SBA-15 was calcined under air
flow for 6 h at 773 K. A heating rate was 1 K/min. SBA-
15-5.6 nm was synthesized under the same conditions as
those of SBA-15-7.6 nm except for the change of aging
temperature from 100 to 40 °C (Valange et al. 2009). SBA-
15-12.5 nm was synthesized by following the procedure
proposed by Kruk et al. (Kruk 2012), wherein triisopropylb-
enzene (TIPB) was added as a swelling agent while mixing
P123 and HCl solution to expand the cylindrical micelle,
followed by stirred at 17 °C and aged at 120 °C.
2.2 Preparation of mesoporous carbons
Soft-templated mesoporous carbon was synthesized by
using pluronic triblock copolymers ­EO100PO65EO100 (F127,
Sigma-Aldrich) as the surfactant for the cylindrical micelle
to form a mesoporous structure and resorcinol as the carbon
precursor. The synthesis procedure proposed by Libbrecht
et al. (2015) was followed. Accordingly, 2.2 g of resorcinol
(Wako) and 2.2 g of F127 were mixed in 9 mL of ethanol
and 9 mL of 3M HCl, and stirred until F127 was fully dis-
solved in a closed vial. Then, 2.6 g of formaldehyde (Wako,
37 wt%) was added and the solution was stirred at 100 rpm
for 15 min in the same closed vial. After the viscosity of the
transparent solution increased, the solution was poured into
a 10 cm-diameter petri dish. Next, ethanol was evaporated at
room temperature for 6 h and subsequently cured at 60 °C in
an oven for 18 h. Subsequently, the resorcinol/formaldehyde
resin deposited at the bottom of the petri-dish was scratched
off, and thereafter calcined under ­N2 flow. First, the tempera-
ture was maintained at 350 °C for 2 h at a heating rate of
1 K/min. Then, the temperature was increased to 800 °C for
3 h to carbonize the resin at the rate of 2 K/min. Half of the
product was oxidized using ozone to increase the oxygen-
containing functional groups on the surface of carbon. The
obtained mesoporous carbon was denoted as MC and its
oxidized sample as OMC.
2.3 Characterization of SBA‑15s and mesoporous
carbons
Nitrogen adsorption (Quantachrome, QUADRSORB evo™)
was performed to analyze the total pore volume Vt , BET sur-
face area SBET  , pore diameter d , and pore size distribution of
the substances used in this study. Pre-treatment of nitrogen
Adsorption (2018) 24:345–355 347
adsorption of mesoporous samples was 300 °C for 3 h, and
that for PCM-confined mesoporous samples was 25 °C for
3 h. Vt is calculated by amount of nitrogen adsorbed when
the relative pressure is 0.95. The pore size distribution was
calculated using the NLDFT method based on a cylindrical
pore model.
X-ray diffraction (XRD) patterns were recorded on a dif-
fractometer (Rigaku, Rint-2100) operating at 40 kV and
40 mA using Cu Kα radiation.
Boehm titration was performed (Boehm et al. 1964) to
characterize the quantity of surface functional groups on
mesoporous carbon. Accordingly, 0.1 g of MC or OMC was
added to 0.1 M NaOH solution and 0.1 M ­NaHCO3 solution.
Subsequently, the mixture was stirred at 300 rpm for 3 days
at 30 °C and carbon powder was recovered via filtration. The
filtered solution was titrated using 0.1 M HCl solution. The
amount of oxygen-containing functional groups was calcu-
lated using titration (Scheibe et al. 2009).
The thermal properties of the PCM confined in SBA-15
were measured using thermogravimetric analysis (TGA;
Rigaku, Thermoplus TG8120) in the temperature range of
room temperature to 250 °C at the heating rate of 1 K/min.
2.4 Confinement of PCM molecules to mesopores
of SBA‑15s and mesoporous carbons
PCMs were confined using vapor transportation. First, a host
material was placed in a vial and dried at 130 °C for more
than 1 h, the weight of which was named as mb as used
below. And glass wool was used to cover the vial to prevent
host materials from escaping during the evacuation step.
The vial with containing the host material was subsequently
placed in the upper part of a corked vacuum desiccator and a
PCM was placed at the bottom of the desiccator separately.
The desiccator was evacuated and maintained at 100–130 °C
in an oven for a few hours such that the vaporized PCM can
be adsorbed and condensed inside the mesopores of host
materials. The resultant solid was recovered, then weighed,
which was defined as ma used below. The vapor pressure of
each PCM was approximately 1 mmHg at the 100–130 °C.
By measuring the weight of the sample before and after the
PCM was confined, the pore filling ratio w of PCM, which
is the ratio of the volume of confined PCM to the total pore
volume of SBA-15, was calculated as follows:
100(ma − mb )
w= (1)
𝜌mb Vt
where ma represents the weight of PCM-confined SBA-
15, mb represents the weight of SBA-15, 𝜌 represents the
density of PCM, and Vt represents the total pore volume of
SBA-15 calculated from nitrogen adsorption. Six species of
PCMs—octadecane, tetradecane, dodecanoic acid, decanoic
acid, tetradecanol, and dodecanol—were confined in each
SBA-15 sample and two species—octadecane and tetrade-
canol—were confined in MC and OMC.
Moreover, octadecane confined in SBA-15 samples with
different mesopore diameters was prepared using the typi-
cal liquid impregnation method according to the method
described in literature (Mitran et al. 2015) to compare the
difference between the melting properties of PCM con-
fined in mesopores using vapor transportation and liquid
impregnation.
2.5 Analysis of the melting properties of PCM
molecules inside the confined nanospace
The melting properties of confined PCM were analyzed
using differential scanning calorimetry (DSC, Shimadzu
DSC-60). Accordingly, 2–3 mg of PCM-confined sample
was used to perform DSC at the heating/cooling rate of
10 K/min.
3 Results and discussion
3.1 PCMs confined in silica hosts
Figure  1 shows the nitrogen adsorption–desorption iso-
therms of synthesized mesoporous silica SBA-15-5.6,
SBA-15-7.6, and SBA-15-12.5 nm and also the pore size
distributions. The corresponding XRD patterns are shown
in Fig. 2. Table 1 shows the porous characteristics of each
SBA-15 sample.
The micropore volume Vmicro of SBA-15 was calculated
using the t-plot method. The mesopore volume Vmeso was
calculated as Vt − Vmicro . Three SBA-15 samples, SBA-15-
5.6, SBA-15-7.6 and SBA-15-12.5 nm, with cylinder-shaped
mesopores were successfully obtained. The pore diameters
of SBA-15-5.6, SBA-15-7.6, and SBA-15-12.5 nm calcu-
lated using the NLDFT method were 5.6, 7.6, and 12.5 nm,
respectively. SBA-15-12.5 nm was observed to have a rela-
tively wide pore size distribution as compared to those of
SBA-15-5.6 and SBA-15-7.6 nm. This is because TIPB,
which works as a swelling agent, was heterogeneously
solved in the micelle. The XRD patterns of all the SBA-15
samples showed a two-dimensional hexagonal periodicity
originating from SBA-15.
Nitrogen adsorption–desorption isotherms of octadecane-
confined SBA-15 are shown in Fig. 3.
Also, Fig. 4 shows the pore filling ratio of confined PCMs
with different pore diameters of SBA-15. The pore filling
ratio was calculated using the weight change of the sam-
ple before and after confining PCM molecules using vapor
transportation (1).
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348 Adsorption (2018) 24:345–355

Fig. 1  a Nitrogen adsorp-

tion–desorption isotherms of
SBA-15s. b Pore size distribu-
tion of SBA-15 calculated by
the NLDFT method

tendency was observed in Fig. 4. Almost 100% of the pores

of SBA-15-5.6 and SBA-15-7.6 nm were filled with PCMs.
However, the pore filling ratio of SBA-15-12.5 nm was only
65%. These indicate that the confinement of PCM with 100%
pore filling ratio becomes difficult with the increase in pore
diameter. This is because the condensation of PCMs inside
the mesopores occur higher relative pressure with increase
of pore diameter. Since we confined PCM in the low vapor
pressure which was approximately 1 mmHg during the vapor
transportation, the relative pressure of PCM in the step of
vapor transportation was not high enough and this causing
difficulty in condensation and fulfillment of PCM inside
mesopores with increase of pore diameter.

3.2 Effect of confining methods on melting

properties
Fig. 2  Low angle XRD patterns of SBA-15s obtained in this study

Octadecane was confined in the mesopore of SBA-15 sam-

The vertical axis in Fig. 3 indicates the adsorbed volume
of nitrogen per weight of SBA-15, which was calculated
by using results from Fig. 4. Figure 3 shows that the total
amount of nitrogen adsorbed on each octadecane-confined
SBA-15 was considerably reduced, when compared to the
total amount of nitrogen adsorbed on pure SBA-15 (Fig. 1),
which suggests that PCMs were filled inside the mesopore.
However, the total volume of nitrogen adsorbed on octade-
cane-confined SBA-15 was different for different pore diam-
eters. The volume of nitrogen adsorbed on SBA-15 samples
increased with the increase in pore diameter. Also, same
ples using the vapor transportation or liquid impregnation
methods to compare their effects on the transportation of
PCM. The melting properties of the octadecane confined in
SBA-15 prepared using the different methods are measured
using the DSC as shown in Fig. 5.
The samples prepared using vapor transportation showed
only one peak of phase change during both cooling and
heating steps. However, the samples prepared using liquid
impregnation demonstrated several peaks. One near the peak
obtained from the samples prepared using vapor transpor-
tation, and at least one more peak near the bulk reference,

Table 1  Characteristics of SBA- Sample SBET ­(m2/g) Vt ­(cm3/g) Vmicro ­(cm3/g) Vmeso ­(cm3/g) d (nm)
15 used in this study
SBA-15-5.6 nm 492 0.444 0.148 0.296 5.6
SBA-15-7.6 nm 941 1.093 0.115 0.978 7.6
SBA-15-12.5 nm 533 1.534 0.000 1.534 12.5

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Adsorption (2018) 24:345–355 349
Fig. 3  Nitrogen adsorption–desorption isotherms of octadecane-con-
fined SBA-15
Fig. 4  Pore filling ratio of PCMs confined in SBA-15s
which is indicated as a colored peak in Fig. 5, during the
cooling or heating steps. Therefore, these colored DSC
peaks, which only exist for the sample prepared using the
liquid impregnation method, originated from a bulk state of
PCM such as an external surface of SBA-15 or intergranu-
lar space of SBA-15 grains because the host material first
mixed with dissolved liquid PCM. DSC peaks that appeared
at a lower temperature originated from nano-confined PCM
inside the mesopore of SBA-15.
The weight loss of both samples shown in Fig. 6 indicates
the vaporization of octadecane via TGA analysis.
The calculated weight ratio of octadecane to SBA-
15 when PCM was confined using vapor transportation
was 66%, which is consistent with the pore filling ratio in
Fig. 4. Further, the calculated weight ratio of octadecane to
SBA-15 when PCM was confined using liquid impregna-
tion was 109%, which is more than 100%. It can be con-
cluded that PCM confined using liquid impregnation was
heterogeneously distributed also on the external surface or
in the intergranular space of SBA-15 owing to the excessive
weight loss of the sample prepared using liquid impregna-
tion. Moreover, the weight loss of the sample prepared using
liquid impregnation began at lower temperature as compared
to the sample prepared using vapor impregnation. This is
because bulk-derived octadecane molecules existing in the
sample prepared using liquid impregnation have weak inter-
action compared to octadecane confined by surface tension,
and hence, the vaporization of octadecane began in a lower
temperature range.
The observed effect of bulk-derived PCM on its melting
properties was a shift of both melting and freezing points
(Fig. 5). When bulk-derived PCM exists, the nano-confined
peaks shifted closer to bulk-derived peak at a high tempera-
ture. Since there was no difference between the two samples
except for their confining methods, the shift of both melting
and freezing points was caused by the method of loading of
PCM on the SBA-15 porous structure. The shift of the freez-
ing point might have been affected by the nucleation of bulk
PCMs (Kittaka et al. 2013). Furthermore, since bulk PCMs
exist on the external surface and in the intergranular space
of its substrate, the meniscus of the confined PCM could
be changed (Schreiber et al. 2001) and this possibly has an
influence on the melting point. As discussed above, confin-
ing PCM using vapor transportation is an effective method
to avoid the effect of excessive bulk residue on its melting
properties. Furthermore, using vapor transportation, the
exact value of pore filling ratio can be calculated as shown in
Fig. 4, and this is an important advantage because the exact
value of the enthalpy of fusion with the unit of J/g-PCM can
be elucidated using the accurate pore filling ratio.
3.3 Changes in enthalpy of fusion and melting
point of PCMs confined in silica host
Figure 7 shows the DSC curves of various organic PCMs
confined in SBA-15 with different pore diameters during
heating.
The enthalpy of fusion ΔHf with the unit of J/g-PCM, and
the melting point ­Tmelting are summarized in Table 2.
ΔHf was calculated by using the pore filling ratio. Notably,
all the values of the enthalpy of fusion and melting points of
the confined PCMs were lower when compared with the cor-
responding values of the bulk PCMs. The enthalpy of fusion
and melting point increased with the increase in pore diameter,
and became closer to the corresponding values of the bulk
PCMs. Specifically, in Fig. 7, no phase change was observed
when fatty alcohols (tetradecanol or dodecanol) were confined
in SBA-15-5.6 nm. This can be explained in two ways: one is
that the phase change of the confined fatty alcohol does not
occur owing to a strong interaction of PCM with the surround-
ing silica wall, and the other is that the enthalpy change of
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350
Fig. 5  DSC curves of octadecane confined in SBA-15 by different methods: liquid impregnation and vapor transportation. a octadecane/SBA-
15-5.6 nm, b octadecane/SBA-15-7.6 nm, c octadecane/SBA-15-12.5 nm
Fig. 6  TGA curves of octadecane-confined SBA-15 prepared by dif-
ferent confining method
the phase change is too low to be detected by DSC. Also, two
endothermic peaks were observed when tetradecanol was con-
fined in SBA-15-12.5 nm. This might be because phase transi-
tion of tetradecanol occurred in 2 steps: solid–solid transition
and solid–liquid transition (Zeng et al. 2009). In this work, we
calculated the enthalpy of fusion of tetradecanol confined in
SBA-15-12.5 nm by sum of the enthalpy of both peaks.
Typically, the difference in the melting points ( ΔT ) of the
confined PCM is expressed by the Gibbs–Thomson equation
(Christenson 2001) (2);
2Tbulk Vm 𝛾sl cos 𝜃
ΔT = (2)
rΔHf
13
Adsorption (2018) 24:345–355
where 𝛾sl represents the surface tension, ΔHf represents the
fusion enthalpy, Vm is the molar volume, Tbulk represents the
bulk melting point, 𝜃 represents the interfacial contact angle
between the nucleating phase and support surface, and r is
the radius of a pore. The Gibbs–Thomson equation shows
that an inverse of pore diameter (d−1) and the differential of
melting point ( ΔT ) have a linear relationship and the extrap-
olation of this linear relationship is converged to zero. The
Gibbs–Thomson equation is a remarkable indication, and
was used in many preceding researches (Christenson 2001;
Mitran et al. 2015). In this study, d−1 and ΔT have a linear
relationship. However, the extrapolation of d−1 and ΔT is not
converged to zero (Fig. 8a). The result of Fig. 8a was plotted
when the pore diameters were at the scale of approximately
10 nm and below.
Hence, this suggests that another appropriate parameter
should be added to the evaluation given by the Gibbs–Thom-
son equation. Other parameters such as non-melting layer
(Morishige et al. 2000; Christenson 2001) or surface rough-
ness (Tanaka et al. 2013) should be considered when phase
change occurs in a nanoscale space.
Figure 8b shows the plot of the enthalpies of fusion of
the confined PCMs versus the pore diameter of the host. The
enthalpy of fusion also has a linear relationship with the pore
diameter of the host. When the pore diameter increased, the
enthalpy of fusion of PCM became closer to the correspond-
ing value of the bulk PCM. The possible reason for the lower
value of the enthalpy of fusion is the effect of the non-melt-
ing layer. A non-melting layer is composed of a few molec-
ular layers that freezing and melting do not occur owing
to the interaction between PCM molecules and the wall of
the host (Churaev et al. 1993). If the pore diameter of the
Adsorption (2018) 24:345–355 351

Fig. 7  DSC curves of a octadecane, b tetradecane, c dodecanoic acid, d decanoic acid, e tetradecanol, and f dodecanol confined in SBA-15s

Table 2  Melting properties of organic PCMs confined in SBA-15s

SBA-15 Octadecane Dodecanoic acid Tetradecanol Tetradecane Decanoic acid Dodecanol

ΔHf (J/g-PCM) 5.6 nm 39.1 19.1 – 54.6 9.0 –

7.6 nm 53.3 30.8 6.4 82.2 33.9 10.3
12.5 nm 103.3 65.9 48.4 124.2 64.3 69.5
Bulk 230 169 198 216 163 196
Tmelting (°C) 5.6 nm 9.3 − 8.86 – − 20.4 − 26.0 –
7.6 nm 11.7 3.6 6.4 − 12.4 − 4.1 − 4.1
12.5 nm 17.4 22.32 11.4 − 7.4 11.1 0.2
Bulk 26.5 44.6 36.0 6.2 30.0 24.0

host decreases, the volume of the non-melting layer inside pore is not exactly the same as that of the bulk liquid phase,
the pore increases, and consequently, the effect of the non- and this could be another possible reason for the decrease
melting layer is significant and the value of the enthalpy of in the enthalpy of fusion. From the results of Fig. 8b, it can
fusion reduces. Moreover, the state of liquid phase inside the be observed that the value of the enthalpy of fusion reaches

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352
Fig. 8  a Experimental ΔTm val-
ues plotted as a function of pore
diameter d−1, and b the relative
enthalpy of fusion of each PCM
to bulk as a function of d 
approximately 40% that of the bulk PCM for pore diameters
more than 10 nm. The value of enthalpy of fusion of tetrade-
cane confined in SBA-15-12.5 nm is almost 60% that of the
bulk PCM. According to the work by Jackson and Mckenna
(1990), the enthalpy of fusion rapidly increases when the
pore diameter d is below 10 nm, and it gradually increases
when d is in the range of approximately 10–25 nm. When d
is larger than 25 nm, the value of enthalpy of fusion is satu-
rated according to the reported results. From these results, it
can be predicted that the enthalpy of fusion of the confined
tetradecane will be saturated at ca. 60% even if d increases
beyond 12.5 nm. Moreover, as discussed above, fully con-
fined PCM within the mesopore is difficult to attain with
the increase in pore diameter. Consequently, 10–20 nm is a
preferable pore diameter for the confinement of PCM, result-
ing in the achievement of high enthalpy of fusion inside the
mesopore.
It is generally accepted that SBA-15 has not only periodic
mesopores but also a micropore between the mesopores.
It can be concluded that a phase change in the micropore
does not occur owing to the effect of small pore diameter.
Hence, the enthalpy of fusion with the unit of J/g-PCM cal-
culated from the weight of PCM existing only mesopores
can increase and further investigation is required.
Fig. 9  a Nitrogen adsorption
and desorption isotherm of
MC and OMC, and b pore size
distribution of MC and OMC
calculated by NLDFT method
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Adsorption (2018) 24:345–355
All six species of PCMs are shown to have a propor-
tional relationship to the pore diameter of the host except
for fatty alcohols confined in SBA-15-5.6 nm. However,
there is a difference between the relationship when paraf-
fin, fatty acids, and fatty alcohol with different functional
groups confined in nanospace in Fig. 8. A silica wall con-
tains silanol groups. Since hydroxyl group and carboxylic
acid group interact more strongly with silanol group via
hydrogen bonding as compared to an alkane group, the
change of melting point and enthalpy of fusion of fatty
acids and fatty alcohol were more significant as compared
to paraffin. This indicates that, if the interaction with PCM
molecules and the wall of host material becomes stronger,
the pore diameter will have a more significant effect on
the melting properties. Therefore, to achieve high enthalpy
of fusion with host material containing hydrophilic walls
such as silica, PCMs should be selected from hydrophobic
molecules such as paraffin.
3.4 Characterization of soft‑templated mesoporous
carbons
Nitrogen adsorption–desorption isotherms and pore size
distribution of synthesized soft-templated mesoporous
Adsorption (2018) 24:345–355 353

carbon MC and OMC are shown in Fig. 9. The shape of
adsorption branch, total amount adsorbed, pore diameter,
and pore size distribution of MC and OMC was exactly
same, which indicates that oxidation with ozone does not
undergo a physical change.
The calculated amount of surface oxygen-containing
groups of MC and OMC using the Boehm titration method
is shown in Table 3.
The amount of phenolic hydroxyl group and carboxylic
acid group on the surface of OMC increased via surface
oxidation with ozone. OMC has a 5–6 times larger amount
of surface oxygen-containing groups as compared with
MC. From the results mentioned above, MC and OMC can
be considered to have exactly the same parameters such as
pore shape, total pore volume, pore diameter, and pore size
distribution with the exception of the amount of functional
groups on the surface. The pore filling ratios of octadecane
and tetradecanol confined in MC and OMC, respectively,
are shown in Fig. 10.
Table 3  Amount of the following functional groups exist on carbon
surface
Functional group Phenolic hydroxyl Carbox-
(mmol/g) ylic acid
(mmol/g)
MC 0.047 1.086
OMC 0.846 4.568
3.5 Changes in enthalpy of fusion and melting
point of PCMs confined in carbon host
The DSC curves of octadecane and tetradecanol confined in
MC and OMC, respectively, are shown in Fig. 11.
The enthalpy of fusion corresponds to the area of the
DSC peak, and the melting point is indicated as the point
crossing the base line and a tangential line of the DSC peak
in Fig. 11. The enthalpy of fusion and melting point of octa-
decane are almost the same irrespective of whether it is con-
fined in the porous structures of MC or OMC. However, a
noticeable difference can be observed between the values
of the enthalpy of fusion and the melting point of tetrade-
canol when confined in the pores of MC or OMC. Specifi-
cally, with the increase in the amount of surface oxygen-
containing functional groups, the enthalpy of fusion of the
tetradecanol became considerably reduced. The calculated
values of the enthalpies with the unit of J/g-PCM of confined
octadecane and tetradecanol are listed in Table 4.
ΔHf ,MC − ΔHf ,OMC represents the difference between
the enthalpies of fusion of MC and OMC. When octa-
decane was confined in OMC, the value of the enthalpy
of fusion was lower only by 1.4 J/g-PCM as compared to
that confined in MC. On the other hand, when tetrade-
canol was confined in OMC, the value of the enthalpy of
fusion was lower by 18.5 J/g-PCM as compared to that
confined in MC. This decrease corresponds to approxi-
mately 50% of the enthalpy of fusion of tetradecanol con-
fined in MC because the amount of oxygen-containing

Table 4  The enthalpies of fusion of PCMs confined in mesoporous

carbons
PCM Host material ΔHf (J/g- ΔHf ,MC − ΔHf ,OMC
PCM) (J/g-PCM)

Octadecane MC 46.1 1.4

OMC 44.7
Tetradecanol MC 30.0 18.5
OMC 11.5
Fig. 10  Pore filling ratio of PCMs confined in mesoporous carbons

Fig. 11  DSC curves of a
octadecane and b tetradecanol
confined in OMC and MC

13

354
functional groups existing on the surface of OMC was 5–6
times larger than that on MC. The hydroxyl group of tet-
radecanol interacts with the oxygen-containing groups of
carbon wall such as phenolic hydroxyl or carboxylic acid
groups. This interaction causes the tetradecanol molecules
near the wall of carbon host to be arranged irregularly, i.e.,
not in order. Moreover, these molecules are restricted from
moving freely. There might be an increase in the thickness
of the non-melting layer, and subsequently, the enthalpy
of fusion can decrease. On the contrary, in case of octa-
decane, which is an alkane with no functional group, the
enthalpy of fusion did not dramatically changed owing to
small interaction.
These results suggest that the interaction between a
functional group on the PCM molecules and a functional
group on the host material strongly affects the enthalpy
of fusion of the confined PCM. If PCM molecules have
a functional group with strong interaction with a surface
functional group, reducing the amount of surface func-
tional groups on the wall of the host or substitution of PCM
into the molecules not yet containing a strongly interacting
functional group are required to achieve a high latent heat.
In particular, PCM, which is composed only of hydrocar-
bon such as paraffin, is preferable to achieve a high latent
heat under any conditions because it has no functional
group to interact with.
4 Conclusions
The melting behavior of a long-chain organic PCM in a
cylindrical mesopore of mesoporous silica and carbon host
is studied. The methods to confine PCM in the mesopore,
pore diameter, functional groups of PCM molecules, and
functional groups of the wall of the host were investigated as
the parameters that affect the melting behavior. Confinement
of PCM using vapor transportation is a promising method
to confining organic PCM only inside the mesopore. When
the pore diameter decreases, the influence of the non-melting
layer on the melting behavior becomes significant, and leads
to the decrease in the enthalpy of fusion of PCM. Moreover,
when the interaction between PCM molecules and the wall
of the host material is strong (e.g., hydrogen bonding), the
PCM molecules cannot be aligned in order and their motion
is strictly limited, resulting in the decrease in the enthalpy
of fusion. Consequently, by selecting the host materials with
mesopores of 10–20 nm in diameter and PCM molecules
with a functional group that weakly interacts with the wall
of the host such as paraffin, enthalpy of fusion more than
50% of the value of the heat generated by the bulk PCM can
be obtained.
13
Adsorption (2018) 24:345–355
Acknowledgements  The authors would like to express sincere grati-
tude to Professor Ryo Shirakashi and research associate Kiyoshi
Takano, IIS, the University of Tokyo, for their support in the experi-
mental section of the DSC measurement.
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