Materials Today: Proceedings xxx (xxxx) xxx

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Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent

for removal of methylene blue from aqueous solution
Ratna Ediati ⇑, Pradena B.F. Laharto, Rosiana Safitri, Hilda Mahfudhah, Dety Oktavia Sulistiono,
Terry Denisa Syukrie, Muhammad Nadjib
Department of Chemistry, Institut Teknologi Sepuluh Nopember, Surabaya, Indonesia

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

Article history: HKUST-1 and Al-MCM-41/HKUST-1 composites were successfully synthesized by a solvothermal method
Received 27 May 2020 in a mixture of N-N0 -dimethylformamide (DMF), ethanol and water in a ratio of 1:1:1 at 100 °C for 10 h,
Accepted 17 June 2020 with mass variations of Al-MCM-41 at 3, 5 and 7% toward the mass of HKUST-1, respectively. The results
Available online xxxx
of the XRD analysis showed characteristic peaks of HKUST-1 at 2h of 6.61, 9.39, 11.51 and 13.31° with
high intensities. The addition of mesoporous aluminosilicate, Al-MCM-41, did not significantly alter
Keywords: the diffraction pattern except for the decrease in the intensity of the characteristic peaks. The FTIR spectra
MOF
showed the presence of absorption bands typical of both HKUST-1 and Al-MCM-41 materials. HKUST-1
HKUST-1
Adsorption
and Al-MCM-41/HKUST-1 composites showed exceptional performance in rapidly removing methylene
Methylene Blue blue at greater than 95% removal in less than 14 min. Isothermal and kinetic adsorption studies follow
Adsorption kinetics the modeling of the Freundlich isotherm and pseudo-second order kinetics.
Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Regional Congress on
Membrane Technology 2020 (RCOM 2020) and Regional Conference Environmental Engineering (RCEnvE
2020). This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/
by-nc-nd/4.0/).

1. Introduction
The amount of waste water from the textile industry has
increased significantly due to the growth of the apparel industry.
Dyes are among the substances contained in industrial waste [1].
Methylene blue is one of the cationic dyes that are widely used
in the clothing industry [2]. Various methods of handling dyes
from industrial waste have been performed, such as physical,
chemical and biological methods [3]. However, some methods that
have been reported to have disadvantages include a method that is
not easy and expensive. Adsorption is suggested to be one of the
most convenient methods of removing waste dye due to its simple
and rapid process [4]. Various materials have been reported as
adsorbents in the removal of dye in the wastewater such as zeolite
[5], metal oxides [6], activated carbon [7], and other porous
materials.
Metal organic framework (MOF) is a porous crystalline inor-
ganic material that has attracted many researchers’ attention in
recent years. MOF consists of metal ions or clusters that form coor-
⇑ Corresponding author.
E-mail addresses: rediati@chem.its.ac.id, ratna.ediati@gmail.com (R. Ediati).
dination bonds with organic ligands, in which types of metals and
organic ligands play an important role, because replacing one of
them results in a different MOF type [8]. The availability of various
metals and organic ligands results in numerous of MOF whose
structures and properties that can be tailored to specific applica-
tion requirements. The high surface area and porosity make MOF
widely used as a catalyst, drug delivery, sensor, and adsorbent [9].
HKUST-1, generally [Cu3(BTC)2(H2O)3].xH2O, is synthesized
using copper nitrate trihydrate precursor [Cu(NO3)23H2O], and
1,3,5-benzene tricarboxylic acid (H3BTC) in the solvent mixture
of water, ethanol and DMF through the solvothermal method at
100 °C for 10 h [10]. HKUST-1 is one type of MOF that has been
developed because of its easy synthesis process, large surface area
and regular pores [11]. However, similar to other porous materials
HKUST-1 has diffusion problems for large molecules because it has
a micropore size [12].
On the other hand, MCM-41 or Mobile Crystalline of Materials is
one type of mesoporous silica, which was first synthesized in 1992
by researchers from Mobil Corporation. MCM-41 with a controlled
mesoporous structure is widely studied because of its wide poten-
tial application which can be as catalysis, separation, adsorption,
microelectronics, drug delivery system and biomedical device

https://doi.org/10.1016/j.matpr.2020.06.361
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Regional Congress on Membrane Technology 2020 (RCOM 2020) and Regional Conference
Environmental Engineering (RCEnvE 2020).

Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
2 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx

[13]. MCM-41 has the characteristics of a large surface area and
mesopore size that allows large molecules to interact into the pore
material. Ordinary MCM-41 has a weak acid side which results in
its active side being weak so it is less efficient in its application.
The addition of Al in during MCM-41 synthesis can change the
properties of the obtained Al-MCM-41 material. The addition, the
presence of Al in the MCM-41 meso structure results in the forma-
tion of Al-MCM-41 with a higher thermal stability, the Al-MCM-41
material has been applied in various applications such as ion
exchange, catalysis and adsorption [14].
Several previous studies have reported that the addition of
mesoporous material during the synthesis of MOF can improve
its performance [1516]. Tari et al. have reported that adding
MCM-41 at the time of Cu(BDC) synthesis can increase the specific
surface area by 73% as compared to Cu(BDC) and increase its per-
formance in CO2 adsorption [17]. Liu et al. have confirmed that the
addition of SBA-15 mesoporous material to Ni-based MOF can
improve its performance in CH4/N2 gas adsorption. Further
research on other types of MOF to achieve excellent adsorption
selectivity and high adsorption capacities is still required [18].
In connection with efforts to modify porous materials to obtain
materials with superior properties, MOF type HKUST-1 also known
as Cu-BTC with the addition of mesoporous aluminum silica has
been introduced as an alternative adsorbent in the methylene blue
adsorption process. Al-MCM-41 is mesoporous aluminum silica
with regular pore structure characteristics, high thermal stability,
and has a Lewis acid active site which is expected to cover the
weaknesses of HKUST-1 when used as an adsorbent of methylene
blue in water.
2. Experimental
2.1. Materials
1,3,5-benzenetricarboxylic acid (H3BTC) and Copper(II) nitrate
trihydrate [Cu(NO3)2.3H2O] were purchased from Sigma Aldrich,
Ethanol, N,N-dimethylformamide (DMF) and Methanol was pur-
chased from MERCK. Al-MCM-41 as supporting material has been
synthesized according to previous research [19]. The Methylene
blue dye was obtained from MERCK.
2.2. Synthesis of HKUST-1 and Al-MCM-41/HKUST-1 composite
2.3. Characterization
The structure of the synthesized materials was characterized by
X-ray diffractometer. The light source used for measurement was
Cu Ka radiation (k = 1.5406 Å), with acceleration and current volt-
ages of 40 kV and 30 mA, respectively. The analysis was performed
at an angle of 2h between 5 and 50° with an interval scan of 0.020°.
Analysis using FTIR spectrophotometer was performed at
wavenumbers of 4000–400 cm1 with KBr pellets. The morpholog-
ical structure and particle size of the synthesized material were
characterized using SEM instruments. The thermal stability of the
synthesized material was tested using TGA with a heating rate of
20 °C/min at temperatures of 30–900 °C under air atmospheric.
Measurement of surface area and pore size distribution were done
by Surface Area Analyzer instrument using BET and BJH equations.
2.4. Adsorption experiments
The experiment on removal of the methylene blue in aqueous
solution was carried out using a batch method, in which HKUST-
1 and AMC/HKUST-1(7) composite were utilized as adsorbents.
The AMC/HKUST-1(7) represented composite with highest Al-
MCM-41 content. The effect of variations in contact time and initial
methylene blue concentration were carried out to determine the
optimum conditions in the adsorption process. The mass of the
adsorbent used was 20 mg in a volume of 20 mL adsorbate for 2
to 14 min, accompanied by stirring using a magnetic stirrer. After
the adsorption process, the solution was centrifuged to separate
the adsorbent from the methylene blue solution. The concentration
of methylene blue in the aqueous solution after adsorption process
was then measured using a UV–Vis spectrophotometer. Data from
variations in contact time and initial concentrations was used to
determine the kinetics and adsorption isotherm.
3. Result and discussion
3.1. Characterization of synthesized materials
The HKUST-1 and AMC/HKUST-1 composites obtained from the
synthesis were then characterized using XRD, and the diffrac-
tograms are shown in Fig. 1. The diffractogram of HKUST-1 has
characteristic peaks at 2h around 6.61, 9.39, 11.51 and 13.31°,
which indicates the successful of HKUST-1 synthesis [11]. Mean-

HKUST-1 was synthesized through the solvothermal method as

performed by previous study [20]. HKUST-1 and Al-MCM-41/
HKUST-1 composites were synthesized using Cu(NO3)2.3H2O
and H3BTC as precursors. The procedure of the HKUST-1 synthesis
was initiated by dissolving 2.077 g of Cu(NO3)2.3H2O in 15 mL of
deionized water in a vial bottle and stirred until a homogeneous
solution was formed. Next, 1.0 g of H3BTC was dissolved in
30 mL of a mixture of ethanol:DMF in a ratio of 1: 1 by volume.
The two solutions were then mixed and stirred for 15 min in a vial
bottle completed with cap, and placed in an oven at 100 °C for 10 h.
The reaction mixture was cooled down at room temperature for
2 days. The obtained blue crystal was immersed in 30 mL of warm
methanol by placing the bottle in an oil bath at  45 °C for 3 days.
Subsequently, the products in the form of blue crystals were dec-
anted and dried at room temperature. Meanwhile, the Al-MCM-
41/HKUST-1 composites were synthesized using the same proce-
dure to that of HKUST-1 synthesis. The Al-MCM-41 was added to
the ligand solution, at 0.0709 g (3%), 0.1181 g (5%) and 0.1653 g
(7%), respectively. Furthermore, the synthesized material is
denoted as AMC/HKUST-1(x) where  is the percentage of Al-
MCM-41 added. Fig. 1. The diffractogram patterns of synthesized materials.

Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx
Fig. 2. FTIR spectra of synthesized materials.
while, the diffractogram patterns of Al-MCM-41/HKUST-1 compos-
ites, shown in Fig. 1, are not significantly different as compared to
that of the HKUST-1, which indicate that the addition of supporting
material Al-MCM-41 does not affect the crystal structure formed.
As the XRD analysis have been performed at an angle of 2h
between 5 and 50°, then the characteristic peak of Al-MCM-41 at
2h of bellow 5°, is not seen in the diffractograms [21]. Furthermore,
as are shown in the diffraction patterns of the HKUST-1 and Al-
MCM-41/HKUST-1 composites, the addition of mesoporous alumi-
nosilicate Al-MCM-41 as a material support results in a decrease in
crystallinity of the composites because of the amorphous structure
of the Al-MCM-41 [22].
The FTIR spectra of Al-MCM-41/HKUST-1 composites, as pre-
sented in Fig. 2, show specific absorption bands that are typical
for HKUST-1 and Al-MCM-41. The specific absorption band of
HKUST-1 appeared in the region of wavenumbers 1644, 1373
and 1447 cm1 came from the stretching vibrations of the C@O,
C-O and OH bending vibrations which indicated the presence of
carboxylic acid groups in the molecule [23]. Al-MCM-41 has char-
acteristic absorption bands in the area around 685–790 and 1217–
1223 cm1. The absorption peak showed the existence of T-O-T
stretching vibration (T = Si/Al), which suggested that Al has been
included in the MCM-41 structure. The absorption bands at the
wavenumber of around 960–968 cm1 showed the stretching
vibration of the Si-OH symmetry. While the absorption band in
the area of 783–796 cm1 showed the presence of Si-O-Al stretch-
ing vibrations. The characteristic absorption peak was in accor-
Fig. 3. SEM Image of (a) HKUST-1 and (b) AMC/HKUST-1(7) composite.
Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
3
dance with the results of previous studies. Wang et al. have
reported that internal and external stretching vibrations asymme-
try of Si-O appeared at wavenumbers of 1089 and 801 cm1 [24].
Meanwhile Chen et al. confirmed that the external stretching
asymmetry vibration of Si-O-Si appeared in the region of
wavenumber 1231–1240 cm1 and the internal stretching asym-
metry vibration of Si-O-Si appeared in the wavenumber region
1070–1078 cm1 [21]. It could be observed that the absorption
band characteristics of Al-MCM-41 in the Al-MCM-41/HKUST-1
composite became increasingly evident when Al-MCM-41 was
added in larger quantities. These results indicated that the struc-
ture of Al-MCM-41 remained unchanged and the presence of Al-
MCM-41 in the Al-MCM-41/HKUST-1 composite was integrated
into HKUST-1.
Surface morphologies of the synthesized HKUST-1 and AMC/
HKUST-1(7) composite are shown in Fig. 3. The SEM images
showed the surface morphology of the synthesized material in
the form of octahedral shape with sharp edges. These results were
in accordance with research reported by Chevalier et al. [25]. After
the addition of Al-MCM-41, the morphology of the surface did not
change significantly (Fig. 3.b), which was in accordance with the
previous XRD analysis. However, the addition of Al-MCM-41 dur-
ing HKUST-1 synthesis could affect the pore structure of the
AMC/HKUST-1(7) composite, as shown by the nitrogen adsorp-
tion–desorption isotherms.
The HKUST-1 sample showed a characteristic type-I adsorp-
tion–desorption isotherms for a microporous material, where the
volume of adsorbed gas was very high at a low relative pressure,
and remained constant at a high relative pressure, as presented
in Fig. 4. A similar type-I nitrogen adsorption–desorption isotherm
was observed for the AMC/HKUST-1(7) composite at the low rela-
tive pressure. At relative pressures of higher than 0.9, however, a
sharp increase in the volume of gas adsorbed was observed, which
indicated the presence of pore-sized distributions of microporous
and mesoporous [26]. As shown in Table 1, the pore volume and
diameter of the samples increased significantly when the Al-
MCM-41 was added during the synthesis of HKUST-1, even though
the specific surface area of the composite slightly decreased. It was
worth noting that the pore diameter of the composite (7.13 nm)
was much higher than that of HKUST-1 (2.36 nm). A similar phe-
nomenon was also observed on the pore volume, in which the pore
volume of AMC/HKUST-1(7) composite was 19-fold higher than
that of HKUST-1. The significant increase in pore volume and diam-
eter was due to the presence of mesoporous Al-MCM-41 with a
pore size of 6–9 nm in composites whose structure did not change
during the synthesis process [27].
Besides affecting the pore characteristics, the addition of Al-
MCM-41 also increased the thermal stability of the material. The
HKUST-1 and AMC/HKUST-1 (7) thermograms showed a similar
curve with a 2-step weight reduction to the heating temperature.
4 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx

3.2. Adsorption performance

The synthesized material was tested for its performance as

methylene blue adsorbent. The results of observations of the influ-
ence of contact time on the %removal showed that the adsorption
process took place very fast, with a % removal of more than 95%
being achieved in less than 14 min, as shown in Fig. 6. It can be
seen that the AMC/HKUST-1(7) composite exhibited a higher
adsorption performance as compared to HKUST-1. The adsorption
process was usually constant after 11 min, indicating that the
adsorbent started in a saturated condition [30]. However, consider-
ing the percent removal of two adsorbents whose value are close to
100%, optimization of the adsorption conditions associated with
the adsorbent dose is still required because the adsorbent may still
absorb more methylene blue.
When the initial concentrations of methylene blue were varied,
the adsorption capacity gradually increased with the increase in
the initial concentrations, as shown in Fig. 7. The AMC/HKUST-1
(7) composite had a slightly higher adsorption capacity than that
Fig. 4. N2 Adsorption-desorption isotherms of HKUST-1 and AMC/HKUST-1 (7)
composite.

Table 1
Textural properties of synthesized material.

Material SBET (m2/g) Vpore (cc/g) Dm (nm)

HKUST-1 1056 6.622  10-2 2.36
AMC/HKUST-1(7) 929.5 125.7  10-2 7.13

In the first stage, there was a weight decrease in the temperature

range of less than 150 °C which came from the decomposition of
the solvent by 41% for HKUST-1 and by 36% for AMC/HKUST-1
(7). Furthermore, at temperatures range of 290–400 °C, a weight
loss of 43% for HKUST-1 and 54% for AMC/HKUST-1(7) composite
were originated from the decomposition of the ligand in the sam-
ple’s framework [28]. The samples were subsequently stable at
temperatures of over 400 °C in the form of CuO [29]. As shown in
Fig. 5, the thermal stability of the AMC/HKUST-1(7) composite
was higher (310 °C) as compared to the HKUST-1 (290 °C). This
result was consistent with the initial hypothesis that the addition
of Al-MCM-41 during HKUST-1 synthesis could increase the ther- Fig. 6. Effect of contact times.
mal stability of the material because Al-MCM-41 was composed
of metals with higher heat resistance such as Si and Al.

Fig. 7. Effect of initial concentrations of methylene blue. (For interpretation of the

references to colour in this figure legend, the reader is referred to the web version of
Fig. 5. Thermograms of HKUST-1 and AMC/HKUST-1 (7) composite. this article.)

Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx
of HKUST-1. The value of the adsorption capacity, which gradually
increased with the increase in the initial concentrations of methy-
lene blue indicated that the adsorbent had many vacant sites avail-
able for the adsorption process [30]. Therefore, it was necessary to
optimize the adsorption conditions to obtain a higher adsorption
capacity value. In this study, from variations in the initial concen-
trations of methylene blue, an adsorption capacity value of 43 mg/
g was achieved with a percent removal of more than 96%.
3.3. Adsorption kinetics study
The adsorption kinetics study was conducted to determine the
adsorption interactions suitable for the methylene blue adsorption
process. The adsorption kinetics modeling in this study was exam-
ined in two types of conventional adsorption kinetics modeling,
pseudo-first order and pseudo-second order [31]. Correlation coef-
ficient values close to 1 in the plot results of each model indicate an
agreement with experimental data. The modeling of pseudo-first
and pseudo-second adsorption kinetics can be expressed in the fol-
lowing equation:
Pseudo-first order kinetic
LnðQ e  Q t Þ ¼ LnQ e  K 1 t
Pseudo-second order kinetic
t 1 t 1
¼ þ
Q t K 2 Q 2e Q e
Where Qe is the adsorption capacity at equilibrium (mg/g), Qt is the
adsorption capacity at t time (mg/g), K1 and K2 are pseudo-first and
pseudo-second order adsorption kinetic constant, respectively. In
this study, by plotting t (minutes) as the x-axis and ln (Qe-Qt) as
the y-axis, the obtained graph was used to determine the K1 param-
eter value from the slope and the calculated Qe values were
obtained from exponential of intercepts. Pseudo-second order
graphs were plots of t (minutes) as the x-axis, and t/Qt as the y-
axis. The K2 value was obtained from slope2/intercept and Qe calcu-
lation of pseudo-second order reaction kinetics were obtained from
1/slope. Plots of pseudo-first order and pseudo-second order
adsorption kinetics are presented in Fig. 8(a) and (b), respectively.
The adsorption kinetics study showed that the correlation coef-
ficient (R2) of pseudo second-order plots was higher than that of
pseudo first-order, which indicated that the adsorption kinetics
of methylene blue by HKUST-1 and AMC/HKUST-1(7) composites
Fig. 8. Plot of (a) Pseudo-first order and (b) Pseudo-second order adsorption kinetics.
Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
5
followed a pseudo second order. In addition, the adsorption capac-
ity of Qe calculated in pseudo-second order was close to the
adsorption capacity value experimentally (Table 2). This result
strengthened the suitability of the adsorption process based on
pseudo-second order kinetics modeling, and that the methylene
blue adsorption mechanism on HKUST-1 and AMC/HKUST-1(7)
composites might be a physical adsorption process [32].
3.4. Adsorption isotherm study
An adsorption isotherm study was performed to determine the
adsorption mechanism of methylene blue that might occur in
HKUST-1 and AMC/HKUST-1(7) composites. The Langmuir adsorp-
tion isotherm showed that the adsorption mechanism occurred
singly on the surface of the adsorbent, which was homogeneous,
with the adsorption mechanism being highly dependent on the
presence of the active center of the adsorbent. While the Fre-
undlich adsorption isotherm showed that the adsorption mecha-
nism occurred multilayered on the surface of heterogeneous
adsorbents [30]. The suitability of the adsorption isotherm plot
was determined based on the value of the correlation coefficient
which was greater and closer to 1. Langmuir and Freundlich iso-
ð1Þ
therm modeling could be expressed in the following equation:
Langmuir adsorption isotherm:
1 1
ð2Þ ¼ þ ð3Þ
Q e Q m Q m  K L  Ce
Freundlich adsorption isotherm
1
LnQ e ¼ LnK F þ LnC e ð4Þ
n
where Qe (mg/g) was the amount of adsorbate per unit mass of
adsorbent, Ce (mg/L) was the concentration of adsorbate at equilib-
rium, Qm (mg/g) was the maximum adsorption capacity, and KL (L/
mg) was the Langmuir constant. The maximum capacity value was
obtained from the intercept plot graph between 1/Qe against 1/Ce.
While the KF value was the Freundlich isotherm (L/mg) constant
obtained from exponential of intercepts, and 1/n was adsorption
intensity obtained from the slope plot graph. The value of 1/n ran-
ged from zero to one that reflects the intensity of adsorption or sur-
face heterogeneity [33].
The obtained correlation coefficient values showed that Fre-
undlich isotherm modeling was more suitable than Langmuir iso-
6 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx

Table 2
Adsorption kinetic study parameters.

Material Pseudoo First-order Pseudo Second-order

2
R QeCal (mg/g) K1 R2 Qecal (mg/g) K2
HKUST-1 0.987 2.308 0.198 1 24.154 3.427
AMC/HKUST-1(7) 0.989 3.976 0.111 1 24.449 2.788

Fig. 9. Plot of (a) Langmuir isotherm and (b) Freundlich isotherm modelling.

therm. Freundlich isotherm showed the presence of multilayer

adsorption on the surface of the pore adsorbent due to the large
pore size, which allowed the accumulation of methylene blue to
saturation. These two results could be used to estimate the mech-
anism of adsorption of methylene blue on HKUST-1 and Al-MCM-
41, which was physically adsorbed via p-p stacking and electro-
static interaction [32]. The pore size of the Al-MCM-41/HKUST-1
composite, which was greater than HKUST-1, resulted in a compos-
ite adsorptive capacity value that was higher than HKUST-1. Other
parameters such as the 1/n value, which was close to 1, confirmed
the suitability of the Freundlich isotherm modeling in the adsorp-
tion of methylene blue using the Al-MCM-41/HKUST-1 as adsor-
bent. Plots of Langmuir isotherm and Freundlich isotherm
modelling are shown in Fig. 9(a) and (b), respectively (Table 3).

3.4.1. Adsorption mechanism

Methylene blue is a kind of cationic dye. The HKUST-1 and Al-
MCM-41/HKUST-1 composites, which act as adsorbents, have open
sites of the active metal, Cu, and an oxygen-active site in the car-
boxyl group. Based on the interaction mechanism shown in
Fig. 10, the interaction between HKUST-1 and methylene blue
could be estimated. When methylene blue was in the form of its
positive charge, which was located at the N+ atom, electrostatic
interactions occurred between the positive charge of methylene
blue and the oxygen atom in the carboxyl group of the adsorbents.
During the adsorption process, weak p-p interactions were also
Fig. 10. Schematic representation of interaction between HKUST-1 and methylene
blue. (For interpretation of the references to colour in this figure legend, the reader
is referred to the web version of this article.)
possible on HKUST-1 benzene rings and the methylene blue. In
addition, methylene blue could be adsorbed into the pore in
HKUST-1 with a pore diameter of 2.1–2.2 nm. In addition, since
the AMC/HKUST-1(7) composite consisted of micropores and

Table 3
Adsorption isotherm parameters.

Material Langmuir Freundlich

2
R Qmax (mg/g) KL R2 1/n KF
HKUST-1 0.967 75.189 0.394 0.980 0.660 1.180
AMC/HKUST-1(7) 0.946 92.593 0.806 0.970 0.613 1.253

Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361
 R. Ediati et al. / Materials Today: Proceedings xxx (xxxx) xxx
mesopores, the mesopores contribution facilitated the adsorption
of the methylene blue molecule in the composite pore so that
the adsorption capacity of the AMC/HKUST-1(7) composite was
higher than that of HKUST-1 without the Al-MCM-41.
4. Conclusion
Al-MCM-41/HKUST-1 composites were successfully synthe-
sized by the solvothermal method in which the Al-MCM-41 was
added to the reaction mixture before the solvothermal process.
The XRD pattern of the Al-MCM-41/HKUST-1 composite exhibited
the characteristic peaks corresponding to the HKUST-1 material.
FTIR spectra of Al-MCM-41/HKUST-1 composites showed the char-
acteristic absorption bands of HKUST-1 and Al-MCM-41, which
indicated the success of Al-MCM-41 impregnation on HKUST-1.
The addition of Al-MCM-41 during HKUST-1 synthesis resulted in
an Al-MCM-41/HKUST-1 composite with a methylene blue adsorp-
tion capacity greater than that of HKUST-1. The characteristic of
methylene blue adsorption on HKUST-1 and Al-MCM-41/HKUST-
1 composites followed the Freundlich isotherm model with the
pseudo-second order adsorption kinetics. The optimum contact
time was reached at 11 min and the maximum adsorption capacity
of methylene blue by AMC/HKUST-1(7) composite was 92.59 mg/g,
which was higher than the maximum adsorption capacity of
HKUST-1. The addition of Al-MCM-41 during HKUST-1 synthesis
may be a new method for production of an effective adsorbent
for the removal of dyes from aqueous solutions. Further studies
are needed on the optimization of adsorption conditions to obtain
a higher adsorption capacity value.
CRediT authorship contribution statement
Ratna Ediati: Conceptualization, Methodology, Supervision,
Writing - review & editing. Pradena B.F. Laharto: Investigation,
Resources, Writing - original draft. Rosiana Safitri: Methodology,
Writing - original draft. Hilda Mahfudhah: Investigation, Writing
- original draft. Dety Oktavia Sulistiono: Resources, Formal analy-
sis. Terry Denisa Syukrie: Writing - review & editing. Muhammad
Nadjib: Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
This work was supported financially by funding from Ministry
of Research, Technology and Higher Education, Republic of Indone-
sia, through Competency Grants No. 849/PKS/ITS/2019. We are
grateful to Material Chemistry and Energy Laboratory, Department
of Chemistry, as well as The Energy Laboratory of Institut Teknologi
Sepuluh Nopember (ITS) Surabaya for facilities supporting this
work.
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Please cite this article as: R. Ediati, P. B. F. Laharto, R. Safitri et al., Synthesis of HKUST-1 with addition of Al-MCM-41 as adsorbent for removal of methylene
blue from aqueous solution, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2020.06.361