Indonesian Journal of Science & Technology 4 (2) (2019) 220-228

Indonesian Journal of Science & Technology
Journal homepage: http://ejournal.upi.edu/index.php/ijost/

Nano Metal-Organic Framework Particles
(i.e. MIL-100(Fe), HKUST-1(Cu), Cu-TPA,
and MOF-5(Zn)) using a Solvothermal Process
Asep Bayu Dani Nandiyanto
Departemen Kimia, Universitas Pendidikan Indonesia, Jl. Dr. Setiabudi no 229, Bandung 40154, Indonesia

Correspondence: E-mail: nandiyanto@upi.edu

ABSTRACT

ARTICLE INFO

Metal-organic framework (MOF) is attractive because of its
representation as a class of crystalline porous materials with
excellent properties, specifically its chemical functionality
and high porosity, making it potentially tailored for various
desired applications. Although the synthesis of MOFs have
been well-documented, most reports are in the bulk and
micrometer sizes. The synthesis of MOFs in the smaller size
is still inevitable. This work reports the synthesis of nano
MOF particles (i.e., MIL-100(Fe), HKUST -1(Cu), Cu-TPA, and
MOF - 5 (Zn)). In the experiment , MOFs were created by
interacting ligands and metal ions in the specific solvent in the
solvothermal process . Different from other reports , this
study used low concentrations of ligands and metal ions, in
which this is effective to control ligand-metal ion interaction,
reaction, nucleation, and growth of MOF. The successful
synthesis was obtained and effective for various MOF
particles by changing types of ligands and metal ions . The
study also obtained that compatibility and dilution of the
ligands and the metal ions in the specific solvent are
important parameters . This information will bring new
strategies and further developments for the synthesis of MOF
materials for wider range of potential applications in
separation, catalysis, dye adsorption, and drug carrier uses.

Article History:
Submitted/Received 01 Feb 2019
First revised 11 Apr 2019
Accepted 11 Jun 2019
First available online 15 Jun 2019
Publication date 01 Sep 2019 16
Aug 2018
Revised 20 Aug 2018
Accepted 25 Aug 2018
____________________
Available online 09 Sep 2018
Keywords
Keywords:
Metal organic framework,
Particle synthesis,
Ligand,
Metal ion,
Powder technology,
Chemical education.

© 2019 Tim Pengembang Jurnal UPI

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1. INTRODUCTION
Metal−organic
framework
(MOF)
materials have emerged as an excellent
material with ultrahigh porosity (up to 90%
free volume) and enormous internal surface
areas. The surface area can extend beyond
6000 m2/g. When these properties combined
together with other various properties, it
makes MOF materials to be applicable for
prospective applications in clean energy,
most significantly as separation and storage
media for gases such as hydrogen and
methane. In addition, MOF is also possibly
applied for membranes, thin-film devices,
catalysis , and biomedical imaging (Zhou
et al., 2012).
The numbers of review articles and
monographs have been documented for the
escalation of the MOF material synthesis. In
short, MOF material was produced by
interacting ligands and metal ions in a
specific solvent (Lee et al., 2009). MOFs have
been available mostly in micron and
millimeter size, and reports on the
production of MOFs in smaller sizes are still
inevitable.
Here, the purpose of this study was to
simply comprehend and investigate the facile
synthesis of nano-sized MOF particles. To
assist the production of MOF materials,
solvothermal process was used. Various
types of ligands and metal ions were tested
to form various types of MOF particles (see
Table 1). The present study also investigated
the interaction of ligands and metal ions
systematically . Then, the results were tested
and examined by several characterizations ,
i.e., a scanning electron microscope (SEM )
and an X-ray diffraction (XRD).
In addition, to evaluate the effect of
combination of ligands and metal ions on the
formation of MOF material, various ligands
and metal ions were tested, which were used

| DOI: http://dx.doi.org/10.17509/ijost.v4i2.18178

to form various types of MOF materials , i.e.,
MIL-100(Fe), HKUST-1(Cu), Cu-TPA, and MOF
-5(Zn). These types of MOF materials were
selected as the models of MOF materials
since they have been classified as one of the
most popular MOF materials. Indeed, this will
bring other prospective innovations in the
further development of MOF materials with
their wider range of potential applications in
separation , catalysis , dye adsorption , and
drug carrier uses.
2. MATERIALS AND METHODS
2.1. Chemicals
Iron (III) chloride (FeCl3.6H2O), iron (III)
nitrate (Fe(NO3)3.6H2O), Iron (II) chloride
(FeCl2.6H2O),
copper
(II)
nitrate
(Cu(NO3)2.6H2O),
and
zinc
nitrate
(Zn(NO3)2.6H2O) were used as metal sources.
Trimesic acid (TMA) and Terephthalic acid
(TPA) were used as ligand components.
These chemicals were used for the
preparation of various types of MOF
materials, i.e., MIL-100(Fe), HKUST-1(Cu), Cu
- TPA, and MOF-5(Zn). Dimethyl formamide
(DMF) was also used as a solvent dissolution
agent for removing unreacted chemcials. All
chemicals were purchased from Sigma Aldrich US and used without further
purification.
2.2. Synthesis procedure
For the synthesis of MOF materials,
ligands were initially diluted in the solvent
(concentration
of
120
mmol/L).
Subsequently, metal sources was inserted
into the solution, mixed, and kept in room
temperature for about 15 minutes. Next, the
mixed solution was introduced into the
solvothermal process using the conventional
solvothermal apparatus. In short, the
apparatus consisted of 150 mL of PTFE
reactor with inner reactor with dimensions
for diameter and height of 35 and 90 mm,
respectively. The teflon reactor was

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equipped with solvothermal metal blanket
(stainless steel reactor).

the formation of MOF materials is shown in
Table 1.

For starting the synthesis process, the
apparatus contained ligands and metal ions
was introduced to the furnace at a
temperature of 150°C for 12 hours. Please
see detailed information regarding the
experimental setup in Figure 1. In this study,
the mole ratio of ligands and metal ions was
fixed at 1.00. The list of chemicals used for

After the reaction process, the product
was purified using a centrifugation process
(three times at 11,000 rpm for 30 minutes
and washed with DMF). This centrifugation
process was used for removing unreacted
chemicals. The centrifuged product was then
dried in a vacuum oven at temperature of
50°C overnight for characterization and use.

Figure 1. Experimental setup.
Table 1. Mean abrasion weight losses of high-performance DSP cementitious mortars with
nano- and/or micro-scale reinforcement.
Sample
A
B
C
D
E
F
G
H
I
J
K

Ligand
TMA
TMA
TMA
TMA
TMA
TPA
TPA
TPA
TPA
TPA
TPA

Metal ion raw material
FeCl3.6H2O
FeCl2.6H2O
Fe(NO3) 3.6H2O
Cu(NO3)2.6H2O
CuCl2.6H2O
FeCl3.6H2O
Cu(NO3)2.6H2O
Zn(NO3)2.6H2O
FeCl3.6H2O
Cu(NO3)2.6H2O
Zn(NO3)2.6H2O

| DOI: http://dx.doi.org/10.17509/ijost.v4i2.18178

Solvent
UPW
UPW
UPW
UPW
UPW
UPW
UPW
UPW
Methanol
Methanol
Methanol

Product
MIL-100(Fe)
MIL-100(Fe)
MIL-100(Fe)
HKUST-1(Cu)
HKUST-1(Cu)
Iron oxide
Unsuccessful
Unsuccessful
Iron oxide
Cu-TPA
MOF-5

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2.3. Characterizations
Several
characterizations
were
conducted: (i) SEM (Hitachi SU-70, Hitachi Co
Ltd.,
Japan)
equipped
with
EDX
measurement for analyzing the morphology
and size of particles; and (ii) X-ray diffraction
(XRD, PANalytical X’Pert Pro MPD X-ray
diffractometer using Cu-Kα radiation) for
analyzing the crystal structure.
3. RESULTS AND DISCUSSION
3.1. Turpis egestas
Figure 2 depicts the analysis of the
synthesis of MOF particles prepared using
TMA (as a ligand) with various Fe sources (as
a metal ions) using the solvothermal method.
Figures 2(a), (b), and (c) are the SEM images
samples prepared from combination of TMA
and various Fe sources (i.e., FeCl3, Fe(NO3)3,
and FeCl2, respectively; detailed combination
is shown as samples A, B, and C in Table 1).
The SEM images confirmed that samples
contained particles with sizes from nano to
submicron,
demonstrating
that
the
combination of TMA and various types of Fe
ions in this low concentration (i.e., 120
mmol/L) is effective to create nanoparticles.
The ferret analysis showed that the particles
prepared with FeCl3, Fe(NO3)3, and FeCl2
have sizes of about 200, 400, and 100 nm,
respectively.
XRD analysis in Figure 2(d) showed that
the present combination of TMA and various
Fe sources have identical XRD patterns for
MIL-100(Fe) materials, confirmed by the
simulated XRD pattern of MIL-100(Fe) and
current literature (Hei et al., 2014).
The study also found the followed
phenomena. Since FeCl3 and Fe(NO3)3 can

| DOI: http://dx.doi.org/10.17509/ijost.v4i2.18178

create Fe3+ ions, it should be no effect of the
interaction and reaction between Fe ions and
TMA on the formation of MIL-100(Fe).
However, different final particle sizes were
found (see different particle morphologies in
Figures 2(a) and (b)). The main reason for the
different sizes are due to the impact of
anions on the substitution of H+ in TMA
molecules by Fe ions and oxygen elements.
Cl- ions disturb more than NO3- ions. In fact,
substitution of Fe ions into the
deprotonation of TMA have a direct impact
to the nucleation and growth rate of the MOF
materials. The use of FeCl3 has higher
nucleation rate (more nuclei to be formed)
than that of Fe(NO3)3. The reactant would
rather create more new nuclei than grow to
increase the weight of the formed nuclei.
In the case of FeCl2 that can form Fe2+
ions, smaller particles were obtained
compared to the process using FeCl3. The
types of anions (i.e., Cl-) in both chemicals
were the same, and the type of XRD pattern
are identical. The main fundamental reason
for the different sizes is due to the type of Fe
ion in converting H+ in the TMA. Fe2+ has
more active to attack and collaborate with
TMA to form MIL-100(Fe) than Fe3+. Further,
atomic scale for the Fe2+ is smaller than Fe3+.
As a result, the increases in the nucleation
rate could be obtained. However, the size
distribution of the sample prepared with Fe2+
is broader than that with Fe3+. This is because
of the need for reconstruction of the crystal
system to obtain the most stable structure.
The circumstance in the missing one positive
ion in the Fe ion (from Fe3+ to Fe2+) has an
impact to the MOF crystal to form the most
stable crystal structure.

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Figure 2. Analysis results of samples prepared with various types of Fe ions using the
solvothermal method. Figures (a), (b), and (c) are the SEM images of samples prepared with
TMA and FeCl3, Fe(NO3)3, and FeCl2, respectively. Figure (d) is the XRD analysis results.
Figure (a) was adopted from reference (Nandiyanto et al., 2019).
To confirm the effect of anionic on the
control of particle size, Figure 3 shows the
analysis results of samples prepared with
TMA and various types of Cu ions using the
solvothermal process (see samples D and E in
Table 1). Two types of Cu sources were used:
CuCl2 and Cu(NO3)2. The SEM images
presented that the CuCl2 led to the formation
of larger particles compared to Cu(NO3)2 (see
Figures 3(a) and (b), respectively). The XRD
analysis results in Figure 3(c) confirmed that
the changes in the types of Cu ions have no
impact on the change in crystalline structure
of the HKUST-1 material, and the XRD
patterns are identical to the samples that
prepared using a conventional method
(Venkatasubramanian et al., 2010).

| DOI: http://dx.doi.org/10.17509/ijost.v4i2.18178

The analysis results for the sizes based
on SEM results in Figures 3(a) and (b) are not
in a good agreement with the above data in
Figure 2. The main reason for the opposite
trends is because the size of Cu (0.120 nm for
covalent type Cu) is larger than that of Fe
(0.102 nm for covalent type Cu). In the
formation of MOFs, The Cl- ions seem to be
unable to give impact on shifting the Cu ions,
while NO3- ion is large enough to make
shifting the Cu ions. As a result, NO3becomes the most disturbing component
that brings great impacts on disturbing
substitution of H+ by Cu ions.

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Figure 3. The SEM (a,b) and XRD (c) analysis results of samples prepared with TMA and
various Cu ions using the solvothermal synthesis method . Figures (a) and (b) are samples
prepared using CuCl2 and Cu(NO3)2, respectively.
To confirm the effectiveness of the
present method on the formation of other
types of MOF materials, we also used TPA as
the ligand component. We found that the
preparation of samples prepared with TPA
and various metal ions in aqueous solution
(see samples F, G, and H in Table 1) did not
create MOF materials. The main reason is
due to the low dissolution of TPA in the
aqueous solution.
To address the above problem, Figure 4
presents the analysis results of the samples
prepared with TPA and various types of ions
(see samples I, J, and K in Table 1) in
methanol solution. The SEM images in
Figures 4(a)-(d) showed particles with sizes
of from nanometer. The XRD analysis results
in Figure 4(e) showed that the use of TPA in
methanol solution is not completely good for
preparing MOF materials. Although some
| DOI: http://dx.doi.org/10.17509/ijost.v4i2.18178

MOFs can be created when conducting
process in samples G and H, the product still
containing impurities and byproduct.
Further, the process using a precursor
containing FeCl3 seemed to be failure in
creating MOF materials. Instead of the
formation MOF materials, the sample create
amorphous materials with iron oxide
component (Chiou et al., 2013). The sample
that used Cu(NO3)2 has some Cu(OH)2 (Wang
et al., 2014), whereas sample with Zn(NO3)2
has ZnO (Zhang et al., 2002) and zinc
terephthalate dehydrate (Rodríguez et al.,
2015 ). In addition , the combination of TPA
and Zn(NO3)2 also creates specific MOFwater composite (Rodríguez et al., 2015), as
assigned at wavenumbers of about 9 and 18°.
These results strengthened the hypothesis
that to form nano MOFs, ligands and metal
ions must be well-dissolved. Otherwise, the

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ligand-metal ion interaction cannot be done.
Thus, it is required to find out an appropriate
solvent.
In addition, in the case of TPA, TPA is
well-dissolved into the DMF. However, the
DMF is classified as a hazardous chemical
(Yang et al., 2014). Further, adding DMF into
the solvothermal process relates to the
additional heat and pressure, resulting
shortcomings in the handling process.
Based on the above results, the main
ideas gained from this study is to get
successful synthesis of smaller-sized MOF
materials (Bosch et al., 2014). several factor

must be considered. The factors are (1) the
use of low-concentration ligands and metal
ions to enhance nucleation rate; (2) the
condition for making well dispersion of
ligands and metal ions in the solvent. Thus,
finding a good solvent that can dissolve these
reactants is important; (3) optimization of
concentrations of ligands and metal ions in
the solution. Optimization will lead to the
typical reaction happening during the
process as well as the formation of the
material (Marimpul , 2017; Muslih et al.,
2017; Nordin et al., 2018); and (4) the
compatibility between ligands and metal
ions to form MOFs.

Figure 4. The SEM (a-d) and XRD (e) analysis results of samples prepared with TPA and
various types of metal ions using the solvothermal synthesis method. Figures (a), (b-c), and
(d) are samples prepared using FeCl3, Cu(NO3)2, and Zn(NO3)2, respectively. Figures (b) and
(c) are the low- and high-magnified SEM images of samples prepared using Cu(NO3)2.

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4. CONCLUSION

The present study has successfully
demonstrated for the formation of nano sized MOF particles (i.e., MIL-100(Fe), HKUST1(Cu ), Cu -TPA , and MOF -5(Zn )) using the
solvothermal processing method . Various
types of ligands and metal ions , as well as
solvents were tested . The experimental
results showed that to get successful
synthesis of smaller -sized MOF particles ,
several factors must be considered : (1) the
use of low-concentration ligands and metal
ions to enhance nucleation rate ; (2) the
condition for making well dispersion of
ligands and metal ions in the solvent ; (3)
optimization of concentrations of ligands and
metal ions in the solution; and (4) the

compatibility between ligands and metal ions
to form MOFs.

5. ACKNOWLEDGEMENTS
A.B.D.N. acknowledged RISTEK DIKTI
Fulbright fellowship. We thank to Dr. WeiNing Wang for supporting this research.
A.B.D.N. also acknowledged PTUPT, PSNI,
and WCR research grant from RISTEK DIKTI.
6. AUTHORS’ NOTE
The author(s) declare(s) that there is no
conflict of interest regarding the publication
of this article. Authors confirmed that the
data and the paper are free of plagiarism.

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