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Different Iron Based Metal Organic Frameworks Synthesis, Characterization

and Using for Amoxicillin Removal from Aqueous Solutions

Conference Paper · October 2017

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 2nd International Mediterranean Science and Engineering Congress (IMSEC 2017)
Çukurova University, Congress Center, October 25-27, 2017, Adana / TURKEY
Pages: 1-7, Paper ID:629

Different Iron Based Metal Organic Frameworks Synthesis,

Characterization and Using for Amoxicillin Removal from Aqueous
Solutions
Utku Bulut Simsek1*, Cihan Gecgel1, Meral Turabik1,2
1
Mersin University Department of Nanotechnology and Advanced Materials, Turkey
U.B.Simsek (utkubulutsimsek@msn.com), C. Gecgel (cihangecgel@hotmail.com),
2
Mersin University Technical and Vocational School Chemical Program, M.Turabik (mturabik@mersin.edu.tr)

Abstract
Metal Organic Frameworks (MOF/MOFs) are a class of highly crystalline materials. The particular interest in
MOF materials is due to the easy tunability of their pore size and shape from a microporous to mesoporous
scale by changing the connectivity of the inorganic moiety and the nature of the organic linkers. Nonetheless,
the versatility in the characteristics of the MOF materials can be imparted through simple modification or
functionaliziation. Because of such unique characteristics, MOFs have many potential application including
drug (antibiotics, antihistaminics etc.) removal, gas separation, catalysis, adsorption of organic molecules,
chemical sensors so on.
In this study, for the removal of amoxicillin in aqueous solutions, an important antibiotic using extensively, iron-
based metal organic frameworks MIL-101 and MOF 235 and also their amino functionalized structures MIL 101-
NH2 and MOF 235–NH2 were used. All MOFs samples were synthesised and characterized by SEM, XRD and
FTIR analysis. According to the SEM results, all MOF samples structures have regular shape and medium size of
approximately 1.5-3.0 µm. The XRD and FTIR results have confirmed the regular shape and characteristic features
of MOF samples. The removal amount of amoxicillin from aqueous solutions was determined by HPLC analysis.
According to the HPLC results the highest amoxicillin removal percent (65.38% and 67.13%) were obtained by
MIL 101 and MOF 235-NH2, respectively. In addition, The effectivity of MOF 235 and NH2-MIL 101 for the
amoxicilin removal was not very high and also have lowest removal percent(42.05% and 40.23) for amoxicillin.

Keywords: Metal organic frameworks (MOFs), MIL 101, MOF 235, MOF modification, amoxicillin.

1. INTRODUCTION
In recent years metal organic frameworks (MOF/MOFs) have gain attention as potentially valuable gas storage, catalysis,
adsorption organic molecules and removal of organic pollutants. MOFs are composed of an organic ligand (dicarboxylic
acid, trimesic acid etc.) and transition metal complex or metal cluster, both units being building blocks that are desig-
ned to assemble a three dimensional open framework [1]. MOFs are a class of highly crystalline materials comprising
ordered, extended one dimensional (1D) particle, fiber and tube design, two dimensional 2D thin film and composite
materials, and three dimensional 3D framework structure networks formed by metal ions or clusters connected to multi-
functional organic ligands [2]. MOFs have great potential materials for many areas due to their high micropore volume,
large pore sizes crystalinity, large BET surface areas (up to 7000 m2/g), high termal stability and high metal content.
These key features offering potentially valuable active sites. Particularly, large pore size within the crystaline framework
and well defined pore view is a pre-requisite for shape selectivity of large molecules [1,2].
Nowadays many MOFs are synthesized by different methods such as hydrotermal/solvothermal microwave iridiation
and electrochemical method. Among these methods solvothermal methods more preferred than others because of simple
preparation techniques, low cost and high product yield. MOFs can be easily modified for various purposes by functi-
onalization using coordinatively unsaturated sites or linkers [3]. Several MOFs and and fuctionalized MOFs have been
used adsorptive removal of hazardous materials. These removal mechanism based on various interaction mechanism such
as simple electrostatic interactions, acid-base interactions, coordination so on [3].
One of the most important progress in MOF chemistry was the exploration of the MIL-101 (MIL = Materiaux de
Institut Lavoiser) by Ferey et al. when reporting the zeotype cubic structure of the hydro/solvothermally synthesized
(*) Corresponding author

2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey
chromium (III) teraphytalate [4]. MIL 101 have synthesized different metal ions such as chromium, iron and aluminum.
Among these metal ions, chromium and iron most preffered metal ions for synthesis MIL 101[3]. MIL 101 have enor-
mous specific improvements such as high surface area, high thermal stability and permanent porosity due to excellent
feature of MIL 101 has led to various applications in water purufication, gas storage, removal of drugs, catalysis and
sensing. Additionally, MIL 101 amino functionalized and this structure (MIL 101-NH2) have been applied in several
fields such as water purification, removal of drug waste, gas sensor, drug delivery and catalysis [4]. Water purification is
potentially field of application of MOFs but functionalization of MOFs is expected to be important in water purification
because of MOFs are usually hydrophilic and inefective for water purification without incorporating functionalities with
quite special interactions [3,4].
Pharmaceuticals and personal care products (PPCPs) have become important emerging contaminants and attracted
much attention due to their hazordous effect of enviroment and also adverse effects on humans and animals. PPCPs
are affected not only humans and animals but also use for livestock, poultry, fishing farm[5]. Up to the present, many
process such as adsorption, degradation have been investigated for the removal of PPCPs from aqueous solution [5].
Among the pharmaceuticals, special attention focused on antibiotics since bacterial resistance and toxic effects on several
organisms such as blue green algae, fish and farm animal have been found not only at high concentration but also at
low concentrations resulting in chronic effects[6]. The presence of antibiotics in the aquatic enviroment is the important
enviromental apprehension because of their weak biodegredability, toxicity, high chemical oxygen demand and develop-
ment of antibiotic resistant bacteria[7]. Amoxicillin is one of the most widely consumed antibiotics in the world. Amoxi-
cillin poorly absorbed in human body and animal body. Thus it is necessary to develop effective process for the removal
of amoxicillin from the waste water[8]. The aim of this study investigation on to removal of amoxicillin from aqueous
solution by four different type metal organic frameworks (MIL 101, NH2-MIL 101, MOF 235, NH2-MOF 235).

2. MATERIAL AND METHODS

All the chemicals used in the study were analytical grade. FeCl .6H O (99%, Merck), Benzene 1-4 dicarboxylic acid (98%
3 2

Sigma), 2- aminobenzene 1-4 dicarboxylic acid (99% Sigma), dimethylformamide (DMF, Sigma) and absolute ethanol
(99% J.T.Baker) were used as received without further purification. Potassium dihydrogen phosphate (99%Merck) and
methanol were used to prepare mobile phases for HPLC analysis. Active ingredient amoxicillin was purchased from
Bilim Pharmaceuticals and analysed by HPLC. Also amoxicillin chemical structure was shown Figure 1. The scanning
electron microscopy (SEM) image for surface morphology of MOFs were performed with a Zeiss Supra 55VP field
emission SEM. The analysis was performed by mounting MOF samples onto pin type SEM stubs using carbon/platinum
adhesive tabs and was coated with carbon/palladium by electro deposition under vacuum prior to analyses to enhance
the surface conductivity. X-ray diffractogram (XRD) of MOFs were obtained using a Rigaku SmartLab model XRD at
Cu-Kα radiation (λ = 1.54 Å). The analysis of MOFs were carried out at continuous scans from 3 to 30° at 2° scan rate
at 2θ min in ambient air.
−1

FTIR analysis of MOFs was recorded using a Perkin-Elmer Model FTIR Frontier spectrophotometer with attenuated
total reflection technique in the 4000–450 cm region. Quantitative analysis of amoxicillin was detected using an Agilent
–1

1200 Series high pressure liquid chromatography (HPLC) system equipped with an ACE C18 Column (250x4.6mm,
partical size 5 μm) using a mobile phase composed of potassium dihydrogen phospate/methanol(90: 10, v/v) at a flow
rate of 1 mL/min, the column temperature was 30 °C Diode Array Detector (DAD) was operated with 270 nm.

Figure 1: Amoxicillin chemical structure

2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey
2.1 Preparation of the MOF Materials
2.1.1 Synthesis of MIL-101
Metal organic framework (MOF) material MIL-101 was prepared by adaptation of the method described by Barbosa
et al. [4]. A mixture containing FeCl3.6H2O (2.45 mmol) and H2bdc (1.24 mmol) in DMF (15 mL) was transferred to
an glass vial and heated at 110 °C for 24 h. After a slow cooling process inside the oven, the brown solid was recovered
by centrifugation, purified by a double treatment with ethanol at 60 °C for 3 h and dried in an oven at 70 °C for 24h.

2.1.2 Synthesis of NH2-MIL-101

The amino-functionalized NH2-MIL-101 MOF was prepared by an adaptation of the method described by Barbosa et
al.[4]. Briefly, a solution of NH2-H2bdc (1.24 mmol) in DMF (7.5 mL) was added to a solution of FeCl3.6H2O (2.50
mmol) in DMF (7.5 mL) and the resulting mixture was transferred to an autoclave and heated at 110 °C for 24 h. The
solid was recovered by centrifugation, double-washed with DMF and ethanol and dried in a oven 24h.

2.1.3 Synthesis of MOF-235

MOF 235 was prepared by an adaptation of method described by Sudik et al. [9]. A equimolar amounts of FeCl3.6H2O
(1.23mmol) and and H2bdc (1.23 mmol) were dissolved in 60 mL of DMF. Glass vial containing 2 mL of the reaction
solution and 2 mL ethanol were flash and placed in 85 °C oven for 24 h. The orange crystal of MOF 235 was collected
and washed 2 times DMF: Ethanol (1:5 v/v) mixture then dried in a oven 80 °C for 24 h.

2.1.4 Synthesis of NH2-MOF-235(Fe)

The amino-functionalized MOF 235 was prepared by an adaptation of the method described by Sudik et al.[9]. A
FeCl3.6H2O (1.23mmol) and NH2-H2bdc (1.23 mmol) were dissolved in 60 mL of DMF. Glass beaker containing 30
mL of the reaction solution and 30 mL ethanol were flash and placed in 85 °C oven for 24 h. The orange crystal of MOF-
235 was collected and washed 3 times DMF: Ethanol (1:5 v/v) mixture then dried in a oven 80 °C for 24 h.

2.2. Preparation of Amoxicillin and Batch Studies

The stock solution of amoxicillin was prepared in 0.1 g/L concentration with ultrapure water and used by diluting
with water further experiments. Removal of the amoxicillin by MOFs was studied air medium. After adding a desired
amount of MOFs, the amoxicillin solution was agitated with a thermostatically controlled shaker (Memmert Waterbath
WHE-45). After the batch studies MOFs were separated in solution by using cooling centrifuge at 13 000 rpm for 10
min. Then, the concentration of amoxicillin was analysed HPLC system. The removal efficiency was calculated using the
following equation:
 C − Ct 
Re moval(%) =  0  x100
 C0  (1)
where Removal (% ) was the amoxicillin removal efficiency, C0 (mg/L) was the initial amoxicillin concentration and
Ct (mg/L) was the concentration of amoxicillin at t min.

3. RESULTS AND DISCUSSION

3.1. Characterization of MOFs
The powder XRD patterns of both MOFs display the typical main diffraction peaks of MOFs structures and are in
accordance with the data reported in literature [4,9] are illustrated in Figure 2a-d, respectively. In accordance with the
XRD patterns a higher degree of crystallinity of the MIL 101 when compared with the other MOFs as shown by the
higher relative intensity of the peaks in the 3-6° range. Also XRD patterns of MOF 235 and amino-functionalized NH2-
MOF-235 showed higher intensity of the peaks in the 9-10° range.

2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey
 Figure 2: Powder XRD patterns of MOFs a) MIL-101 b) NH2-MIL-101 c) MOF-235 d) NH2-MOF-235
Scanning electron microscopy (SEM) was used to characterize the morphology of the MOFs. SEM images illustrated in
Figure 3a-d. Figure 3a show that MOFs are mainly composed by particles with octahedral morphology and particle size
approximately 2.5-3.5 µm. Figure 3b indicate that NH2-MIL-101 are composed by particles with octahedral morpho-
logy but some particles collapses and MOFs have some impurities. Figure 3c indicate that MOF-235 is mainly compo-
sed homogeneous particles and also particle size around 1.5 µm. Figure 3d show that amino functionalized MOF-235
is mainly composed octahedral shape and also materials have homogeneous dispersion and particle size around 2.5 to
3.5 µm. SEM results confirm the different crystallinity of the MOFs samples and they have octahedral shape except that
NH2-MIL-101 have some impurities and these results compatible with literature.

Figure 3: SEM images of the MOFs a) MIL-101 b) NH2-MIL-101 c) MOF-235 d) NH2-MOF-235

FT-IR results have illustrated in Fig4a-d. Figure 4a-b show that the typical asymetric C-O and symmetric C-O streches
of terephthalate ligands in MIL 101 and amino-functionalized MIL 101 structures, assigned to the bands located at
1661, 1595, 1388 cm-1 and 1653, 1559, 1382 cm-1 for MIL-101 and amino-functionalized MIL-101, respectively. Also
presence of amino groups in their free unassociated form is indicated by the bands located at 3470, 3373, 2979 cm-1
corresponding to asymetric N-H and symmetric (N-H strecting modes, respectively[4,10].
Fig 4c-d also indicate that the asymetric C-O and symmetric C-O streches of teraphthalate ligands in MOF 235 and
amino-functionalized MOF 235 structures assigned to the same bands located at 1594, 1386 cm-1. Additionally, pre-
sence of amino groups in their free unassociated form is indicated by the bands located at 3088 cm-1 corresponding to
asymetric N-H strecting bonds whereas symmetric N-H streching was not seen FT-IR spectra [9].

2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey
 Figure 4: FT-IR spectra of the MOFs a) MIL-101 b) NH2-MIL-101 c) MOF-235 (Fe), d) NH2-MOF-235

3.2. Removal of Amoxicillin in aqueous solution by MOFs

The removal of amoxicillin in aqueous solution using MIL-101, NH2-MIL-101, MOF-235 and NH2- MOF-235 were
investigated at a batch system. In the batch system, 40 mg/L amoxicillin and 100 mg/L MOFs was mixed with thermos-
tat shaker at 120 minutes. All stage of this removal study HPLC-DAD analysis were used to observe the removal changes
and also amounts of amoxicillin was determined with time. As shown at HPLC results in Table 1, retention time of
amoxicillin was determined about 2.22 minutes. (Figure 5). It is clearly indicated that 65.38 % and 67.13 of amoxicillin
were removed from the solution within 120 minutes using MIL-101 and NH2-MOF-235 while approximately 40.23%
and 42.05% of amoxicillin was removed from the solution within 120 min. using MOF-235 and NH2-MIL-101, res-
pectively (Figure 6). There are a few reasons for this low removal rate. Firstly, primary concern is MOF instability with
water. Water can either displace the bound ligand, leading to the collapse of some MOF structures, or block the binding
sites and prevent the adsorption of amoxicillin. Because MOFs have three different adsorption mechanisms: reversible
and continuous pre-filling, through capillary condensation and irreversibility arising from the flexibility and possible
structural modification of the host material [11,12]. Water stability is directly affects these mechanism. Secondly, MOFs
are usually hydrophilic and ineffective for water purification without incorporating functionalities with quite special
interactions. Because of water molecules displaced the Secondary Built Unit (SBU) and metal ions or ligands may not be
connected properly to amine functional group [3,4,11] Thirdly, antibiotics are electron rich compounds while metallic
ions are electron deficient as for their chemical structure the amoxicillin is composed of molecules with donor groups
(N, O), which are good complexing agents. However, amoxicillin donor groups may be saturated and as a result MOFs
can’t connected the donor groups [13].
As a conclusion MOF-235 and NH2-MIL-101 less effective than MIL-101 and NH2-MOF-235 for the removal of
amoxicillin in aqueous solution. These results were supported by XRD results. Accordingly, the XRD results NH2-
MIL-101 and MOF-235 have some impurities that it is possible to say these impurities affect the structure as a result
removal percent of amoxicillin decreases.

Figure 5: Retention time of Amoxicillin for provided by HPLC-DAD

2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey
 Table 1. HPLC results of removal of 40 mg/L amoxicillin in aqueous solution by 100 mg/L MOFs.
Removal Percent Removal Removal Per- Removal
Time of Percent of cent of MOF- Percent of
(min) MIL-101 NH2-MIL-101 235 NH2-MOF-235
(%) (%) (%) (%)
0 00.00 00.00 00.00 00.00
15 59.80 24.25 39.80 62.43
30 61.15 27.93 40.45 66.28
60 63.18 38.48 41.65 66.93
120 65.38 40.23 42.05 67.13

Figure 6: Removal percent of Amoxicillin in aqueous solution by MOFs (Initial MOF concentration;100 mg/L, Initial
Amoxicillin concentration; 40 mg/L

4. CONCLUSION
This study has shown that MIL-101 and NH2-MOF-235 are played important role for removal of amoxicillin in aqueous
solution. Also according to HPLC-DAD results their amoxicillin removal percent was found that 65.38% and 67.13%
respectively. Whereas NH2-MIL-101 and MOF-235 have low removal rates for amoxicillin. Because of the water mo-
lecules displaces the ligands or block the binding sites also water molecules displace with the SBU unit and amoxicillin
donor groups may be saturated. SEM results showed that MOFs are mainly composed by particles with octahedral
morphology and particle size approximately 1.5-3 µm but anyway contrary to expectations they have some impurities.
XRD results supported the SEM results so they have typical XRD pattern but we found that some impurities. FT-IR
results show that all MOFs have typical stretching modes consist of metal and terephthalate ligand signals. But only it
was not seen in the symmetric N-H bonds for NH2-MOF-235.

5. ACKNOWLEDGEMENTS
Author’s grateful to Bilim Pharmaceuticals for providing Amoxicillin.

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2nd International Mediterranean Science and Engineering Congress (IMSEC 2017), October 25-27, 2017, Adana/Turkey

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