i

“Chemical Process Design Project”

Title
Synthesis of metal organic framework for dye degradation
Supervisor: Dr. Muhammad Aslam

Group Members

Name Registration #
Syed Zamin Kazmi FA19-CHE-034-LHR
Abdul Hanan Wali FA19-CHE-042-LHR
Muhammad Zubair FA19-CHE-086-LHR
Ashar Ali khan FA19-CHE-096-LHR
Syed M. Taqqi Haider FA19-CHE-100-LHR

Department of Chemical Engineering

COMSATS University Islamabad, Lahore Campus
 ii

Table of Contents
Abstract........................................................................................................................................ 1
Introduction................................................................................................................................... 1
MIL-101(Fe).............................................................................................................................. 2
Literature Review......................................................................................................................... 2
Materials and Methods................................................................................................................. 4
FTIR Analysis........................................................................................................................... 5
Effect of Adsorbents on Adsorption Performance.....................................................................6
Adsorption Kinetics................................................................................................................... 7
Application.................................................................................................................................... 8
Pharmacy.................................................................................................................................. 8
Clean Room.............................................................................................................................. 9
Automotive................................................................................................................................ 9
Mobile Industry and Personal Computers.................................................................................9
Security Applications................................................................................................................ 9
Sensing toxic gases.................................................................................................................. 9
Separating hydrocarbons........................................................................................................ 10
Automotive and toxic gas storage...........................................................................................10
Application of Mil-101(Fe)........................................................................................................... 10
Metal–organic framework MIL-101(Fe) for drug delivery.........................................................10
Metal–organic framework MIL-101(Fe) for artificial kidney application....................................11
Metal–organic framework MIL-101(Fe) for the removal of dyes..................................................11
Conclusion.................................................................................................................................. 12
References................................................................................................................................. 12
 1

CPDP Project Final Report

Abstract

The purpose of this report is the production of Metal-organic framework MIL–101 (Fe).
The main reason for the production is due to the high porosity nature. Other researches
have been done on the production of MOFs which include large families of MOFs with
a large surface area. The MIL was produced by solvothermal approach. By obtaining
FTIR Analysis we have concluded that the peaks were found at 746.92, 1018.48,
1394.06, 1608.68 and 1702cm-1, this showed that our MIL-101(Fe) was synthesized. In
the UV-Vis spectroscopy the amount of absorbed light was observed. This shows the
successful production of our MIL-101(Fe).

Introduction

Metal–organic frameworks gives a remarkable type of chemical structure with ultrahigh

porosity (about 90% empty spaces) and large internal surface areas, more than 6000
m2/g. This complex have both the organic and inorganic components in their structures,
which give MOFs high potential use in cleaning, most remarkably as storage agent for
gases like as hydrogen and methane, and as much effective adsorbents to meet various
separation processes. In addition to this is used in membranes, thin-film equipment,
catalysis, and biomedical imaging are worth taking processes.
Industrial Manufacturer like Paint industry and textile sector on daily basis releases a
large amount of water as wastage which carries highly toxic element and compounds,
includes dyes. This wastage is highly harmful for our environment and ecosystem and
cannot be removed easily because of their chemical properties and complex chemical
structure [1]
 2

MIL-101(Fe)

In 2005 Ferey et. AL[2]. First time invented MIL-101(Fe) which was synthesized from
HF-Cr(NO3)3-1,4-dicarboxylic acid- (H2BDC-) H2O. Since the formation of this
MOF, large number of variant has been added to MOF family. This is due to it
exceptional qualities like largest surface area (4500 m2/g), pore size (29–34 Å), and cell
volume (702.000 Å). Many scientist have tried to form this through gas absorption
method. However, it is hard to form due to its high BET plane which is more than 3200 
m2/g. Methyl orange has a wide range of application in textile industry due to its
reactivity, but has complex structure. Many methods have been introduce to separate
the dye from wastage like electrochemistry, adsorption, and biosorption.

Literature Review

Figure 1; Structure of methyl orange

Metallic–organic frameworks (MOFs), also called porous coordination polymers or

porous coordination networks (PCNs), are metal ions or steel clusters and organic
ligands with multiple binding web sites (N or O atoms), where a self-assembled single-
factor crystal complicated eventually paperwork a two-dimensional (2d) or 3-
dimensional (3D) infinitely extending coordination network in area. An MOF has no
longer only ultrahigh floor region, massive pore volume, and adjustable surface
properties (unsaturated metallic sites) however also excellent structural properties (pore
 3

size and geometry). There are numerous forms of metallic–organic framework

materials, for example, MIL-101(Cr), MIL-88(Fe), MIL-53(Al), cobalt-based totally
material ZIF-8 (ZIF = zeolite imidazole salt skeleton), and copper-based totally material
Cu-BTC, which can be carried out to diverse fields, which includes gas storage and
separation, photocatalysis, drug shipping, and other fields. These days, MOFs have
attracted tremendous attention inside the treatment of pollutants in wastewater. The
iron-primarily based metallic–organic framework material, i.e., MIL101(Fe), is one of
the most consultant substances within the MIL-n collection. MIL-101 (Fe) is a
multistage pore structure, and its huge pore diameter provides remarkable adsorption
capacity. MIL-101(Fe) is greater solid in water since it can bind active components
which includes guest molecules and metallic nanoparticles to restrict it in its pores or in
a cage to enhance its adsorption overall performance. Therefore, in this take a look at,
MIL-101(Fe) was synthesized with graphene oxide (pass) to enhance its adsorption
potential. There are few researchers who have studied the center–shell structure
composite (move-MIL-101(Fe)) that is implemented in photocatalysis; however, none
has genuinely shown and described the shape of the composite (pass-MIL-101(Fe)).
This look at focused on MIL-101(Fe) as an exquisite-small lively polyhedron that may
be synthesized with go and grown at the surface of the material layers with robust solid
homes and a sheet shape; the variety of its lively sites are relatively constrained for the
removal of natural pollutants from waste water. [3]

Materials and Methods

 Synthesis
 4

Figure 2; Mil-101 (Fe)

 Characterization

FTIR Analysis

The characteristic peaks of MIL-101-(Fe) were located at 746.92, 1018.48, 1394.06,

1608.68 and 1702cm-1, which proved that MIL-101(Fe) was successfully synthesized.
The peak at 545 cm-1 was assigned to the Fe–O bond, which appeared in MIL-101(Fe)
peaks at 746.92 and 1018.48 cm-1 was assigned to C–H bending vibrations and C– O –
C, respectively. The peaks located at 1394.06 and 1608.68 cm -1 corresponded to the
symmetric and asymmetric vibrations of O–C═O, and the peak at 1702 cm -1
corresponded to the C═ O bond in carboxyl groups and was in line with the reported
literature.

Figure 3; FTIR Analysis of sample of MIL-101(Fe)

UV-Vis Spectroscopy Analysis:

UV-Vis Spectroscopy (or Spectrophotometry) is a quantitative technique used to

measure how much a chemical substance absorbs light. This is done by measuring
 5

the intensity of light that passes through a sample with respect to the intensity of light
through a reference sample.

Effect of Adsorbents on Adsorption Performance

The effect of Methyl orange and the different concentration ratios of MIL-101(Fe) on
the removal of MO. It can be seen that the adsorption capacity of MO on MIL-101(Fe)
has been significantly improved and the adsorption capacity of (C4) (35mg) MIL-
101(Fe) is the highest. As the concentration ratio of MIL-101(Fe) decreases
continuously, the adsorption performance of MO decreased gradually. Due to the
presence of a small amount of MIL-101(Fe) that occupied the pores of the material, the
pores of the composite and the surface-active sites of the adsorbent decreased, and thus
the adsorption of MO was also reduced. When the concentration is increased, the pores
of the composite and the surface-active sites of absorbent is increased and thus the
absorption of MO is increased.

Concentration change
10
9
8
7
Absorbance

6
5
4
3
2
1
0
200 250 300 350 400 450 500 550 600 650 700
Wavelength(nm)

MO solution C1(10mg) C2(15mg) C3(25mg) C4(35mg)

Figure 4; UV-Vis Spectroscopy Analysis, Effect of changing Concentration of MIL-

101(Fe) on absorption of Methyl Orange.
 6

Figure 5; Absorption of MO on the surface of Mil-101(Fe)

Adsorption Kinetics

The effects of time on the adsorption of MIL-101(Fe). It can be seen that the adsorption
capacity of MO by MIL-101(Fe) increased rapidly before 30 min. This was due to the
large specific surface area of MIL-101(Fe) and a large number of active adsorption sites
on the surface. With the increase of time, most of the adsorptive active sites were
gradually occupied and the adsorption rate slowed down after 60 min, finally reaching
the equilibrium. The adsorption capacity of MO was 60% and higher in MIL-101(Fe).
 7

Effect of change in time on absorption

4

3.5

2.5
Wavelength (nm)

1.5

0.5

0
0 10 20 30 40 50 60 70

Absorbance
MO 10 min 20 min 30 min 40 min

Figure 6; UV-Vis Spectroscopy Analysis, Effect of changing time duration of Absorption

of MO on the surface of MIL-101(Fe).

Application

Metal organic frameworks have many applications in various industries:

Pharmacy
MOFs are used to extract Active Pharmaceutical Substances (API) or drugs in a
centered way or to safety the API in unfavorable conditions gastric acid. A steady
release of active substances such as vaccines are produced by tuning metal-organic
frameworks accordingly.
 8

Clean Room

The conditions in which clean rooms can be tested and controlled by using MOFs in
various applications. This includes humidity manipulate, adsorptions of toxic gases and
air purification process.

Automotive

MOFs growths gasoline storage in CNG-powered automobiles or improve batteries in

electric powered cars. Furthermore, climatization and cabin air change can be supported
by MOFs.

Mobile Industry and Personal Computers

The upgrades on batteries due to MOFs directly transfer to personal PC and your mobile
phones.

Security Applications

Detection and neutralization of toxic materials via metal-organic frameworks offer

many implementations to save lives.

Sensing toxic gases

The detection of toxic gases needs highly sensitive and quick sensing procedures.
Metal-organic frameworks are able to quickly detect gases at small concentrations and
are relevant after quick regeneration. These properties make it perfect for sensor
applications.
 9

Separating hydrocarbons

The separation of hydrocarbons, particularly ethane and ethylene, is a complex process

in the chemical industry. Metal-organic frameworks offer high selectivities toward the
needed gas, which offer new routes to gas separation process.

Automotive and toxic gas storage

Due to their low densities while providing high surface area, MOFs are hired for
gasoline storage like natural gas or toxic gases (e.g., arsines). The fuel molecules get
stacked in the pores and have interaction with the surface of the MOF. This muti
adsorption effect inside the pores significantly increases the amount of gas that is stored
in a gas container.

Furthermore, gases can be properly stored in sub-atmospheric pressure (under 1 atm),

stopping spillage in case of a leak inside the container. [4]

Application of Mil-101(Fe)

Metal–organic framework MIL-101(Fe) for drug delivery

 This is also used in pharmaceutical industry; two members of Tetracycline

family are manufactured through Nanostructures MOF of MIL-101(Fe). Its
structure contains Doxycycline monohydrate and Tetracycline hydrochloride on
each side.
 Large pores and a high surface area make MIL-101 an ideal carrier for drug
delivery purposes used.
 10

 It has been found that it used for encapsulating several drugs such as
doxorubicin, ibuprofen, caffeine, and aspirin in high loading capacities
compared to conventional methods.
 MIL-101 (Fe) as a stable and safe capsule for several small molecule drugs. [5]

Metal–organic framework MIL-101(Fe) for artificial kidney application

 Metal–organic framework MIL-101(Fe) was discovered as a novel sorbent for

artificial kidney application to take out a typical uremic toxin creatinine with
high adsorption capacity and excellent reusability. [6]

Figure 7; Removal of creatinine from the blood using Mil-101 (Fe)

Following is the degradation graph of methyl orange in solution; [7]

 11

Figure 8: Effect of the dosage of MIL-101 (Fe) on the decolorization of

AO7 at different times: (1) 0-24 h, in which 2 mg (a), 3 mg(b), 4 mg(c), 5
mg(d), 6 mg(e), 7 mg(f), 8 mg(g), 9 mg(h), and 0 mg(i) adsorbent were
used; (2) at 4 h. [8]
Conclusion
We conclude that the production of ML-101 (Fe) was successfully completed which can
be shown by the different method tests which were conducted. Different tests were
concluded which include FTIR test, UV-Vis Spectroscopy analysis and Adsorption
kinetics test. All of these tests have shown a positive result confirming that our MOF
MIL-101 (Fe) was synthesized successfully.

References

Introduction to Metal–Organic Frameworks, Hong-Cai Zhou, Jeffrey R.

Long, and Omar M. Yaghi, Chem. Rev. 2012, 112, 2, 673–674, January 26, 2012.

Metal-Organic Framework MIL-101: Synthesis and Photocatalytic Degradation of

Remazol Black B Dye, Pham Dinh Du et. AL, Volume 2019 |Article ID 6061275 |, May
14, 2019.

Revisiting the MIL-101 metal–organic framework: design, synthesis, modifications, advances,

and recent applications, Mahmoud Y. Zorainy et. AL, J. Mater. Chem. A, 2021,9,
22159-22217, Sep 15, 2021.
 12

Nano-Society: Pushing the Boundaries of Technology,  Michael Berger, Volume 8) 1st

Edition, Oct 24, 2009.

Metal–Organic Framework Nanocarriers for Drug Delivery in Biomedical Applications,

Yujia Sun et. AL, Nano-Micro Letters volume 12, Article number: 103 (2020), May 2,
2021.

Metal–organic framework MIL-100(Fe) for artificial kidney application, Cheng-Xiong Yang

et. AL, RSC Adv., 2014,4, 40824-40827, Aug 22, 2014.

Adsorptive removal of acid orange 7 from aqueous solution with metal–organic

framework material, iron (III) trimesate, Fang-Chang Tsai, Yue Xia, Ning Ma, Wen-
Chin Tsen, Desalination and Water Treatment 57(7):1-9
DOI:10.1080/19443994.2014.982199, Nov 14, 2014.