A REPORT

ON

‘Application of Metal-Organic
Frameworks in Wastewater
Filtration’

BY

Name of the Student ID Number

Pratik Srivastava 2017A1PS0901P

Prepared on completion of the

Study Oriented Project, Course No. CHE F266

BIRLA INSTITUTE OF TECHNOLOGY AND SCIENCE, PILANI

April 2019
 ACKNOWLEDGMENT

I want to thank Dr. Bhanu V. Reddy Kuncharam for this excellent opportunity to pursue my interest,
helping me with understanding and in helping him in his research, as well as the Head of the chemical
engineering department, BITS Pilani, Dr. Hare Krishna Mohanta, who allowed me to undertake this
project.
I would also like to thank the Librarian, BITS Pilani, Mr. Giridhar Kunkur without whom, this project
would not have completed.

Page | 1
 ABSTRACT

The increasing concerns of newly commercialized chemicals or heavy usage of the

industrial chemicals has led to severe contamination of water. This has led to prompt
action to find out the most efficient way for a simple model to filter out the impurities.
Purification of wastewater contaminated with organics, oils and heavy metal ions, via
adsorption, was carried out using Metal-Organic Frameworks (MOFs). The MOFs which
are used, have a high surface area and highly porous crystalline structures, which led to
significant adsorption capacity and faster kinetics. The studies taken up in this literature
survey utilized the kinetic and isotherm models to fit their experimental data, and thus
hypothesized the best parameters at which there is maximum adsorption. The adsorption
mechanism is also put into light.

The list of MOFs studied in this project can be found below.

1. MOFs Uses Adsorption capacity (at optimum conditions)

ZnO nanoparticles and Adsorption of Oil
octadecyltrichlorosilane (OTS) from wastewater
coated on quartz sand filter media.

Zn-BDC coated on Magnetic Adsorption of Pb2+ 195.33 mg/g

Montmorillonite
MOF-235, Adsorption of methyl MO - 477 mg/g
[Fe3O(terephthalate)3(DMF)3][FeCl4] orange (MO ) and MB - 187 mg/g
methylene blue (MB)
MIL-101 Adsorption of 132 mg/g
naproxen
UiO-66-NH2 Adsorption of 555 mg/g
diclofenac
DUT-67-Zr Adsorption of The experiment aimed to decrease the
mercury concentration of mercury below 1microg/L
MOF-5 Adsorption of copper 290 mg/g

Page | 2
Chloroform activated UiO-66 Adsorption of 417 mg/g
antibiotics,
sulfachlorpyridazine
(SCP)

HKUST-1 Adsorption of At 318 K, 526 mg/g

sulfachloropyradazine
(SCP)
CDM6-K1000, Carbon derived from Adsorption of DCF - 503 mg/g
MAF-6 Diclofenac and IBP - 408 mg/g
Ibuprofen
Urea-MIL-101 Adsorption of DMZ – 185 mg/g
dimetridazole (DMZ) MNZ – 188 mg/g
and metronidazole
(MNZ)
UiO-66 Adsorption of Arsenic 303.3 mg/g at pH 2
UiO-66-NH2 Selective adsorption The removal rate of cationic dye MB – 97.97%
of cationic dyes whereas for MO – 28.8%
UiO-66-SO3H Adsorption of 263 mg/g
Diclofenac (DCF)
UiO-66 Adsorption of 370 mg/g
methylchlorophenoxy
propionic acid
MIL-101 Adsorption of 312 mg/g
Clofibric acid

Page | 3
TABLE OF CONTENTS
Acknowledgement ................................................................................................. 1
Table of Contents................................................................................................... 4
Introduction ........................................................................................................... 5
Aim ............................................................................................................................................................ 5

Main ...................................................................................................................... 6
*ZnO/OTS (ZnO nanoparticles and octadecyl trichlorosilane) [1.8] ..................................................... 6
*Lead adsorption by Zn-BDC/MMMT (Zn-BDC coated on Magnetic Montmorillonite) [1.16] ............ 8
*Adsorption of Methyl Orange (MO) and Methylene Blue (MB) by MOF-235 [1.7] ......................... 11
UiO-66 for methylchlorophenoxypropionic acid (MCPP) adsorption [1.12] ...................................... 14
UiO-66 for Arsenic adsorption [1.10] .................................................................................................. 17
UiO-66 for sulfachloropyradazine (SCP) adsorption [1.14]................................................................. 20
*UiO-66 and ZIF-8 for fluorine adsorption [1.11] ............................................................................... 23
UiO-66-NH2 for Cationic dyes adsorption [1.9] ................................................................................... 26
*UiO-66-NH2 for Diclofenac (DCF) adsorption [1.15] .......................................................................... 31
UiO-66-SO3H for Diclofenac adsorption [1.13] ................................................................................... 34
DUT-67-Zr for adsorption of Hg2+ and CH3Hg+ [1.1] ......................................................................... 37
MOF-5 for adsorption of Copper ions [1.6] ........................................................................................ 40
HKUST-1 for adsorption of sulfachloropyradazine (SCP) [1.2] ...................................................... 43
*MIL-101 for adsorption of Naproxen (Anti-inflammatory drug) [1.4] .............................................. 46
MIL-101 for adsorption of Dimetridazole (DMZ) and Metronidazole (MNZ) [1.5] ........................... 49
Carbon derived from MAF-6 for Ibuprofen and Diclofenac adsorption [1.3] ..................................... 51

Conclusion ........................................................................................................... 54
References ........................................................................................................... 55

[The papers with * were included in the midsemester of the term]

Page | 4
INTRODUCTION
Dyes, oils, heavy metals, antibiotics, herbicides, all have one thing in common; they all are harmful to the
environment, if present in excess. They can cause a wide range of medical issues if not looked into, as they
are toxic to humans and can lead to poisoning or even cancer. Wastewater generated from the industries,
with these pollutants can cause adverse effects on the environment and the aquatic life. Several types of
research have been conducted and demonstrated the presence of these toxins in our river, lakes, and
groundwater[17][18].

There are many ways to remove these toxins from effluent water before the discharge into the
environment. These include electrolysis, flocculation, photocatalytic degradation, oxidation,
biodegradation, photolysis, and adsorption. Most of these methods are not applicable for commercial
processes, due to the high cost and low efficiency at low concentrations of the adsorbate. However,
adsorption is considered a superior process due to its high removal efficiency, lower price, simplicity of
the process and its ability to remove a wide range of substances simultaneously. Therefore, the
development of adsorbents with high efficiency has been the priority for research in wastewater
treatment.

AIM
This project aims to do a literature review and determine whether MOFs can be utilized for commercial
wastewater filtration.

Page | 5
MAIN
We’ll discuss about each adsorbent in detail and know about its adsorption mechanism.

ZnO/OTS (ZnO nanoparticles and octadecyl trichlorosilane) [1.8]

To remove oil from wastewater, we need to find a surface which is super-oleophilic and since we know
that the super oleophilic surfaces are usually superhydrophobic. Therefore, we coated the surface of a
quartz sand filter with a ZnO nanoparticles and octadecyl trichlorosilane, which made the surface
superhydrophobic.
The OTS/ZnO-coated quartz sand filter showed a very high mechanical stability and acid resistance.
X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM) and Fourier transform
infrared spectroscopy (FTIR) were used to study the chemical composition of the filters and adsorption
capacity.
Oil removal efficiency experiments were performed to assess the oil removal performance.

The image shows the water and oil droplets on the

surface of normal and OTS/ZnO coated quartz sand
filter media. Water is dyed with methylene blue and
oil (dyed with oil red O).

(a) and (c) shows the oleophilic and hydrophilic

properties of the filter.
(b) and (d) shows the oleophilic and
superhydrophobic properties of OTS/ZnO
coated quartz sand filter.

Page | 6
 Oil removal performance

The adsorption is dramatically improved in

almost all cases, this proves that OTS/ZnO
coated quartz sand an excellent oil adsorption
capacity and hydrophobicity.

Durability of OTS/ZnO coating

Ultrasonic processing (ultrasonication) is used

for cleaning materials because it can physically
damage a fragile surface where the chemical
bonding with the substrate is not strong
Ultrasonication is supposed to degrade the
surface and hence decrease the water contact
angle. But as seen from the graph, even after
48 hours, the water contact angle has only
reduced so much. Therefore, the coating has a
good mechanical stability.

After checking the durability of the coating in corrosive

solutions, we find that, from the pH values ranging from 1 to
14, the water contact angle did not decrease significantly
and therefore proved that the coating is also acid resistant.

The OTS/ZnO coating when applied to the inexpensive, non-

toxic, environmentally friendly and stable, quartz sand filter medium, can be potentially used to filter
oily wastewater as it exhibits superhydrophobic and super oleophilic properties, and has a very high
mechanical stability and acid resistance.

Page | 7
Lead adsorption by Zn-BDC/MMMT (Zn-BDC coated on Magnetic
Montmorillonite) [1.16]

Zn-BDC is a type of MOF, which was prepared from Zn2+ and terephthalic acid and catalyzed by
triethylamine at room temperature. Zn-BDC was coated on MMMT to fix the drawbacks of the
adsorbent, that it couldn’t perform effectively when the Pb concentrations were high. After coating,
MMMT@Zn-BDC was obtained, which had a better recyclability but could also cope up with a higher
concentration of Pb.

When pH is greater than 7, Pb precipitates in the form of Pb(OH)2; therefore the pH was adjusted to 2-6
in this study.

With increasing pH, the amount of surface negative

charge of MMMT@Zn-BDC increases, which makes it
favorable to positively charged Pb to get adsorbed.

When the dosage of the adsorbent was low, the

amount of Pb was excessive for the available
adsorption sites; therefore the qe adsorbed was high
but the removal ratio is less because of the
availability of the adsorbent.
When the dosage of the adsorbent is high, more
adsorption sites were available for Pb and thus, qe
decreased but the removal ratio increased because
almost all of the Pb atoms got adsorbed.

Even if the concentration reached 1000 mg/L, the

adsorption was still not saturated but the removal
rate decreased to 71.7% at this concentration.

Page | 8
 The adsorption capacity increased rapidly during
the first 20 mins, and then the Pb ions have
occupied most of the adsorption sites, and
therefore the adsorption capacity increased slowly
in the 2nd half.
After 90 mins, the adsorption reached equilibrium
with adsorption capacity 195.33 mg/g, and the
removal rate of 97.67%.

With the temperature increase, the adsorption

capacity increased from 194.34 to 198.21 mg/g,
and the removal rate increased from 97.17% to
99.11%.

This shows that the adsorption of Pb on

MMMT@Zn-BDC is an endothermic process.

With the increasing number of reuses, the adsorption capacity decreases gradually; after being reused
five times, the capacity decreased to 160.90 mg/g.

However, the adsorption rate remained at 80.45%, which shows that MMMT@Zn-BDC has good
recyclability.

Page | 9
These figures are corresponding to the Langmuir and Freundlich isotherm models, and by observation,
we can see that the adsorption process is better plotted by the Langmuir isotherm model, which shows
that the Pb ions do not interact with each other, the adsorption capacity of each site on the adsorbent is
the same and monolayer adsorption occurs.

We can see from our experiment, that the pseudo-second order fits much better than first order, and
therefore the adsorption taking place is chemical adsorption.

Page | 10
Adsorption of Methyl Orange (MO) and Methylene Blue (MB) by
MOF-235 [1.7]

MOF-235, [Fe3O(terephthalate)3(DMF)3] [FeCl4] (DMF stands for N, N-dimethylformamide) was utilized

to adsorb MO and MB from water.
The adsorption kinetic rate constant was calculated using pseudo-first-order and pseudo-second-order
reaction kinetics.

As shown, the adsorption of MO and MB over MOF-235 is much higher than activated carbon.

dq/dt= k2(qe − qt)2

t/q1 = 1/k2qe^2 + t/qe qe: amount adsorbed at equilibrium (mg/g)

qt: amount adsorbed at time t (mg/g)

t: adsorption time (h)

We find the correlation constant R2 and k2 from the graph.

We discover that the kinetic constant for MB over MOF 235 and activated carbon are nearly similar
even though the adsorption capacity over MOF 235 is larger than activated carbon.
The adsorption data were also analyzed using pseudo first-order kinetic model, but since the
correlation constant of the first order was less than the 2nd order, we choose to use the 2nd order to
map the adsorption data.
Therefore, the adsorption was chemisorption.

Langmuir isotherm was used to plot the adsorption isotherm

Page | 11
 Ce/qe = Ce/Q0 + 1/Q0b Ce: equilibrium concentration of adsorbate (mg/L);
qe: the amount of adsorbate adsorbed (mg/g);
Q0: Langmuir constant (maximum adsorption capacity) (mg/g);
b: Langmuir constant (L/mg or L/mol).

The amount of adsorbed dyes over MOF-235 is higher than that over activated carbon for the
experimental conditions, showing the efficiency of the MOF-235.

The adsorption isotherms for MO over MOF -235 at 25oC, 35oC, 45oC and the corresponding Langmuir
isotherms for them.
It was proved that the increase in temperature resulted in an increase in the amount of adsorption.
Therefore the adsorption was deemed to be chemisorption.

Page | 12
We can find the Langmuir constant b from the slope/intercept of the Langmuir plot and therefore find
the free energy change from the equation,

Delta(G) =−RT ln b

We plot ln b vs. 1/T to get the Van’t Hoff plot, as

shown to the right.
We can find the change in enthalpy(H) and change in
entropy(S) from the slope and the intercept.
The delta(H) values come out to be 99.6 and 63.1
kJ/mol for MO and MB adsorption, respectively, and
entropy change 441 and 300 J/(mol K) for MO and MB,
respectively.

Since the number of desorbed water molecules is more

than the number of adsorbed MO and MB molecules, a Positive delta(S) results (dyes are very bulky
compared with water; therefore, several water molecules may be desorbed by adsorption of a dye
molecule).
Therefore, the driving force for the adsorption of the dye (negative delta(G)) on MOF-235 is due to an
entropy effect (large positive delta(S)) rather than an enthalpy change (delta(H) is positive).

It was seen that the amount of MO adsorbed

decreased with the increase in pH and vice versa was
observed for MB.
The adsorbed may be explained due to the
electrostatic interaction between the dyes and the
adsorbent. MO and MB usually exist in negative and
positive forms, respectively. Since the Zeta potential of
MOF-235 is around 6, we can see that there is an
increased negative charge on the surface of the
adsorbent, due to which the adsorption of the change
in adsorption of MO and MB with pH maybe explained.

The special characteristic of MOF-235 is shown, that it readily adsorbs both cationic and anionic dyes in
the liquid phase.

Page | 13
UiO-66 for methylchlorophenoxypropionic acid (MCPP) adsorption
[1.12]

The amount of MCPP adsorbed at an initial

concentration of 20 ppm, is shown in the figure
given.

The adsorption of MCPP on UiO-66 was much

higher than the other given adsorbents.

The high adsorption of MCPP over UiO-66 might be

a result from the favorable interactions between
them.

The data given below was found experimentally.

Adsorbent SABET m2/g Total Pore Micropore K2 g/mg h Qo mg/g

Volume cc/g Volume cc/g
UiO-66 982 0.50 0.39 2.91 x 10-2 370
Activated 871 0.51 0.30 9.64 x 10-4 303
carbon

The kinetic constant of UiO-66 was found to be around 30 times higher than Activated Carbon; this
shows that there is a rapid uptake of MCPP, even though the micropore volume is less than Activated
Carbon.

The adsorption isotherm for MCPP adsorption by

UiO-66 and AC is shown to the right. The results were
obtained after adsorption over 24 hours
(equilibrium).

In (a), we see that when the concentration of MCPP is

very less, UiO66 is better to adsorb MCPP.

Page | 14
In (b), the adsorption isotherm was plotted to fit the
Langmuir isotherm.

The maximum adsorption capacity was calculated

from (b), and its value is shown in the above table.

The separation factor (RL) was also calculated from

the Langmuir isotherm, and since all the values are
<1, we can say that the adsorption was favorable.

Since the concentration of herbicides and pesticides present in water is deficient, (<0.1 microg/L) we
should focus on the adsorption by UiO-66 as it adsorbs MCPP at low concentrations.

The adsorption of MCPP over UiO-66 increases till it

reaches the maximum value around pH 4-4.8 and then
decreases on increasing pH.

MCPP exists in the neutral form at pH < 3.8 and in

anionic form, at pH > 3.8 due to the fact that the pKa
value of MCPP is around 3.8.

Page | 15
 From the Zeta potential, we found that the isoelectric
point of UiO-66 was around pH~3.9.

Therefore, the favorable adsorption of MCPP over

UiO-66 at a pH of 3 to 4 is maybe explained due to
the electrostatic interactions between the negatively
charged MCPP and positively charged UiO-66.

The figure given on the right will explain the

mechanism.

Even though the adsorbed amount decreased on

increasing the pH, there is a considerable amount
of MCPP adsorbed (~60 mg/g), which can be
explained by the π–π stacking between the
benzene rings of the adsorbent and the
adsorbate.

The adsorption of MCPP on UiO-66 did not decrease

significantly after reusing it for a few cycles.

With this, we can confirm that UiO-66 is a suitable

adsorbent to adsorb MCPP for commercial applications.

Page | 16
UiO-66 for Arsenic adsorption [1.10]

Arsenic is adsorbed over UiO-66 over a broad range of pH, and it achieves an adsorptive capacity of 303
mg/g at the optimal pH =2.

The experimental data was plotted with both, Langmuir and Freundlich isotherms. The Langmuir
isotherm fits better as seen from the correlation constant r2. And thus, this shows that the model is a
monolayer adsorption process.

pH Langmuir isotherm Freundlich isotherm

Qmax mg/g b L/mg R2 K N R2

2.0 303.34 6.13 0.92 217.47 9.16 0.83

7.0 147.71 0.42 0.99 62.31 4.74 0.89

We can see the comparison between other adsorbents and UiO-66 given below. We see that UiO-66
has shown the highest adsorption capacity, with the largest working pH range.

Adsorbent Max. adsorption capacity mg/g Working pH range

Zirconium-based nanoparticle 279.9 at pH 7 4-7
Activated carbon 30.5 at pH 7 6-8
UiO-66 303.3 at pH 2 1-10
ZIF-8 60 at pH 7 6-8

Page | 17
As we can see, the adsorption takes
place in a very broad pH range, 1-
10.
UiO-66 can accomplish adsorption
generally above 75 mg/g. The best
adsorption capacity is observed to
be at pH 2, which is nearly 100
mg/g.
The adsorption capacity decreased
after pH 10, possibly due to the
structural decomposition of UiO-66
under too basic composition.

The zeta potential of UiO-66 was

calculated to be 3.9.

Electrostatic interaction plays a role

in the adsorption as, the negative
charge on the surface of UiO-66
increases with the increase in pH
and so does, on the surface of the
arsenic compound, as shown in the
figure.

Therefore, the adsorptive capacity

decreases with the increase in pH,
due to electrostatic repulsion.

However, at pH 2 electrostatic interaction is not the only controller of adsorption, as there is no charge
on the surface of the arsenic compound.

PXRD (a) and FTIR (b)

experiments were
conducted to characterize
the adsorbents.

There was no change observed in the PXRD patterns after adsorption, which shows the stability of UiO-
66 throughout the test.

Page | 18
In the FTIR spectrum of UiO-66, a new band at 830 cm-1 appeared. The new peak at 815 cm-1 proves the
binding of arsenic to UiO-66, as Zr-O-As coordination bond.

The peak at 865 cm-1 is due to the combination of symmetric and asymmetric stretching vibrations of
the As-O.
A small peak at 660 cm-1 is observed, due to the presence of As-OH asymmetric vibrations.

Therefore, the formation of arsenic complexes within UiO-66 is confirmed via Zr-O-As coordination
bonds.

Page | 19
UiO-66 for sulfachloropyradazine (SCP) adsorption [1.14]

The use of sulfonamide antibiotics is increasing due to their high demand in cattle farming, agriculture,
and other pharmaceutical uses.
the amphoteric nature of the sulphonamide helps them to migrate to the environment easily, and it’s
difficult to treat them in conventional wastewater plants because of their anionic and antibacterial
nature.

Even with the high surface area, there is no

considerable adsorption of SCP on ZIF-67. The
surface area of ZIF-67-CH3OH is 2.6 times higher but
the amount adsorbed of SCP isn’t that different
than ZIF-67-H2O. Therefore, there is no strong
attraction between SCP and ZIF-67.

The non-activated and chloroform activated UiO-66

showed the maximum adsorption between the
adsorbents.

The surface area of chloroform activated UiO-66 is

1.5 times higher than pristine UiO-66; the
adsorption of SCP is around double than pristine
UiO-66.

The effect of time was studied using different initial concentrations of SCP, and it was found that the
pseudo-second-order kinetic model with r2 value 0.999 fits the best for the adsorption model.

The below table was calculated from the given

adsorption vs. time graph.

Page | 20
 Initial concentration Qe exp Pseudo 2nd order

Mg/L Mg/g K2 (g min/mg) Qe cal mg/g R2

5 50 8.8 x 10-2 50 1

25 221 6.1 x 10-3 220 0.998

45 408 2.2 x 10-3 404 0.999

As it has been found, the adsorption is very fast, and most of the SCP uptake is completed in 10 mins,
using UiO66. The faster kinetics is due to the attraction between UiO-66 and SCP.
It is to be noted that UiO-66 removes almost all the SCP in 10 min even at very low concentrations i.e.,
5 mg/L, making it a suitable adsorbent for SCP on a larger scale.

The adsorption isotherms were studied at different temperatures for SCP adsorption on UiO66, and the
max adsorption capacity was found using Langmuir
isotherm.

The below table was found from the given figure.

Temperature Qm exp Langmuir model

0
C
Mg/g Qm calculated KL L/mg RL R2
mg/g

25 403 417 0.75 0.017 0.997

35 339 357 0.41 0.029 0.995

45 312 330 0.16 0.059 0.996

It can be seen that the maximum adsorption capacity and adsorption constant decrease with increasing
temperature and the highest adsorption capacity of 417 mg/g is achieved at 25 °C.
Page | 21
The adsorption favorability factor (RL) is in the range 0 < RL < 1 at all three temperatures for UiO-66,
suggesting the favorable adsorption of SCP.

The adsorption capacity decreases with the

increase in pH, showing the electrostatic
repulsion between negatively charged
adsorbent and anionic adsorbate at pH > 5.5.

It is interesting to mention that pH of isoelectric

point (pHiep) for UiO-66 is 5.5, the same as the
pKa value of SCP. At this pH, adsorbent and
adsorbate in suspension have no charge, but
adsorption is very high, suggesting some other
factors in adsorptive removal of SCP.

There will be a neutral solution at pH 5.5 as the pKa value of SCP and pHiep for UiO-66 is 5.5. Due to the
low solubility of SCP at low pH, the main factor in the adsorption mechanism is hydrophobic interaction,

The solubility of SCP increases with increase in pH. Therefore there is a decrease in the adsorption.
Therefore, hydrophobic interactions along with π-π interaction are used to explain the adsorption

The below diagram explains the adsorption mechanism.

Page | 22
UiO-66 and ZIF-8 for fluorine adsorption [1.11]

Adsorbent SABET m2/g SALangmuir m2/g Total pore Mean pore

volume m3/g diameter (nm)
ZIF-8 1050 1150 0.57 4.5
UiO-66 800 970 0.45 3.2

The surface area and the pore volume of ZIF-8 are larger than UiO-66, and thus we expect the former to
adsorb more fluoride.

The removal efficiency of ZIF

-8 decreases on increasing
the dosage because the
fluoride ions have already
occupied the available space
and thus the extra ions are
not adsorbed, on the
contrary, the removal
efficiency of UiO-66 hits the
peak at 0.6g/L dosage, this
proves that UiO-66 can
adsorb more fluoride ions per unit of the adsorbate.

The best pH for the adsorption to happen is neutral; this proves that the adsorption is taking place with
some other forces than electrostatic, like hydrogen bonding.

Page | 23
We find that when the initial concentration of fluoride is increased, the amount of adsorbed is
increased, but the removal efficiency is decreased as the adsorbent is in less and cannot adsorb all of the
fluorides.

Kinetics Constants Fluoride Kinetics Constants Fluoride concentration

ZIF-8 concentration mg/L UiO-66 mg/L

2 4 2 4
Pseudo 1st K1 0.0156 0.0167 K1 0.0187 0.0196
Pseudo 1st
order R2 0.745 0.667 R2 0.765 0.798
order
QCal 5.678 12.674 QCal 6.576 14.243

Pseudo 2nd K2 0.0443 0.0465 Pseudo 2nd K2 0.0456 0.0645

order r2 0.895 0.834 order r2 0.886 0.978
qe cal 12.6 17.5 qe cal 13 15.7

When we use the kinetics model, we see that the correlation constant (R2) is more for the pseudo-
second-order model for both of the MOFs. Therefore, we find that the pseudo-second-order is a better
fit. (chemisorption)

Isotherm Constants Fluoride Kinetics Constants Fluoride concentration

ZIF-8 concentration UiO-66 mg/L
mg/L

2 4 2 4

n 3.5 5.3 n 2.7 3.6

Freundlich R2 0.775 0.845 Freundlich R2 0.675 0.778
Kf 18.5 18.9 Kf 19 19.8

Page | 24
 Langmuir KL 1.5 1.8 Langmuir KL 0.576 0.657
r2 0.897 0.898 r2 0.879 0.898
qm 25 29 qm 20 28

When we use the isotherm model, we find that the Langmuir isotherm model fits better than the
Freundlich as the correlation constant is greater in both the MOFs. Therefore, we use the Langmuir
isotherm to explain the adsorption

We find that ZIF-8 has a better removal performance then Uio-66, but as there is no data given about
the regeneration of the MOFs, we say that ZIF-8 is a better adsorbent for the removal of fluoride ions
from wastewater.

Page | 25
UiO-66-NH2 for Cationic dyes adsorption [1.9]
The adsorption of 5 hydrophilic dyes was studied, in which there are 3 cationic and 2 anionic dyes

The figure shows the

adsorption of Methylene blue.

The absorbance rapidly

decreased in the 150 mins,
showing that MB was
effectively adsorbed

(a) and (c) displays the UV–vis

spectra during MB adsorption
on UiO-66 and UiO-66-NH2,
respectively.

(b) and (d), show the

concentration of MB vs time.

The figure shows the

adsorption for anionic dye
methyl orange.

The UV–vis spectra during MO

adsorption on UiO-66 and UiO-
66-NH2 are shown in (a) and
(c).

The removal rates of the MO

dye on UiO-66 and UiO-66-
NH2 are 38.24 and 28.79%,
respectively.

Page | 26
It can be seen that UiO-66 displays higher adsorption performance for cationic dye MB than for anionic
dye MO, whereas, in contrast with UiO-66, UiO-66-NH2 shows an even stronger affinity for cationic dye
MB.

Neutral Red (NR), Rhodamine B (RhB) and Acid Chrome Blue K (ACBK) were selected to test the affinity
for cationic dyes.

Dyes Removal rate %

UiO-66 UiO-66-NH2
Cationic Methylene blue 90.59 97.97
Rhodamine B 77.47 82.69
Neutral Red 74.84 75.85
Anionic Methyl orange 39.24 28.80
Acid Chrome Blue K 31.61 22.53

We see that the removal rate of all the cationic dyes with NH2 was better than the original one.
We also see that the original one was better in adsorbing anionic dyes than the modified one, which
already has been shown above.

The adsorption of mixed dyes (cationic dye MB and anionic dye MO) on UiO-66 and UiO-66-NH2 was
also studied.

(A) and (C) show the UV–vis

spectra for the adsorption on
UiO-66 and UiO-66-NH2,
respectively.

The removal rates of MB and

MO are about 98.15 and
26.41%, respectively, after
150 min adsorption.

This shows that there is preferential adsorption of cationic dyes to anionic dyes and the modified UiO66

Page | 27
has a better adsorption capacity for cationic dyes.

Adsorption kinetics

As shown, both UiO-66 and UiO-66-NH2 display

preferential adsorption for cationic dye MB.

For pseudo 1st order model

Adsorbent Dye Qe exp K1 Qe cal R2

UiO-66 MB 90.88 2.921 x10-2 66.46 96.27
MO 39.42 2.249 x10-2 25.41 86.64
UiO-66-NH2 MB 96.45 3.584 x10-2 48.28 87.66
MB 28.97 3.776 x10-2 19.93 96.08

For pseudo 2nd order

UiO-66 MB 90.88 8.228 x10-4 95.33 99.97

MO 39.42 1.856 x10-4 41.98 99.57
UiO-66-NH2 MB 96.45 2.613 x10-3 97.66 99.99
MB 28.97 4.933 x10-3 30.29 99.99

It can be seen that the R2 is highest for the pseudo 2nd order model, and thus we see that the adsorption
of MB and MO follows pseudo 2nd order.

Page | 28
Recycling

We see that the removal rate of MB and MO decreases

after each cycle, and they generally stabilize at about 92
and 28%.

Mechanism

BET UiO-66 UiO-66-NH2

BET surface area 837.91 616.55
External surface area 274.57 304.28
Micropore area 563.34 312.27

UiO-66-NH2 has bigger external surface area than UiO-66, and this may be one reason why UiO-66-NH2
can adsorb MB more effectively than UiO-66 for MB.
However, the external surface area is not the only mechanism for the adsorption capacity, UiO-66-NH2
exhibits larger adsorption capacity than UiO-66 for MO, although it has a bigger external surface area.

Protons from the dyes get inside the MOF through its micropores, and they get captured by NH2 to yield
NH3+, and this causes the inside of the MOF to be positively charged. Therefore, the surface should be
negatively charged and thus cationic dye is easily adsorbed.

Page | 29
Page | 30
UiO-66-NH2 for Diclofenac (DCF) adsorption [1.15]
Diclofenac is a common non-steroidal anti-inflammatory agent for treating various kinds of
inflammatory disorders. Despite a certain dose of DCF is taken in by bodies, most are discharged into the
waters eventually, leading to chronic human exposure risks.

DCF solution (600mg/L, pH 5.6) was used in the experiments

Materials Surface area Average pore Average pore pHpzc

(activation temp) m2/g volume size
UiO-66 (25) 274.2 0.221 0.55 7.4
UiO-66-NH2 (25) 383.1 0.886 0.57 7.6
UiO-66-NH2 (90) 320.6 1.130 0.57 7.6

Higher activation temperature for UiO-66-NH2 could slightly decrease its surface area but increase its
average pore volumes, which should be due to the disappearance of small holes into the bigger holes.

The experiment showed that the activation

temperature has a great effect on DCF
adsorption.
On increasing the activation temperature
from 25C to 90C, the adsorption increased by
33%.

The effect of contact time on DCF removal by these

adsorbents is shown.

Page | 31
For pseudo 1st order model

Adsorbents Qexp K1 Qe1 R2

UiO-66 (25) 96.2 9.21 x10-3 52.2 0.930
UiO-66-NH2 (25) 237 8.52 x10-3 178 0.922
UiO-66-NH2 (90) 317 9.67 x10-3 233 0.970
UiO-66-NH2 320 9.67 x10-3 252 0.965
(130)

For pseudo 2nd order

Adsorbents Qexp K1 Qe1 R2

UiO-66 (25) 96.2 6.51 x10-4 98 0.996
UiO-66-NH2 (25) 237 1.73 x10-4 238 0.991
UiO-66-NH2 (90) 317 1.35 x10-4 323 0.989
UiO-66-NH2 320 1.23 x10-4 323 0.989
(130)

The pseudo second-order model fitted all adsorption process better than that of the pseudo-first-order
model in terms of correlation factor (R2).

Adsorbents Freundlich model Langmuir model

Kf N R2 Qm KL R2
UiO-66-NH2 90.2 3.81 0.973 357 9.06 x10-2 0.998
(25)
UiO-66-NH2 201 5.69 0.978 555 6.89 x10-2 0.990
(90)

The correlation constant of the Langmuir model was the largest.

Adsorbents T 0C Delta(G) Delta(H) Delta(S)

UiO-66-NH2(90) 35 -7.74 33.5 134
45 -9.08
55 -10.42

The negative values of ΔG indicated the adsorption reaction was spontaneous at these given
temperatures.
Higher adsorption temp is good for DCF removal; therefore, this process is an endothermic process.

Page | 32
 The maximum adsorption takes place at a pH of
5.2

During the pH range, DCF was negatively charged, UiO-66-NH2 showed higher pHpzc (∼7.6)
Therefore, UiO-66-NH2 was positively charged at that pH range. Electrostatic interaction takes place, and
DCF is adsorbed.

The uptake of DCF over this pH range could also be explained by H-bonding mechanism, where UiO-66-
NH2 worked as H-donor and DCF worked as H-receptor. The H of DCF can be removed at pH > 4, while
the H of amino in UiO- 66-NH2 can be stable up to pH ∼8.

Page | 33
UiO-66-SO3H for Diclofenac adsorption [1.13]

XRD patterns are shown in the given figure; it is

confirmed from the figure that the structure of the
MOF was not affected by NH2 or SO3H

The nitrogen adsorption isotherm shows that the functionalization has decreased the porosity of UiO-
66, in the order: UiO-66 > 18%-SO3H-UiO-66 > NH2-UiO-66

The functionalization of UiO-66 with NH2 and SO3H groups was also verified with FTIR spectra.

Page | 34
UiO-66 was compared against other MOFs in DCF
adsorption.

Further work is needed to understand why other

MOFs exhibit poor results for the adsorption of
DCF.

A pseudo 2nd order kinetic model was used.

Adsorbent K2 R2 Q0 for B (L/mg) R2

Langmuir plot Langmuir
(mg/g) plot
AC 0.004 0.998 76 0.199 0.999
UiO-66 0.014 0.998 189 0.039 0.997
18% SO3H-UiO- 0.017 0.999 263 0.008 0.999
66

The high value of the correlation constant confirms that the pseudo 2nd order model fits the adsorption
model.

Pristine UiO-66 adsorbs DCF much more than

AC; this shows the potential of UiO-66 in
adsorption.

The max adsorptive capacity of UiO66 is

189mg/g and for 18%SO3H-UiO-66 is 263 mg/g.

It’s important for the adsorbent to adsorb at

low concentrations, as DCF is itself present in
very low concentrations in water. Thus, as
seen from the graph, the DCF is readily
adsorbed by the 18%SO3H-UiO-66 at low
concentrations.

Page | 35
The possible
mechanism is shown
as follows.

There is favorable adsorption of DCF over UiO-66 at pH < 5.5 because the isoelectric point of UiO-66 is
5.5 and pka of DCF is around 4, this means that the surface of the adsorbent remains positively charged,
while DCF remains negatively charged at pH > 4.
Both DCF and UiO-66 become negatively charged at pH > 5.5 and due to electrostatic repulsion, the
adsorption decreases.

Page | 36
DUT-67-Zr for adsorption of Hg2+ and CH3Hg+ [1.1]

DUT-67 (Zr) was successfully able to remove Hg and CH3Hg+ with a removal efficiency of 90% and 55%
respectively.

We chose 20ug/L as the concentration as the average wastewater has around that concentration of Hg.

The effect of temperature and varying pH was studied at a temp range of 15 to 55 C and a pH range of 2
to 7.

Effect of pH

When the pH is less than 3, mercury exists as

Hg2+.
When the pH is greater than 6, Hg(OH)2 exists.
When the pH is between 3 to 6, Hg2+, Hg(OH)2,
Hg(OH)+ exists.

The result shows that there was relatively

lower removal efficiency of Hg at low pH, and
as the pH kept increasing the adsorption
efficiency increased and reached a high at pH 6.

This result was mainly caused by the protonation of the active sites of DUT-67 (Zr) under the lower pH.
The protonation of active sites of DUT-67 (Zr) decreased with the pH increases, and the active sites
became more beneficial for sorption of Hg2+ to DUT-67 (Zr). When the pH > 6, the adsorption efficiency
of Hg2+ decreased due to the hydrolysis of metal ion, and it competed for the metal ion adsorption on
DUT-67 (Zr).

Effect of temperature

With an increase in temperature, the removal

efficiency of Hg increased from 47 to 65%. The
increase implies that the adsorption is an
endothermic process, which means that
chemisorption is taking place.

Therefore, we took the optimum temperature as

55C.

Page | 37
 Adsorbate Delta(H) Delta(S) Delta(G)

Hg+2 14.73 101.76 -14.59 -15.61 -16.63 -17.64 -18.66

CH3Hg+ 10.18 90.23 -15.82 -16.72 -17.62 -18.53 -19.43

According to the slope and intercept of the plot of lnKd against 1/T, the results of ∆H and ∆S were
obtained respectively. The values of ∆S, ∆H, and ∆G were shown in Table.

The adsorption process is endothermic and spontaneous.

Adsorption Kinetics

The adsorption rate increased rapidly during

the first 20 mins and then increased slowly.

The pseudo first order and second order model

were used to evaluate the effect of contact
time.

Adsorbate Kinetics model Parameter Quantitative value

Hg+2 Q exp 0.0451
Pseudo 1st order Q calculated 0.0169
K1 0.0414
R2 0.5627
Pseudo 2nd order Q calculated 0.0461
K2 5.6916
R2 0.9977

Therefore, we chose a pseudo 2nd order kinetic model as the correlation constant is much closer to 1.

Page | 38
Removal of Hg2+ and CH3Hg+ with DUT-67 (Zr) in real water samples

Sample Real Adsorbate Added Found Residual Removal

mercury (microg/L) (microg/L) (microg/L) efficient
sample (%)
River water 0.67 Hg+2 10 8.8 0.4 95.45
20 17.96 0.73 95.93
50 53.78 5.24 90.26
CH3Hg+ 10 11.07 3.31 70.10
20 22.38 11.09 50.45
50 49.2 34.2 30.49

Lake water 0.51 Hg+2 10 10.59 0.84 92.07

20 21.73 0.98 95.49
50 60.58 4.81 92.06
CH3Hg+ 10 9.07 2.12 76.63
20 18.28 9.82 46.28
50 48.61 22.87 52.95

When the concentration of Hg2+ was lower than 20 μg L−1, the remaining Hg2+ levels could reach the
standard of WHO (1 μg L−1).

Page | 39
MOF-5 for adsorption of Copper ions [1.6]

The data in the table below was found experimentally.

Sample BET surface area Pore volume Average pore size

MOF-5 888.5 m2/g 0.434 cc/g 1.04 nm

The copper ion uptake into MOF-5 is

rapid at the first 30 min, and then it
reaches to the equilibrium. This
observation may be due to that at
the initial time, the numbers of
available sites for adsorption of
Cu2 + are larger than close to
equilibrium

Kinetic model Alpha K1 K2 Qe R3

Pseudo 1st - 0.3430 - 173.5 0.9844

order
Pseudo 2nd - - 0.0038 181.0 0.9966
order
Fractal like 0.3285 0.8851 - 183.4 0.9985
pseudo 1st
order

Fractal-like pseudo 1st order kinetic model was used as the value of correlation constant was the highest.
this model indicates that the rate constant of the system is time dependent, which is due to the
presence of different active site for adsorption (heterogenous surface) and therefore changing of
favorable active sites of adsorption with time.

Page | 40
Adsorption Isotherms

Isotherm Qm KL 1/n R2
Langmuir 236.12 0.149 - 0.9704
Freundlich - - 0.1485 0.9805
Langmuir- 289.88 0.082 - 0.9911
Freundlich

It was seen that the max adsorption capacity of MOF5 is 290mg/g, and the results of the isotherm data
are that the Langmuir-Freundlich isotherm fits the best.

The kinetic data and isotherm data agree on the fact that the surface of the adsorbent is heterogenous;
there are different active sites for adsorption.

Effect of temperature

The removal percentage was found

at different temp, and it shows that
the removal efficiency increases with
the increase in temp. This can be
because of the endothermic nature
of the adsorption.

Page | 41
Effect of pH

pHpzc of MOF-5 was obtained around

7.2
As above pH>6, copper ion
precipitates as copper hydroxide, we
keep the pH below 5.5

Where the pH range is lower than pHpzc,

the surface charge of the adsorbent is
positive.

Thus, increasing of pH leads to decreasing repulsion between Cu2 + and positive surface, and also the
removal percentage of copper ions increase by decreasing hydrogen ion concentration that competes
with Cu2 + ions for the adsorption sites.

The maximum removal efficiency of copper ion by MOF-5 is at pH = 5.2

Page | 42
HKUST-1 for adsorption of sulfachlorpyridazine (SCP) [1.2]

Activated HKUST-1 was used in adsorption tests for SCP as the surface area increased from 1100 m2/g to
1700 m2/g after methanol activation with an average pore size of 1.7 nm and the single point
(P/P0 = 0.995) total pore volume was also increased from 0.42 cm3/g to 0.78 cm3/g after activation with
methanol.

Effect of pH

The maximum adsorption was seen at pH of 3 and

then it constantly decreased.

The pH of point of zero charges for HKUST1 is 4.0,

while the pKa value of SCP is 5.5.

The surface of HKUST-1 will be positively charged at

pH 3.5 and negatively charged at pH > 4. Larger
amount of anionic SCP is expected at pH ⩾ 5.5.

With the increase of pH (>4–5.5), the anionic form

of SCP exists. Due to the electrostatic repulsion
between the anionic SCP and negatively charged surface of HKUST-1, the adsorption decreases.

Adsorption kinetics

We find that the experimental data fit the pseudo 2nd order the best, with the largest r2.

Initial concentration Qe exp Pseudo 2nd order

K2 Qe cal R2

6.2 x 10-3 160 1.00

20 161

40 289 2.2 x 10-3 286 0.999

Adsorption takes place very fast due to the high surface area, large number of pores, large pore volume
and open metal sites of HKUST-1.

Page | 43
Adsorption Isotherm

Temperature K Qm exp Langmuir model

Qm KL RL R2

384 0.40 0.027 0.996

298 365

308 429 413 0.41 0.026 0.994

318 501 526 0.61 0.017 0.998

We find that the Langmuir isotherm fits better as compared to Freundlich isotherm.

As we can see, with the increase in temperature the adsorption capacity also increases and can go as
high as 526 mg/g.

Adsorption mechanism

The higher adsorption capacity at pH 3.5 is due to electrostatic bonding and π-π interactions.
The existence of hydrogen bonding is taken into consideration, given that there is still significant
adsorption in the pH range of 3.5 to 11.5.

The adsorption mechanism is shown below.

Page | 44
 Therefore, it can be
concluded from the
pH and FTIR studies
that high adsorption
of SCP on HKUST-1 is
attributed to
electrostatic
interaction, hydrogen
bonding, and π-π
interactions.

Thermodynamic parameters were found from the plot of Van’t Hoff’s equation.

Temperature Delta(G) Delta(H) Delta(S)

298 -28.8 4.0 110.3
308 -29.8 - -
318 -40.9 - -

Therefore, the isothermal data at different temperatures revealed that adsorption of SCP on HKUST-1 is
a spontaneous and endothermic process.

Page | 45
MIL-101 for adsorption of Naproxen (Anti-inflammatory drug) [1.4]

The table below shows the summarized textural properties.

Adsorbent BET surface area Langmuir surface area Total pore volume
Activated carbon 871 1280 0.51
MIL-100-Fe 1492 2233 0.76
MIL-101 3014 4910 1.82

The naproxen adsorption (a) over activated carbon,

MIL-100-Fe and MIL-100 was rapid at the initial
stages of the contact period, and afterward it
approached equilibrium.
The dynamics of naproxen adsorption can be
interpreted by the pseudo second-order model.

MIL-101 Activated carbon

Initial concentration

10 13 15 10 13 15

92.1 111.0 119.1 44.7 51.4 54.5

QE EXP

Qe cal 94.7 113.1 121.8 45.3 52.6 55.7

K2 1.45 x10-3 1.47 x10-3 1.55 x10-3 2.30 x10-4 2.40 x10-4 2.50 x10-4

R2 0.984 0.985 0.996 0.997 0.996 0.997

The importance of pore size is seen from this result, as the kinetic constant of adsorption generally
increases with increasing pore size.

Page | 46
Langmuir isotherm is used in this study to describe the
adsorption isotherms

Adsorbent Langmuir parameter

B L/mg Q0 mg/g R2
Activated carbon 0.22 81 0.999
MIL-101-Fe 1.78 115 0.999
MIL-101 2.92 132 0.999

This shows that the Q0 values of naproxen over MIL-101 are 132 mg/g, which is 1.15 times and 1.63
times higher than that of MIL-100-Fe and activated carbon, respectively.

Naproxen exists in ionic form as its pKa is 4.

With increasing pH, the positive surface charge density
of MIL-101 decreases.
As the surface charge density decreases, the
electrostatic interaction decreases, and thus the amount
adsorbed decreases.
The mechanism of naproxen adsorption on MIL-101 may
be explained with a simple electrostatic interaction
between naproxen and the adsorbent.

Adsorption of clofibric acid

MIL-101 shows better performance than Activated

carbon in kinetics and adsorption capacity.

Page | 47
The adsorption is very similar to Naproxen as they have
the same functional group (-COOH).

Adsorbents Langmuir parameters

B (L/mg) Q0 mg/g R2
Activated carbon 0.029 244 0.995
MIL-101 0.025 312 0.992

Page | 48
MIL-101 for adsorption of Dimetridazole (DMZ) and Metronidazole
(MNZ) [1.5]

Effect of adsorption times on the adsorbed amounts of (a) dimetridazole, and (c) metronidazole over
MIL-101s.

The below figure (a) and (b) shows the adsorption isotherms of DMZ over MIL-101s based on unit weight
and BET
surface area of
the adsorbent,
respectively.

Page | 49
In the above figure, (c) and (d) show the adsorption capacities calculated using Langmuir isotherm.

The Q0 value of DMZ and MNZ over Urea-MIL-101 was found to be 185 and 188, respectively.

Due to the presence of NO2 group on the

adsorbate and NH2 on the adsorbent, H
bonding was taken into consideration as a
potential mechanism.

The decrease of qt over MIL 101 and urea- MIL

101 with increasing pH is due to the inclusion
of electrostatic interaction.

The mechanism is shown on the left.

Page | 50
Carbon derived from MAF-6 for Ibuprofen and Diclofenac adsorption
[1.3]
Ibuprofen (IBF) and Diclofenac (DCF) were studied in this model.

CDM6s were obtained after pyrolysis of MAF6 in the presence of KOH.

With increasing pyrolysis temperature (in the presence of KOH), the adsorbed N2 (accordingly, the BET
surface area and total pore volume) increased, and the pore diameter increased similarly.

Adsorbents SABET PVtotal PVmicro Composition

C wt% N wt% O wt%
Activated 1016 0.56 0.29 - - -
carbon
MAF-6 1401 0.62 0.57 - - -
CDM6- 1484 0.72 0.63 82.1 5.0 5.0
1000
CDM6- 2911 1.47 0.11 90.2 4.0 3.9
K850
CDM6- 3123 1.77 0.06 94.6 0.9 1.9
K1000

In (a), ibuprofen is getting adsorbed.

in (b), diclofenac sodium is getting adsorbed.

The adsorbed quantities (q12h) of IBP and DCF

increased in the order of the adsorbents
AC < CDM6-1000 < CDM6-K700 < CDM6-
K850 < CDM6-K1000

Page | 51
 (a) IBF
(b) DCF

Irrespective of the adsorption time, CDM6-K1000 showed

much higher adsorbed quantities (qt) than did Activated
carbon.

We choose the Langmuir isotherm for the adsorption isotherm model.

Adsorbents IBP DCF

Q0 mg/g B mg/L R2 Q0 mg/g B mg/L R2
Activated 168 0.21 0.998 79 0.05 0.999
carbon
CDM6- 408 0.23 0.999 503 0.27 0.999
K1000

We see that the correlation constant is very close to 1. Therefore the Langmuir isotherm model fits well.

Page | 52
Adsorption mechanism

As we can see, the amount adsorbed doesn’t ever go to

zero. Therefore we can say that π-π interactions take
place, as both IBF and CDM6-K1000 have aromatic
rings.
The electrostatic interaction cannot explain the
adsorption at low pH as IBF is neutral at pH <4.9

Due to the low content of N and O in CDM6-K1000, we

rule out H bonding.

In (a), water is
being adsorbed
in (b), octane is
being adsorbed.

We can see that in (a) the amount of water adsorbed is higher in AC then CDM6-K1000, and it is the
opposite in (b).
With (c) it is confirmed that CDM6-K1000 is selectively adsorbing octane than water.
This shows that CDM6-K1000 is much more hydrophobic than AC, and therefore the adsorption maybe
explained by hydrophobic interaction.

Page | 53
CONCLUSION
In this study, the adsorbents were used to adsorb a variety of substances, with some having a higher
adsorptive capacity than most other reported adsorbents. High surface area, large pore volume, and
unsaturated metal sites are the ones which are most important in the adsorbent. They decide the
kinetics of the adsorption model though there are some exceptions which take place due to H bonding,
aromatic rings, etc.
Pseudo second-order kinetic model was the norm for every adsorbent, as the adsorption was taking
place due to some chemical reaction. There was one exception [1.6] In which fractal-like pseudo first
order was used, as the surface was heterogenous.
All the adsorbent models fit themselves with the Langmuir model, except [1.6] which follows the
Langmuir-Freundlich isotherm, due to the heterogenous surface. The Langmuir adsorption capacity of all
the adsorbents was determined and is shown in the table [1].
The mechanism of the adsorption model varied from acid-base interactions to H bonding and formation
of complexes.
Due to the high recoverable rate of the adsorbents, it was determined that they could be used for
commercial applications as they have a high removal efficiency, lower cost, simplicity of the process and
the ability to remove several substances at once [1.1] [1.5] [1.9].

Page | 54
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