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Research Paper
Research Paper
a
Department of Chemistry, Government College for Women University Sialkot, Pakistan
b
Department of Chemistry, University of Jhang, Pakistan
*
Corresponding Author: Tayyaba Shahzadi, E-mail: tayyaba332@gmail.com;
A novel, recyclable and ecofriendly MOFs-biopolymer hydrogel doped with nano catalyst based
nano adsorbent was successfully synthesized. Nano catalyst of Mn/Ni oxide was prepared using
D. sissoo as a source of capping and reducing agent. Copper MOF was prepared via aqueous
synthesis and incorporated onto CMC hydrogel. Doping of nanoparticles was carried out onto the
matrix of MOF-biopolymer through physical stirring and heating methods. Morphology,
composition and structure of synthesized material verified by UV-Vis spectroscopy, SEM, FTIR,
XRD, and EDX techniques. The synthesized nanomaterial was porous and amorphous having
size 15.5nm with energy band gap 3.125. Prepared nano adsorbent showed 99% removal
efficiency for ciprofloxacin at pH=8 in 60min and at room temperature. To summarize the
mechanism, linear form of Langmuir, Freundlich, Dubinin-Radushkevich (DR), Temkin,
Redlich-Peterson (R-P), Halsey, and Harkins-Jura (HJ) isotherm models were applied. The
results from adsorption isotherm models revealed that the process was physisorption and
adsorbent was heterogenous and porous. Spontaneity and exothermic nature of the process was
confirmed by the values of thermodynamic parameters. Swelling ratio of the MOFs-biopolymer
hydrogel doped with nano catalyst was calculated and the effect of different factors optimized.
MOFs-biopolymer hydrogel doped with nano catalyst showed good results after five cycles.
KEYWORDS
O O
F
OH
HN
NOVELTY STATEMENT
Novel nano adsorbent was prepared for the removal of ciprofloxacin using MOF incorporated
onto hydrogel of biopolymer and doped with nano catalyst implying ecofriendly methodology.
The leaves extract of D.sissoo was used for the synthesis of nano catalyst of Mn and Ni oxide for
the first time and prepared a novel MOF of copper via aqueous synthesis. This research work has
not been previously reported in literature.
INTRODUCTION
In recent years, pharmaceuticals, human health and personal-care related products including
antibiotics have been recognized as emerging pollutants in the environment. Antibiotic
concentration in water bodies is rising steadily owing to increase in urbanization, population,
unsafe disposal and mistaken agricultural practices. Rise of antibiotic pollutants created the
abundance of resistant bacteria which have been detected in domestic sewage, hospital
wastewater and livestock which is danger to the human health (Khetan et al. 2007). Antibiotics
are being used for treatment of both humans as well as animals, but incomplete digestion of
antibiotics lead to excretion of active antibiotics into wastewater. Active compounds of
antibiotics in wastewater promote the growth of bacteria (Skoumal et al. 2009). The presence of
antibiotics in drinking water causes allergic reactions in some people (K. Kümmerer 2009). One
of the issues associated with antibiotics is bacterial resistance which is a hazard for the health of
humans as 90% of the antibiotics from human body dispose into wastewater and this changes the
structure of bacteria. Bacteria resistance intrinsically develops when microorganisms that are
susceptible to antibiotics become resistant due to mutation in the DNA or by obtaining antibiotic
resistance genes from other bacteria. Antibiotic resistant bacteria can replicate and transfer
antibiotic resistant genes to other bacteria to produce superbugs. The inconsiderate discarding of
antibiotics can create ferocious superbugs and makes it difficult to control infections caused by
superbugs (Anthony A et al. 2018).
Ciprofloxacin (CIP) has been extensively used for the treatment of infections caused by bacteria,
and it prevents the replication of bacteria. CIP is also the first choice among other
fluoroquinolones as chemotherapeutic antibiotic. CIP was detected in sewage, hospitals, and
industrial wastewater in unaltered chemical structures, posing a threat (Gothwal and Shashidhar
2016).
For the elimination of antibiotics from wastewater, physical, chemical, and biological methods
have been used. Toxic transition metals are used in advanced oxidation processes which form
intermediate compounds which are more toxic than pollutants to be removed. In biological
methods activated sludge is used to remove organic pollutants but this method is not applicable
for the removal of antibiotics and it’s not reliable. Physico-chemical methods are also not
reliable and applicable for the removal of pharmaceutical drugs from wastewater (Phoon BL et
al. 2020). Application of adsorbent for the removal of antibiotics from pharmaceutical
wastewater is an emerging technique due to its operational simplicity, low cost, and
effectiveness. Different types of adsorbents i.e., nanoparticles, nanocomposites, hydrogels, rGO
and MOFs have been used for the removal of antibiotics (Wang et al. 2019). To enhance the
properties of nanoparticles, nanocomposites are being synthesized using polymers, rGO and
MOFs as matrix that stabilized the nanoparticles and increased the surface area (Kefeni &
Mamba 2020). Manganese oxides (MnO, MnO2, Mn3O4) are captivating nanocomposites and
have been utilized in sensors, catalysis, and wastewater treatment. Metal organic frameworks
are not of just crystalline nature they could be of amorphous, liquid and glass nature which show
more enhanced properties over crystalline (Ricco et al. 2013). NCs with biopolymer and
nanoparticles increase the surface area as well as porosity of material and recyclability. MOFs
incorporated onto hydrogels of cellulose, starch, chitosan and alginate reported for the removal
of pollutants from wastewater (Chai et al. 2022).
D. sissoo is an evergreen plant and rich in phytochemicals which act as reducing and capping
agent (Sarg et al. 1999; Singh 2012). Sissooic acid, biochanin A, caviunin (Li, L. et al. 2009),
quercetin 3-rutinoside, caviunin-7-O-beta-D-glycopyranoside, kaempferol-3-O-rutinoside,
kaempferol-3-O-beta-D-glycopyranoside, genistein (Sato et al. 2006), Dalbergin, 2,5-
Dihyroxydalbergiquinol, 3'-methoxygenistein, Quercetin-3-O-beta-D-glucopyranoside,
stigmasterol, beta-Sitosterol, linolenic acid, palmiteolic acid, irisolidone and dalsissooside were
reported (Salwa F Farag et al. 2001). Aim of research was to prepare eco-friendly recyclable
MOF incorporated onto biopolymer hydrogel and doped with nano catalyst for the removal of
antibiotic by using plant leaf extract of D. sissoo.
All analytical grade chemical reagents used in this study for MOFs-biopolymer hydrogel doped
with nano catalyst preparation include glutaric acid (C 3H6(COOH)2, sodium hydroxide (NaOH),
copper (II) acetate monohydrate (Cu (CH3COO)2.H2O), potassium permanganate (KMnO4),
nickel chloride hexahydrate (NiCl2.6H2O), sodium salt of carboxymethylated cellulose, citric
acid monohydrate (HOC(COOH)(CH2COOH)2.H2O). Ciprofloxacin was used for adsorption
studies. Ferric (III) chloride hexahydrate (FeCl 3.6H2O) and ethanol (CH3OH) were used for the
spectrophotometric determination of ciprofloxacin. All chemicals were purchased from Sigma
Aldrich and utilized without any further purification.
Preparation of MOFs
0.1M solution of glutaric acid was prepared in 1M NaOH. 10mM aqueous solution of copper
acetate was added drop wise into the solution of glutaric acid in NaOH under continuous stirring
and heating at 35˚C. Then precipitates of prepared MOFs centrifuged and washed again and
again with distilled water. After complete washing poured into the petridish and dried in oven at
40˚C for 3hrs.
The leaves of Dalbergia sissoo were collected from local field areas of Sialkot, Pakistan. The
collected leaves washed thoroughly with distilled water. The washed plant leaves were dried
under shade for seven days. The dried plant leaves were crushed and ground by electronic
blender to obtain fine powder. Then 5g of dried powder was added into 500ml of distilled water
and heated for 15min at 70˚C. Prepared extract centrifuged twice and then filtered. Filtered plant
extract was stored at 4˚C for further use.
Nano catalyst of manganese nickel oxide was prepared using plant extract. 10mM solution of
NiCl2.6H2O and 10mM solution of KMnO4 was prepared and mixed in 1:1. Prepared solution
heated and stirred at 80˚C for 15min. After that extract was added and the mixture was heated
and stirred for 26min at 80˚C. Prepared nanoparticles were centrifuged and washed. Washed
nanoparticles were dried in oven at 50˚C for 2hours, dark brown colored nanoparticles were
obtained and stored for further use.
Characterization
Different characterization techniques were carried out to evaluate size, morphology, composition
and structure of synthesized MOFs-biopolymer hydrogel doped with nano catalyst. The
characterization techniques including UV-Vis spectroscopy, X-ray diffraction, energy dispersive
X-ray spectroscopy, fourier transform infrared spectroscopy and scanning electron microscopy
were carried out.
Adsorption Studies
MOFs-biopolymer hydrogel doped with nano catalyst was used for the adsorption and
degradation of ciprofloxacin. A stock solution of ciprofloxacin with a 25ppm concentration was
made by adding 0.025 g ciprofloxacin in 1000 mL distilled water. Further, solutions of different
concentrations were prepared by dissolving stock solution using a dilution formula. To check the
degradation activity of ciprofloxacin, 5 ppm ciprofloxacin’s stock solution was prepared by
dissolving 0.005 g ciprofloxacin in 1000 ml distilled water. For each experiment a constant
amount of catalyst was added in 25 mL ciprofloxacin solution and the mixture was stirred on an
orbital shaker at 150 rpm for 60 min. After adsorption, the mixture was centrifuged and filtered
to remove ciprofloxacin’s adsorbed. In this procedure, 0.5ml of 1% solution of ferric chloride
hexahydrate in ethanol was added into ciprofloxacin solution (1-5 mL) and diluted to 50 mL with
distilled water. The adsorption of colored products was checked after 30minutes against the
blank solution at 435 nm using a UV-Visible spectrometer. The blank solution was made in the
same way as but without the ciprofloxacin. The adsorption capacity (qe, mg/g) was estimated
using the following equation.
The swelling ratio (SRO) of MOFs-biopolymer hydrogel doped with nano catalyst was
calculated under distinct conditions of time, temperature, pH, and ionic strength. To estimate the
effect of time, temperature, pH, and ionic strength, weight of dried gel was measured and then
placed in water at different conditions and measured the weight of swelled gel to calculate the
swelling ratio. To check the effect of time, swelling ratio was measured after a 30min interval
from 30-150min. To estimate effect of temperature, pH, and ionic strength after 120min
calculated swelling ratio at 25-65˚C for temperature, at different pH from 2-12, at different molar
solutions of NaOH and MgCl2 from 0.1M to 1.5M for ionic strength.
MOFs-biopolymer hydrogel doped with nano catalyst loaded with ciprofloxacin was regenerated
by washing with dilute solution of HCl and then with distilled water. Recyclability of the
adsorbent was monitored after five cycles using 1mg of adsorbent at 35˚C, 60mint and 25ml of
5ppm CIP solution in distilled water.
To calculate point zero charge, 40ml of 0.1M NaCl was taken and adjusted pH from 2 to 12
using 0.1M NaOH and 0.1MHCl. After adjusting initial pH, fixed amount of catalyst was added
in all solutions under 150rpm shaking at room temperature for 24hours. After 24hours final pH
was measured and calculated pHpzc by plotting pHi vs ΔpH.
Cu MOF was prepared using glutaric acid as ligand via aqueous synthesis. Sodium hydroxide
was used as a base to make solution alkaline that dissociated the organic ligand to interact with
metal ions to produce amorphous Cu Mofs as shown in Fig. 2(c). MOF-hydrogel-NPs were
prepared by physical stirring and heating method which has been shown in Fig. 2(d) (Challa et
al. 2022). MOFs were incorporated onto the biopolymer hydrogel by via physical and chemical
interactions and nanoparticles were embedded into the spaces and pores present in MOFs
biopolymer hydrogel matrices.
Characterization
UV-Visible Spectroscopy
The absorption spectra of hydrogel, MOFs, nano catalyst and MOFs-biopolymer hydrogel doped
with nano catalyst have been shown in Fig. 2(a). which were recorded at 200-800 nm range. As
in the structure of biopolymer hydrogel no chromophoric group was present, so no absorption
peak was found in the spectra (Chen et al. 2019). In the absorption spectrum of Mn/Ni oxide
NPs, peaks at 273nm and 335nm were noticed for the reason of Surface Plasmon Resonance
which consensus with literature (Indulal et al. 2011). Peak at 335nm was broad due to the huge
size distribution. Peak at 260nm and hump at 321nm was observed in the absorption spectrum of
leaf extract of D.sissoo due to π→π* transition of aromatic –C=C bonds and n→π* transition of
carboxyl and carbonyl groups (–C=O). Plant extract was taken as reference to zero out these
background peaks (Nivedha et al. 2022; Dessie, Y. et al. 2021). MOFs showed a broad peak at
359nm and no sharp peak because metal organic frameworks were not strong enough to absorb
radiation. Peaks at 270nm and 359nm were noticed in the spectrum of MOFs-biopolymer
hydrogel doped with nanoparticles which showed the doping of nanocatalyst (Chang et al. 2019).
The Tauc and Davis-Mott relation used to probe energy band of the material which was Eg=
3.125 by the formula
(αhυ)n=K ¿ ) (3)
E g=hc / λ (4)
Eg = ((1240) eVnm) / λ
I/Io = e-αL
A= αL log(e)
α= 2.303 A/L
α= 2.303 A (cm-1)
The characteristic peaks at 3250, 2910, 1570, 1390, 1040, 908, 842, 665, 588 cm -1 appeared in
the FTIR spectrum of MOFs-biopolymer hydrogel doped with Mn/Ni oxide NPs as shown in
Fig. 3. Broad band at 3250 cm-1 (-OH stretching) was due to -OH group present in the structure
of CMC and MOFs indicated hydrogen bonding present in the structure of material. Peak
observed at 2910 cm-1 was due to -CH stretching, at 1570 cm-1 was due to C=O stretching (-
COONa), at 1390 cm-1 was due to -CH bending and -OH bending vibration. Peak at 1040 cm -1
was due to C-O stretching, 908cm-1 due to C=C bending. Peaks at 908 and 842 cm-1 were in the
range of 700-900 cm-1 which was associated with glucosidic bond (C-O-C) due to O-C stretching
vibrations. Peaks in the range 400-800 cm -1 were associated with metal oxide vibrations. The
peaks noted between 451 and 616 cm-1 were assigned to Cu-O in Cu-MOFs. Peak at 665 cm -1
was assigned to copper ions in Cu-MOF and metal oxides in bimetallic nanoparticle. Peak at
604cm-1 was assigned to Mn-O-Ni bond in bimetallic nanoparticles (Abdullah et al. 2018;
Zeerati et al. 2021; Akhavan-sigari et al. 2022; Dessie, Y. et al. 2021)
Scanning Electron Microscopic analysis was carried out to check the morphology of adsorbent
that was prepared using leaf extract of D. sissoo. SEM images at different magnifications have
been shown in Fig. 4. The SEM images showed random, porous morphology and non-uniform
distribution. SEM of synthesized material showed pores and pits present on the surface of the
amorphous material.
The EDX analysis was carried out to check the chemical composition of the sample which has
been shown in Fig. 5 and table 1. The EDX spectrum of adsorbent showed the peaks of the
elements that were present in the sample. The peaks in the spectrum of adsorbent are of copper,
oxygen, Mn, Ni, and carbon constituents.
The XRD analysis of adsorbent have been demonstrated in Fig. 6. The XRD spectrum had broad
prominent peak at 2θ = 11.2˚ and small broad peaks at 2θ =15.6˚, 17.1˚, 20.3˚, 24.4˚, 26.8˚,
29.7˚, 35.5˚, 38.7˚, 42.5˚, 47˚. There were broad peaks in the XRD spectrum which confirmed
the amorphous nature of synthesized material. Peaks at 2θ = 11.2˚, 15.6˚, 17.1˚, 20.3˚, 24.4˚,
26.8˚ were associated with copper MOFs. Peaks at 29.7˚, 38.7˚ and 42.5˚ were characteristic of
Mn/Ni oxide nanoparticles. Peaks at 35.5˚, 42.5˚, 47˚ were assigned to CMC hydrogel. There
was no sharp peak at 20˚ which confirmed the crosslinking of CMC polymer chains. Peaks
present at small angles indicated the presence of micropores and cavities on the structure of
material (Akram et al. 2016; Dessie, Y. et al. 2021; Yang et al. 2021)
Average particle sizes of the was 15.5nm, which was calculated by Debye–Scherrer equation.
The adsorbent amount is a key factor affecting antibiotic removal efficiency. It is essential for
the cost-effective application of adsorbents to use an optimal dosage for the effective degradation
of antibiotics from the environment. Removal efficiency of ciprofloxacin was studied in the
range of 1-5mg by keeping ciprofloxacin solutions concentration constant (5 mg/L, V = 25 mL).
The removal efficiency of ciprofloxacin using 1mg catalyst amount within 60 minutes reaction
time was 97% but the removal efficiency increased to 99% by increasing the dosage of catalyst
from 1-5mg due to increased surface area and availability of more binding sites for ciprofloxacin
adsorption. The results have been shown in Fig. 7(a) which showed 97 % removal efficiency at
1mg and 99 % at 5 mg. There was not a remarkable difference that’s why for further studies 1mg
catalyst was used.
Effect of pH
The pH of the solution affects the adsorption of ciprofloxacin onto the nano adsorbent as it
effects the ionization of drug and charge on the surface of the adsorbent. To optimize the effect
of pH on CIP removal, prepared solutions of different pH from 2 to 10, maintaining the 5ppm
concentration of CIP solution, 25 mL volume and 1mg nano adsorbent during the whole
experiment.
Removal of CIP increased as the pH increased up to 8 pH and after that started decreasing. The
calculated point zero charge of the nano adsorbent is 7.4 as shown in Fig. 7(c). Below pH=6 and
above pH=8.7 same charges repelled each other and removal efficiency decreased. In
zwitterionic form, CIP was hydrophobic and formed hydrogen bonds with hydroxyl groups
present on the surface the nano adsorbent. The removal efficiency of CIP was maximum at pH=8
as shown in Fig. 8 as at this pH CIP in zwitterionic form (Liu et al. 2020).
Effect of Temperature
Effect of temperature on CIP removal was studied by using 25mL (5ppm) of CIP solution and
1mg nano adsorbent at different temperature from 25 to 65˚C Fig. 7(d). With the increase of
temperature, the kinetic energy of adsorbate and adsorbent increased which led to decrease in the
interactions between adsorbate and adsorbent. Decrease in removal efficiency of antibiotic with
increase in temperature indicated exothermic process and physical adsorption (Muhammad et al.
2021).
The maximum removal efficiency of CIP was achieved under optimal conditions as shown in
table 2.
Adsorption Isotherms
ε = RT ln(1+1/Ce)
E = 1/(2B)1/2
Here B and A are the R-P parameters and can be measured from the intercept and Slope of plot
lnCe/qe Vs lnCe as shown in Fig. 9(e).
The Halsey isotherm is applied to estimate multilayer adsorption with large distance from the
surface of the heterogeneous adsorbent. The linear equation of the model is:
q e=1/nlnK H – 1/n lnC e (11)
Here KH and n are the Halsey parameters and can be measured from the intercept and Slope of
plot qe Vs lnCe as shown in Fig. 9(f).
The Harkin-Jura isotherm model presumes multilayer adsorption onto the absorbents which have
heterogeneous distribution of pores. The linear equation of the model is:
1/q e 2=B/ A – 1 / A log C e (12)
Here A and B are the Harkin Jura parameters and can be measured from the intercept and Slope
of plot 1/qe2 Vs log Ce as shown in Fig. 9(g).
From the above data it is noted that the best fitted model is Freundlich isotherm model. The order
of regression values R2 is
Freundlich (0.9958) > DR (0.93415) > Temkin = Halsey (0.9039) > H-J (0.8620) > R-P
(0.6108) > Langmuir (0.34868)
High regression value of Freundlich isotherm model indicated that adsorption was multilayer
onto heterogenous adsorbent. Mean free energy calculated using DR model was 0.29 which was
less than 8kJ/mol which indicated the physical adsorption. The value of R-P parameter B was
0.08 which was closer to 0, at this condition R-P isotherm equation resembled with equation of
Freundlich isotherm. Halsey, Freundlich and Harkin Jura model confirmed the multilayer
adsorption onto heterogenous adsorbent. DR isotherm model also indicated the microporous
structure of adsorbent. Harkin Jura isotherm model indicated the heterogenous distribution of
pores on adsorbent. The values of constants were shown in table 3.
Thermodynamics Studies
∆ G=−RTlnKd (13)
Kd = qe/Ce
Here, R is the general gas constant (J/mol.K), T is absolute temperature (K), K is the distribution
coefficient.
From the linear plot of lnKd vs 1/T, Enthalpy change (∆H), entropy change (∆S), Gibbs free
energy (ΔG) were calculated. The values of thermodynamic parameters have been shown in
Table 4. At different temperatures, negative values of Gibbs free energy change indicated the
spontaneity and feasibility of adsorption process. Moreover, negative values of ∆G decreased
with rise of temperature indicated process is less favorable at high temperature. Adsorption is
assumed to be physical if the enthalpy change is less than 84kJ/mol. The value of enthalpy
change was -17.035kJ/mol which indicated exothermic process and physisorption. Positive value
of entropy also indicated that the process was spontaneous.
The experiment for the degradation of ciprofloxacin using MOFs-biopolymer hydrogel doped
with nano catalyst was conducted under diffused light. Diffused light excited the electrons of
nano adsorbent from valence band to conduction band and created electrons in CB and holes in
VB. These electrons were captured at the porous surface and react with oxygen to produce
superoxide radical (•O2-). Holes reacted with water and produced hydroxyl radicals which
degraded the ciprofloxacin into various possible products. The porous heterogeneous structure of
MOFs-biopolymer hydrogel doped with nano catalyst decreased the rate of combination of
electron hole pair to accelerate degradation (Yu et al. 2019).
Swelling Ratio
Swelling ratio is an important parameter which affects the adsorption capacity. As increasing the
swelling ratio, porosity of hydrogel increases (Tang C et al. 2007). Swelling ratio of the MOFs-
hydrogel-NPs was calculated using the following equation:
It was observed that time showed a positive effect on swelling ratio as shown in Fig. 11(a).
Increasing the time of contact of absorbent with water increased the swelling ratio and water
holding capacity.
It is noticed that temperature directly affects the swelling behavior of hydrogel as shown in Fig.
11(b). Swelling ratio increased by increasing temperature due to detangling the chains of
biopolymer by breaking hydrogen bonds. The network of the biopolymer expands on increasing
the temperature leading to an increase in water uptake capacity (Zhao Y et al. 2005).
As shown in Fig. 11(d), swelling ratio of MOF-hydrogel-NPs decreased with an increase in ionic
strength of solution. The decrease in swelling was more for MgCl 2 as compared to NaCl. Charge
screening effect increased by increasing the ionic strength which decreased the swelling ratio by
decreasing the osmotic pressure in the network of polymer. Multivalent cations involved in ionic
crosslinking leading to decrease in swelling of biopolymer. (Lu et al. 2016).
Conclusion
A novel, recyclable and ecofriendly MOFs-biopolymer hydrogel doped with nano was
successfully synthesized via aqueous synthesis. Composition of synthesized material was
verified by UV-Vis spectroscopy, SEM, FTIR, XRD, and EDX techniques. The size of the nano
adsorbent was found to be 15.5nm with energy band gap 3.125. The impact of temperature, pH,
dosage and initial concentration were optimized. Synthesized nano adsorbent showed 99%
removal of ciprofloxacin under mild conditions. The adsorption isotherm models showed the
regression values of all those models which were related to multi-layer adsorption, physical
adsorption, heterogenous and porous adsorbent were high. The best fitted adsorption model was
Freundlich isotherm model. The values of Gibbs free energy, enthalpy and entropy were
calculated using Van’t Hoff equation which revealed that the process was exothermic and
spontaneous. Effect of pH, ionic strength, temperature, and time on swelling ratio of the MOFs-
biopolymer hydrogel doped with nano catalyst was evaluated. Novel MOFs-biopolymer
hydrogel doped with nano catalyst proved excellent adsorbent and can be used to remove other
pollutants from the wastewater.
References
Element Weight %
C 36.76
O 25.01
Mn 22.68
Ni 9.12
Cu 6.43
Total 100
Table 2. Maximum removal efficiency of AMX under optimal conditions
(mg) (ppm)
MOFs- 1 mg 5 ppm 8 60 35 °C 99 %
biopolymer
hydrogel doped
with nano
catalyst
Table 3. Isotherm parameters
KL 0.2254
Kf (L mg-1) 859.80
n 1.087
B 5.8214
E 0.2930
AT (L g-1) 11.49
B 268.91
A 859.19
KH 0.0869
A 10460.27
B -2772.38
Table 4. Thermodynamics parameters
∆G ∆H ∆S
Fig. 1.
(a) (b) O
O OH O OH
O O OH O O
O OH CMC OH
-H2O
HO OH O HO O
OH OH
O
Citric acid CMC
-H2O
O OH
O O
CMC OH O
O O
O O
OH
O O
OH
CMC CMC
CMC
CMC Hydrogel
(c) (d)
O O
HO OH
H O
glutaric acid H H
+ O H
HO OH
Cu+2 O O
O Cu O
O O
Fig. 2.
absorbance
1
Eg= 3.125
0
1 2 3 4 5
Energy (eV)
0
300 400 500 600 700 800 200 300 400 500 600 700 800
Wavelength (nm) wavelength (nm)
Fig. 3.
Fig. 4.
(a) (b)
(c) (d)
Fig. 5.
Fig. 6.
Fig. 7 .
(a) 100
(b) 98
96
% Removal efficiency
% Removal efficiency
94
99
92
90
98 88
86
1 2 3 4 5
10 20
Adsorbent dose (mg)
concentration (mg/L)
(c) 100
98
(d) 98
%Removal efficiency
96
94 % Removal efficiency
92
90
97
88
86
84
82
80 96
2 4 6 8 10
40 60 80
pH
Temperature (C)
˚
Fig. 8.
4
O O
F
O
3 N
H2N
2 O O
Zwitterionic O O
F
OH F
O
N
N
1 H2N
HN
Cationic Anionic
ΔpH
0
2 3 4 5 6 7 8 9 10 11 12 13
pHi
-1
pHpzc = 7.4
-2 pKa2= 8.7
pKa1=6.1
Fig. 9.
0.00110 2.7
6.4 (d) 600
0.00108 6.2
2.6
6.0 500
0.00106
2.5
5.8
0.00104
400
2.4
logqe
5.6
Ce/qe
0.00102
lnqe
qe
2.3 5.4
0.00100 300
5.2
0.00098 2.2
5.0 200
0.00096 2.1
4.8
0.00094 100
2.0
-1.0 -0.9 -0.8 -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 4.6
0.1 0.2 0.3 0.4 0.5 0.6 0.7 5000000 10000000 15000000 20000000 25000000 30000000 35000000
-2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2
logCe
Ce e² lnCe
-6.78
-0.2
-6.82
500 -0.3
-6.84
-6.86 -0.4
400
-6.88 -0.5
lnCe/qe
qe
logCe
-6.90 300 -0.6
-6.92 -0.7
200
-6.94 -0.8
-6.96 -0.9
100
-6.98
-1.0
-2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 -2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.00000 0.00001 0.00002 0.00003 0.00004 0.00005 0.00006 0.00007
lnCe lnCe 1/qe²
Fig. 10.
Fig. 11.
900 950
(a) (b)
900
850
800
800
Swelling ratio%
Swelling ratio %
750
700
650
700
600
550
750
550
swelling ratio %
swelling ratio %
700
650 500
600
450
550
500 400
450
2 4 6 8 10 12 350
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
pH
concentration (M)
Fig. 12.
Figure Captions
Figure 1. (a) Scheme for the preparation of Cu MOF (b) for the preparation of leaf extract (c) for
the preparation of nano catalyst (d) for the preparation of MOFs-biopolymer hydrogel
doped with nano catalyst
Figure 2. (a) UV- Visible spectra of samples (b) Band gap of Adsorbent
Figure 3. FTIR spectrum of green synthesized MOFs-biopolymer hydrogel doped with nano
catalyst
Figure 4. SEM images of MOFs-biopolymer hydrogel doped with nano catalyst (a) at 500nm (b)
at 2µm (c) 5µm (d) 20µm
Figure 5. EDX spectrum of MOFs-biopolymer hydrogel doped with nano catalyst
Figure 6. X-ray diffractogram of synthesized MOFs-biopolymer hydrogel doped with
nanocatalyst
Figure 7. (a) Effect of adsorbent amount on ciprofloxacin removal efficiency (b) Influence of
initial ciprofloxacin concentration on its removal efficiency (c) Effect of pH on the CIP
removal efficiency (d) Effect of temperature on CIP removal effiency
Figure 8. pHpzc of nano Adsorbent
Figure 9. (a) Langmuir adsorption isotherm (b) Freundlich adsorption isotherm (c) DR
adsorption isotherm (d) Temkin adsorption isotherm (e) R-P adsorption isotherm (f) Halsey
adsorption isotherm (g) HJ adsorption isotherm
Figure 10. Van’t Hoff plot for adsorbent
Figure 11. (a) Effect of time on swelling ratio% (b) Effect of temperature on swelling ratio% (c)
Effect of pH on swelling ratio% (d) Effect of ionic strength on swelling ratio%
Figure 12. Regeneration of adsorbent