Final Defense

by:
IBRAHIM TOBI
17BB004948/1701444
REMOVAL OF CONGO RED DYE FROM AQUEOUS SOLUTION
BY ZINC TEREPHTHALATE METAL ORGANIC FRAMEWORK
DECORATED ON SILVER NANOPARTICLES-LOADED BIOCHAR

Project Supervisor: ENGR. K.S. OBAYOMI

OUTLINE

• BACKGROUND

• AIM AND OBJECTIVES

• METHODOLOGY

• RESULTS

• CONCLUSION
BACKGROUND OF STUDY
• Wastewater effluent that is released without any form of treatment can
negatively affect the environment including the air, water, soil, and food.
The most essential resource for human survival is water, which must be
protected against contamination in order to maintain environmental
sustainability and public health in the face of enormous challenges.

• Dyes are employed extensively in several industries which includes

pharmaceutical, food, paper, plastic tannery, printing and textile.
Subsequently, they are discharged into the aquatic environment
containing harmful aromatic structures which makes them highly
carcinogenic and mutagenic capable of damaging human and aquatic life.
Therefore, organic dye pollution is one of the most urgent issues that has
to be addressed because it poses a long-term threat to human health and
environmental ecosystems.

• Hence, the need to completely remove dye from wastewater is necessary

BACKGROUND OF STUDY CONT..

PICTORIAL REPRESENTATION OF DYE EFFLUENT DISCHARGED INTO WATER BODIES

AIM AND OBJECTIVES
This study aims to develop biochar from poultry manure supported with AgNPs
and ZT-MOF to effectively remove congo red in aqueous solution. This aim will
be achieved through the following objectives;
•Prepare biochar from Poultry manure
•Synthesize AgNPs via the green route using Anacardium occidentale extract
•Synthesize ZT-MOF decorated on AgNPs-loaded biochar
(ZTMOF/AgNPs/AC)
•Evaluate the performance of the synthesized nanocomposite in Congo red
removal.
METHODOLOGY `
RAW MATERIALS INVOLVED EQUIPMENTS INVOLVED
Poultry Manure Muffle furnace
   
Potassium Hydroxide (KOH) Oven
   
zinc terephthalate acid (C8H6O4Zn) pH meter
   
Dimethylformamide (CH3)2NCH Weighing balance
   
zinc nitrate hexahydrate (Zn(NO3)2.6H2O) AAS (Atomic Adsorption
  Spectrophotometer)
Aqueous silver nitrate   
(AgNO3) Measuring Cylinder
 
  Water bath isothermal shaker
Anarcadium occidentale (Cashew leaves)  
  Crucible
Distilled water  
 
Filter Paper
RESULTS AND DISCUSSIONS;
FTIR (FOURIER TRANSFORM INFRARED
SPECTROSCOPY) ANALYSIS
Fourier transform Infra-Red (FTIR)
spectra was used to investigate the
functional groups of the materials. The
FTIR peaks were observed and
recorded over the range of 4000-500
cm−1. The FTIR spectrum of
AgNPs/PMBC showed adsorption peak
at 3440 cm−1 which is related to -OH
stretching vibration.

Fig 4.1
XRD (X-RAY DIFFRACTION)
The Xrd (X-Ray Diffraction) is a
non-destructive test method for
examining the structure of crystalline
materials. By examining the crystal
structure, XRD analysis identifies the
crystalline phases present in a
material and reveals information
about its chemical composition. The
X-ray diffraction patterns of PMBC,
AgNPs/PMBC, ZT-MOF and ZT-
MOF/AgNPs/PMBC are shown in
Fig. 4.3.

Fig 4.2
SEM/EDS (SCANNING ELECTRON MICROSCOPE BRUKER ENERGY DISPERSIVE X-RAY
ADSORPTION EQUILIBRIUM STUDIES
EFFECT OF PH EFFECT OF ADSORBENT DOSAGE
The adsorptive performance of
The effect of ZT-MOF/AgNPs/PMBC dosage as
ZT-MOF/AgNPs/PMBC on CR removal was assessed
regarding the removal of CR was conducted in a
at various pH values. The ZT-MOF/AgNPs/PMBC
group process at a varied dosage of 10-100 mg,
pH-dependent experiment was performed in the
for 60 min, at a pH of 5, CR initial concentration
range of pH 2–11, 60 min adsorption time, 10 mg
of 50 mg/L and at 308 K.
adsorbent dosage, 50 mg/L initial CR
concentration, and at 308 K.
ADSORPTION EQUILIBRIUM STUDIES CONT’D
EFFECT OF TEMPERATURE
The temperature as well has an effect of on the CR
removal by ZT-MOF/AgNPs/PMBC which was
examined at varied temperature from 298-348 K,
adsorption time of 60 min, at pH 5 as well as an
initial CR of 50 mg/L concentration. It can be
examined from the plot, that the removal
percentage of CR decreases as the temperature
increases from 318-348 K. This observation
suggested that the kinetic energy of molecules
might have increased enough as the temperature
increases thereby lowering the interaction chances
between adsorbent and adsorbate, thus leading to
reduced removal percentage of CR. The declined
removal percentage of CR observed as the
temperature increases, also suggested an
exothermic (heat-releasing) reaction following the
adsorption of CR onto ZT-MOF/AgNPs/PMBC
ADSORPTION EQUILIBRIUM STUDIES CONT’D
EFFECT OF CONTACT TIME AND INITIAL CONCENTRATION
The adsorption time as well as the CR initial
concentration effect on the removal of CR from
ZT-MOF/AgNPs/PMBC was investigated using a
time range of 0-120 min, CR initial concentration
of 10-50 mg/L, pH 5, 10 mg adsorbent dosage,
and at temperature of 308 K, as depicted in Fig.
4.6c-d. The increase observed in the adsorption
time, results to a continuous increase in the
adsorption capacity of CR. In 30 and 45 min,
equilibrium was reached at 10 and 20 mg/L
concentrations respectively, whereas at 30, 40,
and 50 mg/L concentrations, equilibrium was
attained in 60 min. This observation could be due
to the fact that there were more vacant sites on
the ZT-MOF/AgNPs/PMBC with fewer adsorbate
molecules to occupy, so the few CR molecules
that were available are quickly adsorbed
ADSORPTION ISOTHERM Isotherm model Linear Form Plot Parame References
The adsorption of CR from aqueous solution
ters
by ZT-MOF/AgNPs/PMBC in a batch test was
obtained and fitted using the following Langmuir vs Qmax,KL (Langmuir,
isotherm models; Langmuir, Freundlich, and
Dubinin-Radushkevich (D-R). Adsorption 1918)

isotherms describe the interaction between

adsorbate molecules and the surface of the
adsorbent, as well as the process, nature, and
practicability.

Freundlich vs KF, (Freundlich,

1906)

Dubinin- , ε, R, T, (Dubinin,

Radushkevich 1947)

(D-R)
 Temperature (K) (L/mg)  

EQUILIBRIUM Langmuir isotherm

ISOTHERM STUDIES  
308 416.67 0.0833 0.981  
PARAMETERS  
318 400.00 0.0480 0.975  
 
328 333.33 0.0300 0952  
 
         

Temperature (K)  

Freundlich isotherm
 
308 338.14 0.384 0.921  
 
318 316.52 0.348 0.893  
 
328 291.47 0.330 0.874  
 
         
 
Temperature (K) (kJ/mol)
 Comparison of CR adsorption capacity onto various adsorbents

Adsorbent Isotherm Kinetic model Adsorption capacity References

Model (mg/g)

KAC Langmuir Pseudo-second-order 14.156 (Mandal et al., 2021)

BFE Freundlich Pseudo-second-order 130 (Nguyen et al., 2021)

Ag2O-N2O3-ZrO2/rGO Langmuir Pseudo-second-order 333.32 (Sharma et al., 2021)

ZnCr2O4 Oxide -- Pseudo-second-order 44.038 (Gao et al., 2021)

Zn(Cur)O -- Pseudo-second-order 89.85 (Arab et al., 2021)

Fe3O4@bacteria Langmuir Pseudo-first-order 320.01 (Pi et al., 2022)

Fe3O4/AC Freundlich Intraparticle diffusion 122.22 (Priyan et al., 2022)

Hr-Cao-MgO Langmuir Pseudo-second-order 357.14 (Nagpal & Kakkar, 2022)

g-Al2O3 nano shells Langmuir Pseudo-second-order 370.4 (Al-Salihi et al., 2022)

AgNPs/HBAC Freundlich Pseudo-second-order 161.29 (K. Obayomi et al., 2022)

 ADSORPTION
THERMODYNAMICS ΔHo ΔSo (J/K   ΔGo (kJ/  
This is an important adsorption parameter that impacts the
(kJ/mol) mol) mol)
adsorption of CR onto ZT-MOF/AgNPs/PMBC by
influencing the adsorbate’s solubility, mobility and
equilibrium adsorption capacity is the adsorption
temperature. The adsorption thermodynamic studies were
investigated at different reaction temperature (308 K, 318 K,
328 K) The negative values of ΔH0 and ΔS0 as demonstrated     308 K 318 K 328 K
in the table signifies that adsorption is exothermic nature and
degrees of freedom decrease during the adsorption process.
The negative ΔG0 values shows the adsorption is feasible, -21.238 -21.901 -14.493 -14.274 14.055
and spontaneous
ADSORBENT REGENERABILITY
AND REUSABILITY STUDY
• The performance and practical application of any
adsorbent is determined by its reusability. The
more reusable the adsorbent is, the more widely
applicable it is on an industrial scale. The
reusability of ZT-MOF/AgNPs/PMBC was
investigated through six adsorption-desorption
cycles, and the results are depicted in Figure.

• This excellent percentage removal of CR towards

ZT-MOF/AgNPs/PMBC suggests that the
adsorbent is stable, easily regenarated with
excellent economic value and can be employed
effectively for CR treatment in aqueous solution.
 CONCLUSION

In conclusion, modification of poultry manure bio char with ZT-MOF/AgNPs increased

the sorption surface area. The influence of pH, Time, dosage on the adsorption of CR
were succesfully studied. The isothermal and kinetics studies revealed that langmuir
and Second order kinetic model described the adsoption process. The maximum
adsorption capacity was calculated to be 416.67mg/g. The thermodynamic studies
carried out reveals that the adsorption process is spontaneous, feasible and exothermic
and also from the reusability study the percentage removal of CR decreases after 6
cycles. From the results obtained, ZT-MOF/AgNPs/PMBC can be regarded as a
suitable adsorbent for CR dye in aqueous solution. The ZT-MOF@AgNPS@PMBC can
be economically and efficiently employed mitigate pollution challenges caused by CR
dye molecules
REFERENCES
Dubinin, M. (1947). The equation of the characteristic curve of activated
charcoal. 55, 327–329.

Freundlich, H. (1906). Over the adsorption in solution. J. Phys. Chem,

57(385471), 1100–1107.

Langmuir, I. (1918). The adsorption of gases on plane surfaces of glass,

mica and platinum. Journal of the American Chemical Society, 40(9), 1361–
1403.

Hu, H., & Xu, K. (2020). Chapter 8—Physicochemical technologies for

HRPs and risk control. In H. Ren & X. Zhang (Eds.), High-Risk Pollutants
in Wastewater (pp. 169–207). Elsevier. https://doi.org/10.1016/B978-0-12-
816448-8.00008-3