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Utilizing graphene and its numerous composites to
remove dyes from textile effluent by using adsorption
techniques.
Bapi Mondal
Id No:20151207052
Session: 2019-20
M.Sc. (Engineering) 3rd
Semester
Supervisor
Md. MEHEDI HASAN BABU
Dept. of Applied Chemistry and Chemical Engineering
Bangabandhu Sheikh Mujibur Rahman Science & Technology University
CONTENTS
2
DYE Introduction
01
Techniques of Dye separation
02
Adsorption Dye removal
03
Synthesis of Graphene and its
derivatives
04
DYE Removal Mechanism
05
Factors Affecting Adsorption
06
Kinetic and Isotherm analysis
07
Graphene based composites
adsorption capacities
08
Conclusion
09
Future Perspectives and Challenges
10
3
DYE
β–Έ A dye is a substance that is used to
impart colors to materials like
fabrics, paper, leather, and other
things so that the colors won't be
easily changed by washing, heat,
light, or other elements to which
the material is likely to be
exposed.
Transition Headline
DYE Classification
DYE
Acid dye
Basic dyes
Direct dyes
Mordant dye
Sulfur dye
Vat dyes
Reactive dye
Based on
 Source of Production
 Application Methods
 Bond with fiber
 Chemical Structure
 Solubility
5
Routes and fates of dyes in the environment
Fig: Routes and fates of dyes in the environment (JanuΓ‘rio et al., 2021)
6
Techniques of Dye separation
DYE Separation Methods
Physical
Adsorption Ion Exchange
Membrane
Filtration
Coagulation and
flocculation
Irradiation
Chemical
Oxidative
Process
Ozonation
Photochemical Photo catalyst
Biological
Aerobic
degradation
anaerobic
remediation
Living/dead
microbial biomass
adsorption
Fig: Various Dye separation methods (Cserhati et al., 2004)
7
Graphene and its derivatives for Dye removal
Figure: Graphene Oxide Structure Figure: Reduced Graphene Oxide Structure
8
Graphene and its derivatives for Dye removal
9
Synthesis
Graphite
Oxidation
Graphene Oxide
Sonication/
Stirring GO Dispersion
Reducing
agent
Reduced Graphene Oxide
Reduction via
PPT, Stirring,
sonication
Fig: Synthesis of GO and rGO (Zhu et al., 2010)
10
Mechanism of DYE Adsorption
 Electrostatic Interaction
 Hydrogen Bonding
 Ion Exchange
 Surface Complexation
 Van der Waals force
 Ο€- Ο€ Interaction
Fig: Dye removal mechanism (Yagub et al., 2014)
11
Mechanism of DYE Adsorption
Fig: MB Adsorption on GO (Bradder et al., 2011) Fig: MB Adsorption on rGO (Bradder et al., 2011)
12
Factors Affecting Adsorption
 pH
 Temperature
 Contact Time
 Initial Dye Concentration
Fig: pH Effect on Adsorption process
(Li et al., 2013)
Fig: Contact time Effect on Adsorption process
(Sarkar et al., 2014)
13
Factors Affecting Adsorption
 pH
 Temperature
 Contact Time
 Initial Dye Concentration
Fig: Temperature Effect on Adsorption
process (Lee et al., 2008)
Fig: Initial Dye Concentration Effect on Adsorption
process (Han et al., 2021)
14
Kinetics of Adsorption
οƒ˜ Adsorption kinetics model is used to investigate the mechanism of adsorption.
οƒ˜ Pseudo First and Second order equation is used mainly to analyze adsorption kinetics.
Pseudo-first-order model Pseudo-Second-order model
log( π‘žπ‘’ βˆ’ π‘žπ‘‘) = log π‘žπ‘’ βˆ’
π‘˜1
2.303
𝑑
𝑑
π‘žπ‘‘
=
1
π‘˜2π‘žπ‘’
2 +
1
π‘žπ‘’
𝑑
Where,
π‘žπ‘‘ and π‘žπ‘’= π΄π‘‘π‘ π‘œπ‘Ÿπ‘π‘‘π‘–π‘œπ‘› πΆπ‘Žπ‘π‘Žπ‘π‘–π‘‘π‘¦
π‘˜1 = π‘…π‘Žπ‘‘π‘’ πΆπ‘œπ‘›π‘ π‘‘π‘Žπ‘›π‘‘
𝑑 = π‘‡π‘–π‘šπ‘’
Where,
π‘žπ‘‘ and π‘žπ‘’= π΄π‘‘π‘ π‘œπ‘Ÿπ‘π‘‘π‘–π‘œπ‘› πΆπ‘Žπ‘π‘Žπ‘π‘–π‘‘π‘¦
π‘˜2 = π‘…π‘Žπ‘‘π‘’ πΆπ‘œπ‘›π‘ π‘‘π‘Žπ‘›π‘‘
𝑑 = π‘‡π‘–π‘šπ‘’
 A straight line of π’π’π’ˆ( 𝒒𝒆 βˆ’ 𝒒𝒕) versus 𝒕 suggests
that process followed first order kinetics.
 If the second order kinetic model is applicable, a
straight line should appear on the plot of
𝒕
𝒒𝒕
vs 𝒕.
15
Adsorption Isotherm
Langmuir Isotherm
1 Freundlich Isotherm
2
 The Langmuir adsorption model is predicated on the notion
that maximum adsorption corresponds to an uninterrupted
saturated monolayer of solute molecules on the adsorbent
surface.
 The Freundlich model can be applied to multilayer
adsorption with non-uniform distribution of adsorption heat
and affinities over the heterogeneous surface.
𝒒𝒆 =
π’’π’Žπ‘²π’‚π‘ͺ𝒆
𝟏 + 𝑲𝒂π‘ͺ𝒆
π₯𝐧 𝒒𝒆 = π₯𝐧 𝑲𝒇 +
𝟏
𝒏
π₯𝐧 π‘ͺ𝒆
πΎπ‘Ž = Langmuir constant
π‘Šβ„Žπ‘’π‘Ÿπ‘’,
𝑲𝒇 = Freundlich constant
𝟏
𝒏
= Adsorption Intensity.
π‘Šβ„Žπ‘’π‘Ÿπ‘’,
οƒΌ R2 > 0.99 indicates that the data is fit with the Langmuir
model.
οƒΌ π‘ͺ𝒆 vs π‘ͺ𝒆/𝒒𝒆 should yield a straight line. οƒΌ Log π‘ͺ𝒆 vs Log 𝒒𝒆 should yield a straight line.
16
Temkin Isotherm
3 D-R Isotherm
4 Henry Isotherm
5
Adsorption Isotherm
 Indirect adsorbate/adsorbate
interactions might affect
adsorption isotherms.
 Adsorption involves multiple
layers
 Adsorption is characterized by a
uniform distribution of binding
energies.
 Used to represent the adsorption
mechanism on heterogeneous
surfaces.
 This isotherm is only applicable
for middle ranges of adsorbate
concentrations.
 This isotherm model explains a
suitable fit to adsorbate adsorption
at low concentrations.
 Describes the relationship between
the equilibrium adsorbate
concentrations in the liquid and
adsorbed phases.
17
Graphene based composites adsorption capacities
243.9
183.15
49.29
357.14
423.15
276.5
MB on GO
MB on Carboxy methyl cellulose
Anionic DR 23 on GO-polyethyleneimine
MB on GO-Sodium alginate composite
MO onGO@AC
MB on GO@AC
Adsorption Capacity (mg/g)
Dye
adsorb
on
Adsorbents
18
Graphene based composites adsorption capacities
Name of dye Type of Composite Removal capacity (% or mg/g)
MG GO and rGO High adsorption capacity
MB GO-MNP 99.6% Removal effectiveness
MB rGO 160 Photocatalytic activity 98.57 %
MG GO and RGO -
MB Magnetic Graphene Oxide
significant removal efficiency around
99.6 % for MB.
MB graphene oxide 243.90 mg/g adsorption capacity
FA
graphene oxide/chitosan
composite fibers
91.3 % removal efficiency
MB and MV Three-Dimensional Graphene Oxide Nanostructure
99.1% removal efficiency for MB and
98.8% of MV.
Anionic DR 23 GO-polyethyleneimine 49.29 mg/g
Indigo Carmin dye GO and Chitosan composite 90% removal efficiency
CR Graphene oxide and Fe3O4 98% removal efficiency
RhB
Nanocomposite of nickel made of graphene
oxide(Ni-GO)
90% removal efficiency
19
Conclusion & Future Perspectives
Fig: Distinct adsorbents used in adsorption procedures (Dutta et al., 2021)
20
References
1. Bradder, P., Ling, S. K., Wang, S., & Liu, S. (2011). Dye Adsorption on Layered Graphite Oxide. Journal of Chemical & Engineering Data, 56(1),
138–141. https://doi.org/10.1021/je101049g
2. Cserhati, E., Frogacs, E., & Oros, G. (2004). Removal of synthetic dyes from wastewater: a review. J. Environ. Int., 953–971.
3. Han, M., Xu, B., Zhang, M., Yao, J., Li, Q., Chen, W., & Zhou, W. (2021). Preparation of biologically reduced graphene oxide-based aerogel and
its application in dye adsorption. Science of The Total Environment, 783, 147028. https://doi.org/https://doi.org/10.1016/j.scitotenv.2021.147028
4. JanuΓ‘rio, E. F. D., Vidovix, T. B., de Camargo Lima Beluci, N., PaixΓ£o, R. M., da Silva, L. H. B. R., Homem, N. C., Bergamasco, R., & Vieira, A.
M. S. (2021). Advanced graphene oxide-based membranes as a potential alternative for dyes removal: A review. Science of The Total Environment,
789, 147957. https://doi.org/https://doi.org/10.1016/j.scitotenv.2021.147957
5. Lee, C.-K., Lin, K.-S., Wu, C.-F., Lyu, M.-D., & Lo, C.-C. (2008). Effects of synthesis temperature on the microstructures and basic dyes
adsorption of titanate nanotubes. Journal of Hazardous Materials, 150(3), 494–503. https://doi.org/https://doi.org/10.1016/j.jhazmat.2007.04.129
6. Li, Y., Du, Q., Liu, T., Peng, X., Wang, J., Sun, J., Wang, Y., Wu, S., Wang, Z., Xia, Y., & Xia, L. (2013). Comparative study of methylene blue
dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes. Chemical Engineering Research and Design, 91(2), 361–368.
https://doi.org/https://doi.org/10.1016/j.cherd.2012.07.007
7. Sarkar, C., Bora, C., & Dolui, S. K. (2014). Selective Dye Adsorption by pH Modulation on Amine-Functionalized Reduced Graphene Oxide–
Carbon Nanotube Hybrid. Industrial & Engineering Chemistry Research, 53(42), 16148–16155. https://doi.org/10.1021/ie502653t
8. Yagub, M. T., Sen, T. K., Afroze, S., & Ang, H. M. (2014). Dye and its removal from aqueous solution by adsorption: A review. Advances in
Colloid and Interface Science, 209, 172–184. https://doi.org/https://doi.org/10.1016/j.cis.2014.04.002
9. Zhu, Y., Murali, S., Cai, W., Li, X., Suk, J. W., Potts, J. R., & Ruoff, R. S. (2010). Graphene and graphene oxide: Synthesis, properties, and
applications. Advanced Materials, 22(35), 3906–3924. https://doi.org/10.1002/adma.201001068
10. Dutta, S., Gupta, B., Srivastava, S. K., & Gupta, A. K. (2021). Recent advances on the removal of dyes from wastewater using various adsorbents:
A critical review. Materials Advances, 2(14), 4497–4531. https://doi.org/10.1039/d1ma00354b
β€œ ANY
QUESTIONS
???
21

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Graphene and its derivatives for Dye removal_Bapi mondal.pdf

  • 1. Utilizing graphene and its numerous composites to remove dyes from textile effluent by using adsorption techniques. Bapi Mondal Id No:20151207052 Session: 2019-20 M.Sc. (Engineering) 3rd Semester Supervisor Md. MEHEDI HASAN BABU Dept. of Applied Chemistry and Chemical Engineering Bangabandhu Sheikh Mujibur Rahman Science & Technology University
  • 2. CONTENTS 2 DYE Introduction 01 Techniques of Dye separation 02 Adsorption Dye removal 03 Synthesis of Graphene and its derivatives 04 DYE Removal Mechanism 05 Factors Affecting Adsorption 06 Kinetic and Isotherm analysis 07 Graphene based composites adsorption capacities 08 Conclusion 09 Future Perspectives and Challenges 10
  • 3. 3 DYE β–Έ A dye is a substance that is used to impart colors to materials like fabrics, paper, leather, and other things so that the colors won't be easily changed by washing, heat, light, or other elements to which the material is likely to be exposed.
  • 4. Transition Headline DYE Classification DYE Acid dye Basic dyes Direct dyes Mordant dye Sulfur dye Vat dyes Reactive dye Based on  Source of Production  Application Methods  Bond with fiber  Chemical Structure  Solubility
  • 5. 5 Routes and fates of dyes in the environment Fig: Routes and fates of dyes in the environment (JanuΓ‘rio et al., 2021)
  • 6. 6 Techniques of Dye separation DYE Separation Methods Physical Adsorption Ion Exchange Membrane Filtration Coagulation and flocculation Irradiation Chemical Oxidative Process Ozonation Photochemical Photo catalyst Biological Aerobic degradation anaerobic remediation Living/dead microbial biomass adsorption Fig: Various Dye separation methods (Cserhati et al., 2004)
  • 7. 7 Graphene and its derivatives for Dye removal Figure: Graphene Oxide Structure Figure: Reduced Graphene Oxide Structure
  • 8. 8 Graphene and its derivatives for Dye removal
  • 9. 9 Synthesis Graphite Oxidation Graphene Oxide Sonication/ Stirring GO Dispersion Reducing agent Reduced Graphene Oxide Reduction via PPT, Stirring, sonication Fig: Synthesis of GO and rGO (Zhu et al., 2010)
  • 10. 10 Mechanism of DYE Adsorption  Electrostatic Interaction  Hydrogen Bonding  Ion Exchange  Surface Complexation  Van der Waals force  Ο€- Ο€ Interaction Fig: Dye removal mechanism (Yagub et al., 2014)
  • 11. 11 Mechanism of DYE Adsorption Fig: MB Adsorption on GO (Bradder et al., 2011) Fig: MB Adsorption on rGO (Bradder et al., 2011)
  • 12. 12 Factors Affecting Adsorption  pH  Temperature  Contact Time  Initial Dye Concentration Fig: pH Effect on Adsorption process (Li et al., 2013) Fig: Contact time Effect on Adsorption process (Sarkar et al., 2014)
  • 13. 13 Factors Affecting Adsorption  pH  Temperature  Contact Time  Initial Dye Concentration Fig: Temperature Effect on Adsorption process (Lee et al., 2008) Fig: Initial Dye Concentration Effect on Adsorption process (Han et al., 2021)
  • 14. 14 Kinetics of Adsorption οƒ˜ Adsorption kinetics model is used to investigate the mechanism of adsorption. οƒ˜ Pseudo First and Second order equation is used mainly to analyze adsorption kinetics. Pseudo-first-order model Pseudo-Second-order model log( π‘žπ‘’ βˆ’ π‘žπ‘‘) = log π‘žπ‘’ βˆ’ π‘˜1 2.303 𝑑 𝑑 π‘žπ‘‘ = 1 π‘˜2π‘žπ‘’ 2 + 1 π‘žπ‘’ 𝑑 Where, π‘žπ‘‘ and π‘žπ‘’= π΄π‘‘π‘ π‘œπ‘Ÿπ‘π‘‘π‘–π‘œπ‘› πΆπ‘Žπ‘π‘Žπ‘π‘–π‘‘π‘¦ π‘˜1 = π‘…π‘Žπ‘‘π‘’ πΆπ‘œπ‘›π‘ π‘‘π‘Žπ‘›π‘‘ 𝑑 = π‘‡π‘–π‘šπ‘’ Where, π‘žπ‘‘ and π‘žπ‘’= π΄π‘‘π‘ π‘œπ‘Ÿπ‘π‘‘π‘–π‘œπ‘› πΆπ‘Žπ‘π‘Žπ‘π‘–π‘‘π‘¦ π‘˜2 = π‘…π‘Žπ‘‘π‘’ πΆπ‘œπ‘›π‘ π‘‘π‘Žπ‘›π‘‘ 𝑑 = π‘‡π‘–π‘šπ‘’  A straight line of π’π’π’ˆ( 𝒒𝒆 βˆ’ 𝒒𝒕) versus 𝒕 suggests that process followed first order kinetics.  If the second order kinetic model is applicable, a straight line should appear on the plot of 𝒕 𝒒𝒕 vs 𝒕.
  • 15. 15 Adsorption Isotherm Langmuir Isotherm 1 Freundlich Isotherm 2  The Langmuir adsorption model is predicated on the notion that maximum adsorption corresponds to an uninterrupted saturated monolayer of solute molecules on the adsorbent surface.  The Freundlich model can be applied to multilayer adsorption with non-uniform distribution of adsorption heat and affinities over the heterogeneous surface. 𝒒𝒆 = π’’π’Žπ‘²π’‚π‘ͺ𝒆 𝟏 + 𝑲𝒂π‘ͺ𝒆 π₯𝐧 𝒒𝒆 = π₯𝐧 𝑲𝒇 + 𝟏 𝒏 π₯𝐧 π‘ͺ𝒆 πΎπ‘Ž = Langmuir constant π‘Šβ„Žπ‘’π‘Ÿπ‘’, 𝑲𝒇 = Freundlich constant 𝟏 𝒏 = Adsorption Intensity. π‘Šβ„Žπ‘’π‘Ÿπ‘’, οƒΌ R2 > 0.99 indicates that the data is fit with the Langmuir model. οƒΌ π‘ͺ𝒆 vs π‘ͺ𝒆/𝒒𝒆 should yield a straight line. οƒΌ Log π‘ͺ𝒆 vs Log 𝒒𝒆 should yield a straight line.
  • 16. 16 Temkin Isotherm 3 D-R Isotherm 4 Henry Isotherm 5 Adsorption Isotherm  Indirect adsorbate/adsorbate interactions might affect adsorption isotherms.  Adsorption involves multiple layers  Adsorption is characterized by a uniform distribution of binding energies.  Used to represent the adsorption mechanism on heterogeneous surfaces.  This isotherm is only applicable for middle ranges of adsorbate concentrations.  This isotherm model explains a suitable fit to adsorbate adsorption at low concentrations.  Describes the relationship between the equilibrium adsorbate concentrations in the liquid and adsorbed phases.
  • 17. 17 Graphene based composites adsorption capacities 243.9 183.15 49.29 357.14 423.15 276.5 MB on GO MB on Carboxy methyl cellulose Anionic DR 23 on GO-polyethyleneimine MB on GO-Sodium alginate composite MO onGO@AC MB on GO@AC Adsorption Capacity (mg/g) Dye adsorb on Adsorbents
  • 18. 18 Graphene based composites adsorption capacities Name of dye Type of Composite Removal capacity (% or mg/g) MG GO and rGO High adsorption capacity MB GO-MNP 99.6% Removal effectiveness MB rGO 160 Photocatalytic activity 98.57 % MG GO and RGO - MB Magnetic Graphene Oxide significant removal efficiency around 99.6 % for MB. MB graphene oxide 243.90 mg/g adsorption capacity FA graphene oxide/chitosan composite fibers 91.3 % removal efficiency MB and MV Three-Dimensional Graphene Oxide Nanostructure 99.1% removal efficiency for MB and 98.8% of MV. Anionic DR 23 GO-polyethyleneimine 49.29 mg/g Indigo Carmin dye GO and Chitosan composite 90% removal efficiency CR Graphene oxide and Fe3O4 98% removal efficiency RhB Nanocomposite of nickel made of graphene oxide(Ni-GO) 90% removal efficiency
  • 19. 19 Conclusion & Future Perspectives Fig: Distinct adsorbents used in adsorption procedures (Dutta et al., 2021)
  • 20. 20 References 1. Bradder, P., Ling, S. K., Wang, S., & Liu, S. (2011). Dye Adsorption on Layered Graphite Oxide. Journal of Chemical & Engineering Data, 56(1), 138–141. https://doi.org/10.1021/je101049g 2. Cserhati, E., Frogacs, E., & Oros, G. (2004). Removal of synthetic dyes from wastewater: a review. J. Environ. Int., 953–971. 3. Han, M., Xu, B., Zhang, M., Yao, J., Li, Q., Chen, W., & Zhou, W. (2021). Preparation of biologically reduced graphene oxide-based aerogel and its application in dye adsorption. Science of The Total Environment, 783, 147028. https://doi.org/https://doi.org/10.1016/j.scitotenv.2021.147028 4. JanuΓ‘rio, E. F. D., Vidovix, T. B., de Camargo Lima Beluci, N., PaixΓ£o, R. M., da Silva, L. H. B. R., Homem, N. C., Bergamasco, R., & Vieira, A. M. S. (2021). Advanced graphene oxide-based membranes as a potential alternative for dyes removal: A review. Science of The Total Environment, 789, 147957. https://doi.org/https://doi.org/10.1016/j.scitotenv.2021.147957 5. Lee, C.-K., Lin, K.-S., Wu, C.-F., Lyu, M.-D., & Lo, C.-C. (2008). Effects of synthesis temperature on the microstructures and basic dyes adsorption of titanate nanotubes. Journal of Hazardous Materials, 150(3), 494–503. https://doi.org/https://doi.org/10.1016/j.jhazmat.2007.04.129 6. Li, Y., Du, Q., Liu, T., Peng, X., Wang, J., Sun, J., Wang, Y., Wu, S., Wang, Z., Xia, Y., & Xia, L. (2013). Comparative study of methylene blue dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes. Chemical Engineering Research and Design, 91(2), 361–368. https://doi.org/https://doi.org/10.1016/j.cherd.2012.07.007 7. Sarkar, C., Bora, C., & Dolui, S. K. (2014). Selective Dye Adsorption by pH Modulation on Amine-Functionalized Reduced Graphene Oxide– Carbon Nanotube Hybrid. Industrial & Engineering Chemistry Research, 53(42), 16148–16155. https://doi.org/10.1021/ie502653t 8. Yagub, M. T., Sen, T. K., Afroze, S., & Ang, H. M. (2014). Dye and its removal from aqueous solution by adsorption: A review. Advances in Colloid and Interface Science, 209, 172–184. https://doi.org/https://doi.org/10.1016/j.cis.2014.04.002 9. Zhu, Y., Murali, S., Cai, W., Li, X., Suk, J. W., Potts, J. R., & Ruoff, R. S. (2010). Graphene and graphene oxide: Synthesis, properties, and applications. Advanced Materials, 22(35), 3906–3924. https://doi.org/10.1002/adma.201001068 10. Dutta, S., Gupta, B., Srivastava, S. K., & Gupta, A. K. (2021). Recent advances on the removal of dyes from wastewater using various adsorbents: A critical review. Materials Advances, 2(14), 4497–4531. https://doi.org/10.1039/d1ma00354b