Graphene Quantum Dots Decorated Metal and

Nonmetal Doped Nanomaterials for

Photocatalysis of Azo Dyes

Dr Muhammad Bilal

Environmental Nanosciences and Material Research Laboratory, Department of Environmental Sciences

 Contents
Study Context

Statement of the Problem

Purpose of Study

Objectives

Methodology

Results and Discussion

Conclusion

Recommendations

17/12/2021 Ph.D Defense

 Study Context
What is photocatalysis?

 Wastewater treatment

 Air purification

 Energy production

 Titanium dioxide (TiO2), also known as titanium

oxide or titania is most widely used.

(Ngoepe et al., 2020; Zou et al., 2020; Gogoi et al., 2020)

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 Limitations of TiO2 as Photocatalyst

Large band gap (>3.2 eV)

Conduction band CB UV light

(<390 nm)

UV light active only (<390 nm)

Photocatalyst

Valance band VB
+- +- +- +- +-

High recombination rate of e-/h+

(Kosuke, et al., 2020; Yang et al., 2018)

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 Solution to These Limitations

Surface modifications

 Noble metal deposition (Ag, Au, Pd, Pt)

 Semiconductor coupling (ZnO, WO3 etc)

Bulk modifications
 Doping with metal (Fe, Mn, Cu, Ni etc)

 Non-metal (N, S, P, C, Graphene quantum dots (GQDs))

(Kumar et al., 2017; Pathaki et al., 2019; Bansal et al., 2020, Khan et al., 2014; Khan et al., 2021a, b, Iftikhar et al., 2020; Khan et al., 2020)

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 Why Graphene Quantum Dots (GQDs)?

 Excellent solubility

 Chemical inertness

 Stable photoluminescence

 Low toxicity

 Tunable band-gap

 Very well electron donor and accepter

 Ultrafast charge carrier mobility

 Up-conversion luminescence

(Safardoust-Hojaghan and Salavati-Niasari 2017; Nie et al., 2018, Tour et al., 2018)

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 What does doping result?

1. Greater absorbance in the visible region

2. Introduced new occupied (i.e. electron rich) orbitals in between the VB and CB

3. Narrow the gap between the VB and CB of titania

- Visible light (400-700 nm)

CB
Doping species
acts as electron
and/or hole
traps
New orbital

VB
+
(Matějová et al., 2018; Shivaramu et al., 2020)

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Dye as a Colored Substance

 Dyes are organic compounds of natural or synthetic origin

• Absorb visible light selectively in the range 400–700 nm

• Capable of dying various materials (fabrics, paper,

leather, wood, plastic, food, cosmetics)

RB5 (double azo dye)

(Gamallo et al., 2018)

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 TiO2 Photocatalytic Mechanism
Pollutant
•OH
Reduction O2 , H 2 O O2 - H 2 O2 Byproducts
CO2 + H2O

CB Light

Photocatalyst

VB
+- +- +- +- +-
Oxidation Pollutant
O2, H2O H+, •OH Byproducts
CO2 + H2O (Devi and Anitha 2018)

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Statement of the Problem

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Purpose of the Study

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General Objective

Specific Objectives

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17/12/2021 Ph.D Defense 13
Methodology
Experimental Layout

1. TiO2 photocatalyst synthesis

2. TiO2 3. Dye
photocatalyst decolorization
characterization studies

Sol gel synthesis method

(Anderson et al., 1995)

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 Synthesis of photocatalysts

Metal/nonmetal doped TiO2 GQDs metal/nonmetal doped TiO2

(0.2-5 wt % GQD loading and 300°C calcination)
22

Fe-TiO2 9
9
(0.01-5 wt %)
(200, 300 and 400°C) 22 GQDs-TiO2 9
GQDs-Fe-TiO2

N-TiO2
5
(5-30 mol%)
(200, 300 and 400°C) GQDs-N-TiO2 8
Fe-N-TiO2
0.1Fe-20N-TiO2
n=84 (200, 300 and 400°C)

GQDs-Fe-N-TiO2
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 Photocatalysts Characterization

Analysis Instrument

Absorption and bandgap energy Diffuse Reflectance Spectroscopy (DRS)

Identification of phases, crystallinity X-ray Diffraction (XRD)

Functional group Fourier Transform Infrared Spectroscopy (FTIR)

Photoluminescence analysis Flouromax Plus

Scanning Electron Microscopy (SEM)

Surface morphology
Transmission Electron Microscopy (TEM)

Surface chemistry X-ray Photoelectron Spectroscopy (XPS)

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 Photocatalytic Experimental Setup

1. Visible light source, 2. Reaction vessel, 3. Water bath, 4. Photocatalysts,

5. Magnetic stirrer, 6. Stirring hotplate, 7. Cooling fan Khan et al., 2020

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 Screening Optimization

Fe-TiO2 = 22
Screening studies for
metal and nonmetal N-TiO2 = 22 3
doped photocatalysts
Fe-N-TiO2 = 5
Photocatalyst dose

Variable pH

GQDs-TiO2 = 9 Initial dye concentration

Screening studies for GQDs-Fe-TiO2 = 9

GQDs decorated 4
photocatalysts GQDs-N-TiO2 = 9

GQDs-Fe-N-TiO2 = 8

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 Adsorption Isotherm

Langmuir Qe= Adsorption capacity at equilibrium

Qm= Maximum adsorption capacity
1 1 1 1
   Kads = Langmuir adsorption constant
Qe Qm K adsQm Ce Ce= RB5 concentration at equilibrium

Freundlich

1
ln Qe  ln  K F   lnCe
KF= Adsorption capacity

n n= Heterogeneity factor

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 Kinetic Studies

Pseudo first order model

[RB5]e = RB5 concentration at equilibrium
[ RB5]e [RB5]t = RB5 concentration at time t
ln  kapp t
[ RB5]t Kapp = Apparent rate constant
t = Time

Langmuir-Hinshelwood model
r0 = Initial rate of reaction
1 1  1 1 
   KC = L-H constant
r0 K c  K c K ads [ RB5]e 
KLH = L-H adsorption constant
[RB5]e = RB5 concentration at equilibrium

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Recycling Study

Multiple recycling studies for selected photocatalysts were conducted

with the same experimental setup and conditions.

Energy Efficiency and Cost Analysis

(𝑝𝑡)1000
𝐸𝐸/𝑂 =
𝐶0
[(𝑉)60 𝑙𝑛
𝐶𝑓

(Mancuso et al., 2020)

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Results and Discussion
 Characterization
Absorbance spectra Tauc plot

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 1.5
TiO₂-300
1.2 0.1Fe-TiO₂-300
Absorbance (a.u.)

GQD-0.1Fe-TiO₂-300
0.9

0.6

0.3

0
200 300 400 500 600 700 800
Wavelength (nm)

Photocatalyst Bandgap (eV)

TiO2-300 3.19
0.1Fe-TiO2-300 2.99
GQD-0.1Fe-TiO2-300 2.94

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 Characterization

Bandgap analysis

Photocatalyst Bandgap (eV)

GQD-0.1Fe-20N-TiO2 2.85
GQD-20N-TiO2 2.91
GQD-0.1Fe-TiO2 2.94
0.1Fe-20N-TiO2 2.92
20N-TiO2 2.95
0.1Fe-TiO2 2.99
TiO2 3.19

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X-ray Diffraction Analysis

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X-ray Diffraction Analysis

Crystallite size
Photocatalyst
(nm)
GQD-0.1Fe-20N-TiO2 5.37
GQD-20N-TiO2 7.37
GQD-0.1Fe-TiO2 5.32
0.1Fe-20N-TiO2 8.05
20N-TiO2 7.38
0.1Fe-TiO2 7.31
TiO2 36.85

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Functional Group Analysis

Intensity (a.u)

Wavelength (nm)
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Functional Group Analysis

Nanomaterials
GQD-
Functional 0.1Fe- 20N- 0.1Fe-20N- GQD-0.1Fe- GQD-20N- 0.1Fe-
TiO2
groups TiO2 TiO2 TiO2 TiO2 TiO2
20N-TiO2

Ti-O-Ti

Ti-O-N

Ti-N

Ti-O-C

C-N

O-H

C=C
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PL Analysis

Intensity (a.u.)

Wavelength (nm)
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Surface Morphology
Fe-TiO2 GQD-Fe-TiO2

Khan et al., 2021a Khan et al., 2021b

20N-TiO2 GQD-N-TiO2

Khan et al., 2020

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Surface Morphology

Fe-N-TiO2 GQD-Fe-N-TiO2

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SEM Particle Size of Synthesized Photocatalysts

Photocatalyst SEM (particle size nm)

GQD-0.1Fe-20N-TiO2-300 10-25

GQD-20N-TiO2-300 20-55

GQD-0.1Fe-TiO2-300 20-50

0.1Fe-20N-TiO2-300 40-80

20N-TiO2-300 20-30

TiO2-300 97-150

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Surface Morphology

Average particle size = 4.03 ± 1.2 nm

Frequency (%)
3 4 5 6 7 8

d=0.415
nm

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Surface Chemistry

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 Screening Studies for Fe-N-TiO2 and GQD-Fe-N-TiO2

Fe-N-TiO2 GQD-Fe-N-TiO2

100 100
RB5 decolorization (%)

RB5 decolorization (%)

80
90
60

in 30 min
80
40

20 70

0 60
200 300 400 500 0.0 0.2 0.5 1.0 1.5 2.0 3.0 4.0 5.0
Calcination temperature (°C) GDS’s contents (wt%)

Reaction Conditions: Dye Conc. 30 mg L-1, reaction temperature 22 °C, photocatalyst dose 1 g L-1, pH 6.2, illumination 500 w halogen lamp
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 Optimization Fe-N-TiO2 and GQD-Fe-N-TiO2 Photocatalysts

Effect of photocatalyst dose Effect of initial RB5 concentration

0.1Fe-20N-TiO₂-300 0.1Fe-20N-TiO₂-300
RB5 decolorization (%)

100 100

RB5 decolorization (%)

80 80
60 60
40 40
20 20
0 0
0 0.25 0.5 1 2 4 8 10 20 30 40 50 60 100
-1
Photocatalyst dose (mg mL ) RB5 concentration (mg L-1)

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Adsorption Isotherm

Langmuir

0.15 y = 0.3391x + 0.0234

R² = 0.9696 Langmuir Freundlich
Photocatalyst
R2 R2
0.12
0.1Fe-TiO₂-300 0.9696 0.9446
1/Qe (mg g-1)

0.09
20N-TiO₂-300 0.9127 0.9116

0.06 0.1Fe-20N-TiO₂-300 0.9812 0.9475

GQD-0.1Fe-20N-TiO₂-300 0.9825 0.8546

0.03

0.00
0.00 0.10 0.20 0.30 0.40
1/Ce (mg L-1)

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Maximum Adsorption Capacity

70
62.63
60

50
42
Qm (mg g-1)

40 40.16
40

30

20

10

0
0.1Fe-TiO₂-300 20N-TiO₂-300 0.1Fe-20N-TiO₂-300 GQDs-0.1Fe-20N-TiO₂-300

Photocatalysts
Reaction Conditions: Dye Conc. 30mgL-1, reaction temperature 22 °C, photocatalyst dose 1gL-1, pH 6.2, illumination 500w halogen lamp

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Langmuir Adsorption Constant

0.008

0.006
Kads ( L mg-1)

0.004

0.002

0
0.1Fe-TiO₂-300 20N-TiO₂-300 0.1Fe-20N-TiO₂-300 GQDs-0.1Fe-20N-TiO₂-300
Photocatalysts

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 Order of Reaction Kinetics

GQD-0.1Fe-20N-TiO2-300
Pseudo first order
10 20 30 40 50 60 100
50 RB5 Concentration Kapp R2
10 0.75 0.9448
40
ln([RB]₀/[RB]t)

20 0.32 0.9570
30
30 0.21 0.9922
20
40 0.11 0.9607
10
50 0.10 0.9517
0
0 10 20 30 40 50 60 60 0.08 0.9173
Time (min)
100 0.06 0.9534

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Photocatalytic Kinetics

L-H isotherm GQD-0.1Fe-20N-TiO2-300

60 y = 0.5077x + 7.4904
R² = 0.9433

45
1/kapp (min-1)

30
KC = 5.6529 mg L-1 min-1
15 KLH = 0.5133 L mg-1

0
0 20 40 60 80 100
[RB]o (mg L-1)

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Langmuir-Hinshelwood Reaction Constant (Kc)

5
KC (mg∙L–1∙h–1)

0
0.1Fe-TiO₂-300 20N-TiO₂-300 0.1Fe-20N-TiO₂-300 GQDs-0.1Fe-20N-TiO₂-300
Photocatalysts

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Langmuir-Hinshelwood Adsorption Constant (KLH)

0.6

0.5

0.4
KLH (L mg–1)

0.3

0.2

0.1

0
0.1Fe-TiO₂-300 20N-TiO₂-300 0.1Fe-20N-TiO₂-300 GQDs-0.1Fe-20N-TiO₂-300

Photocatalysts

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 Comparison of Different Photocatalysts on RB5 Initial Concentration
0.1Fe-20N-TiO2
0.1Fe-TiO2 20N-TiO2

RB5 decolorization (%)

100
RB5 decolorization (%)

RB5 decoloration (%)

100 100
80 80 80

60 60 60

40 40 40

20 20 20

0 0 0
10 20 30 40 50 60 100 10 20 30 40 50 60 100 10 20 30 40 50 60 100
RB5 concentration (mg L-1) RB5 concentration (mg L-1) RB5 concentration (mg L-1)
GQD-0.1Fe-TiO2 GQD-20N-TiO2 GQD-0.1Fe-20N-TiO2

RB5 decolorization (%)

RB5 decorization (%)

100 100 100

RB5 decolorization (%)

80 80 80
60 60 60
40 40 40
20 20 20
0 0 0
10 20 30 40 50 60 100 10 20 30 40 50 60 100 10 20 30 40 50 60 100
RB5 concentration (mg L-1) RB5 concentration (mg L-1)
RB5 concentration (mg L⎻1)
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 Comparison of Different Photocatalysts on RB5 Initial Concentration
0.1Fe-20N-TiO2
0.1Fe-TiO2 20N-TiO2

RB5 decolorization (%)

100
RB5 decolorization (%)

RB5 decoloration (%)

100 100
80 80 80
58.2 55.7
60 60 50.8 60

40 40 40

20 20 20

0 0 0
10 20 30 40 50 60 100 10 20 30 40 50 60 100 10 20 30 40 50 60 100
RB5 concentration (mg L-1) RB5 concentration (mg L-1) RB5 concentration (mg L-1)
GQD-0.1Fe-TiO2 GQD-20N-TiO2 GQD-0.1Fe-20N-TiO2

RB5 decolorization (%)

RB5 decorization (%)

100 100 100

RB5 decolorization (%)

81.4
80 80 80
65.6
60
58.9
60 60
40 40 40
20 20 20
0 0 0
10 20 30 40 50 60 100 10 20 30 40 50 60 100 10 20 30 40 50 60 100
RB5 concentration (mg L-1)
RB5 concentration (mg L-1)
RB5 concentration (mg L⎻1)
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Decolorization Reaction Mechanism of RB5 Dye

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RB5 Decolorization Mechanism

Absorbance (a.u.)

Wavenumber (cm-1)

Khan et al., 2020

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Radical Trapping Experiments

1.0 Blank IPA AgNO₃ EDTA

.OH
0.8
e-
0.6 h+
C/Co

0.4

0.2

0.0 Blank
0 10 20 30 40 50 60
t (min)
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 -4 Proposed Reaction Mechanism

-3
Fe-TiO2
Reaction at CB
-2 N-TiO2
Energy vs NHE

-1
GQDs
e−
0 O2
2.94 eV
1 2.95 eV

2 2.81 eV

3
Reaction at VB
4

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Recycling of the Photocatalyst

TiO₂-300 0.1Fe-20N-TiO₂-300 GQD-0.1Fe-20N-TiO₂-300

100

RB5 decolorization (%)

80

60

40

20

0
C1 C2 C3 C4
Number of cycles

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Energy Consumption and Cost Analysis for Photocatalytic
Reaction

Cost m-3
Photocatalyst EE/O kWh m-3
(PKR)

0.1Fe-TiO2-300 207.00 5309 Khan et al., 2021a

20N-TiO2-300 166.15 4261 Khan et al., 2020

0.1Fe-20N-TiO2-300 136.03 3489

GQD-0.1Fe-TiO2-300 137.47 3526 Khan et al., 2021b

GQD-20N-TiO2-300 89.15 2286

GQD-0.1Fe-20N-TiO2-300 19.82 508

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 Comparative Analysis of Photocatalysts for RB5 Decolorization

100 99.9
92.9
85.3
82.6
80 73.5 77.3
RB5 decolorization (%)

60

43.5
40
32.8

20

0.4
0
RB5 T GQD-T FeT NT FeNT GQD-FeT GQD-NT GQD-FeNT
Photocatalysts

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Conclusions

1. Successfully synthesized with required characteristics and screened as well

as optimized the best dye decolorizing photocatalysts for different reaction
parameters.

2. Optimized photocatalysts displayed the decolorization efficiency in the order:

TiO2 < GQD-TiO2 < 0.1Fe-TiO2 < 20N-TiO2 < GQD-0.1Fe-TiO2 < 0.1Fe-20N-TiO2 <
GQD-20N-TiO2 < GQD-0.1Fe-20N-TiO2, confirming the heterogenous
photocatalysis and chemisorptive interaction between photocatalysts and RB5
dye.

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Conclusions

3. The photocatalytic reaction exhibited the indirect Z scheme in RB5 dye

decolorization through generating holes, super oxides and OH radicals as main
photocatalytic active species.

4. Graphene quantum dots decorated metal and nonmetal doped nanomaterials

for photocatalysis of azo dyes pave a new horizon in photocatalysis of
hazardous pollutant with lowest reaction cost and energy consumption.

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Recommendations

 The highly efficient GQD-0.1Fe-20N-TiO2-300 are recommended for real textile

wastewater treatment.

 Future studies should focus on the large-scale production and application of

GQD-0.1Fe-20N-TiO2-300 photocatalysts under artificial as well as sun light.

 Effect of different surfactants can be studied to control the size and shape of
the synthesized photocatalysts.

 Application of the synthesized photocatalyst can be broaden by applying the

synthesized photocatalyst in degradation of pesticides and pharmaceutical
waste.

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Publications

Journal Publications
1. Khan, M.S., et al., 2020. “Photocatalytic Decolorization and Biocidal Applications of
Nonmetal Doped TiO2: Isotherm, Kinetic Modeling and Insilco Molecular Docking Studies”.
Molecules, 25(19), 4468. (IF. 4.411).

2. Khan, M.S., et al., 2021. Synthesis and Characterization of Fe-TiO2 Nanomaterial:

Performance Evaluation for RB5 Decolorization and Invitro Antibacterial Studies. Nanomaterials
2021. 11(2), 436. (IF. 5.076).

3. Khan, M.S., et al., 2021. Graphene Quantum Dot and Iron Co-doped TiO2 Photocatalysts:
Synthesis, Performance Evaluation and Phytotoxicity Studies. Ecotoxicology and
Environmental Safety, 226, 112855. (IF. 6.291).

4. Khan, M.S., et al., 2021 Synthesis, Characterization, Photocatalytic, Bactericidal and

Molecular Docking Analysis of Cu-Fe/TiO2 Photocatalysts: Influence of Metallic Impurities and
Calcination Temperature on Charge Recombination. ACS Omega, 6(40), 26108-26118. (IF.
3.512).

17/12/2021 Ph.D Defense 58

Publication

Journal Publications (Group)

5. Riaz N., Khan M.S. et al., 2021. “Iron-Zinc Co-Doped Titania Nanocomposite:
Photocatalytic and Photobiocidal Potential in Combination with Molecular Docking Studies”.
Catalysts, 11(9), 1112. (IF. 4.146).

6. Ajum W., Khan M. S. et al., 2021. Occupational health impacts of transport industry:
collagen degrader, blood lead, and respiratory illnesses. Arabian Journal of Geosciences,
14(15), 1-8. (IF. 1.827).

7. Shah, S.H., Khan M.S., Bilal*, M., et al., 2021. Nano-Porous Zirconia Membranes for
Separation of Hydrogen from Carbon Dioxide, Polish Journal of Environmental Studies, 30(3).
2313–2323 (IF. 1.77).

8. Sarwar, A., Khan, M.S., et al., 2021. Iron oxide (Fe3O4) supported SiO2 magnetic
nanocomposites for efficient Adsorption of Fluoride from Drinking Water: Synthesis,
Characterization and Adsorption Isotherm Analysis. Water. 13, 1514. (IF. 3.103).

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Publication

Journal Publications (Group)

9. Shah J. A., Khan, M.S., Bilal, M*., et al., 2020. Melia azedarach Activated Carbon and its
novel TiO2 Nanocomposite for Chemisorption and Photodecoloration of Reactive Orange 16:
Isotherm and Kinetic Modeling. Current Analytical Chemistry, 17(1), 107-119. (IF. 1.896).

10. Haroon, H. Khan, M.S., Bilal, M*., et al., 2020. "Activated carbon from a specific plant
precursor biomass for hazardous Cr (VI) adsorption and recovery studies in batch and column
reactors: Isotherm and kinetic modeling." Journal of Water Process Engineering 38, 101577.
(IF. 5.460).

11. Shah J. A. Khan M.S. Bilal M*., et al., 2020. Tobacco Stalk Waste Biomass Holds
Multilayer and Spontaneous Adsorption Capabilities for Reactive Black 5 Dye: Equilibrium
Modelling and Error Function Analysis, Polish Journal of Environmental Studies, 30(3). (IF.
1.77).

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 Publication

Journal Publications (Group)

12. Riaz N., Khan M.S., Bilal M., et al., 2020. Photocatalytic Inactivation of Bioaerosols: A Short
Review on Emerging Technologies. Current Analytical Chemistry 16, 1-7. (IF. 1.896).

13. Iftikhar, A., M.S. Khan, Bilal M., et al., 2020. Influence of Metallic Species for Efficient
Photocatalytic Water Disinfection: Bactericidal Mechanism of In Vitro Results using Docking
Simulation. Environmental Science and Pollution Research, 27(32), 39819-39831. (IF. 4.223).

14. Shah, J. A., Khan, M. S., Bilal, M., et al., 2020. Phosphoric Acid Activated Carbon from Melia
azedarach Waste Sawdust for Adsorptive Removal of Reactive Orange 16: Equilibrium Modelling
and Thermodynamic Analysis. Molecules, 25, 2118. (IF. 4.411).

15. Riaz, N., Khan, M. S., Bilal, M., et al., 2020. Photocatalytic Degradation and Kinetic
Modelling of Azo Dye using Bimetallic Photocatalysts: Effect of Synthesis and Operational
Parameters. Environmental Science and Pollution Research. 27(3):2992-3006 (IF 4.223).

17/12/2021 Ph.D Defense 61

Publications

Conference Publications

1. Khan, M.S., Bilal, M., et al., 2019. Dual Effect of Adsorption and Photodegradation of
Reactive Black 5 Azo dye using Fe-TiO2 Nanomaterials under Visible Light Irradiation: Kinetics
and Isotherm Modelling, Proceedings of VII International Conference on “Environmentally
Sustainable Development” (ES-Dev 2019) organized by Department of Environmental
Sciences, CU, Abbottabad Campus, Pakistan.

2. Khan, M.S., Bilal, M., et al., 2019. Photocatalytic Degradation of Azo dyes using N-TiO2
Photocatalyst: Effect of Nitrogen Loading and Calcination Temperature, February 2019,
Conference: ESCON 2019, Environmental Toxicology and Health. CUI Vehari Campus.

3. Shah, J. A., Khan, M.S., Bilal, M., et al., 2019. Exploring the Potential of Agricultural Waste
Based Activated Carbon for Treatment of Reactive Orange 16 Dye: Isotherm, Kinetic and
Thermodynamic Studies, February 2019, Conference: ESCON 2019, Environmental
Toxicology and Health. February 25-27, 2019. COMSATS University Islamabad, Vehari
CampusAt: ESCON 2019, Environmental Toxicology and Health. CUI Vehari Campus.

17/12/2021 Ph.D Defense 62

Publication

Conference Publications

4. Javid, L., Khan, M.S., Bilal, M., et al., 2019. Thermodynamic, Kinetic and Isotherm Studies
of Reactive Dye Adsorption onto Hemp Carbon: Linear and Non-linear Modeling. February
2019, Conference: ESCON 2019, Environmental Toxicology and Health. February 25-27,
2019. COMSATS University Islamabad, Vehari Campus, ESCON 2019, Environmental
Toxicology and Health. CUI Vehari Campus.

5. Iftikhar, A., Khan, M.S. et al., 2019. Adsorption and Photocatalytic efficiency of Modified
Titania for Textile Azo dyes under the Visible light Irradiation, February 2019, Conference:
ESCON 2019, Environmental Toxicology and Health, CUI Vehari Campus.

17/12/2021 Ph.D Defense 63

Research Project

Enhancement of Adsorption and Photocatalytic Activity of TiO2 Photocatalyst by doping with

metal and non-metal for Azo Dyes Degradation. 2018. Funding agency- COMSATS IIT, 0.27
million PKR, As Principal Investigator (PI). Status – 2018.

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Summary

Publication as first Author 4 (IF:19)

Publications in lab research group 11 (IF:37.565)

Conference publications (Thesis) 2

Conference publication (Group) 3

Publication in preparation (Thesis) 5

Publication submitted (Group) 4

17/12/2021 Ph.D Defense 65

Acknowledgements

Higher Education Commission of Pakistan under National Research Projects for

Universities (NRPU) project#20-1915

COMSATS University Islamabad Research Grant Program No. 16 79/ CRGP/

CIIT/ATD/17/1141

Pollution management with waste adsorbent, RG191313, University of Hails,

Ministry of Education, KSA

17/12/2021 Ph.D Defense 66

Acknowledgements

Supervisory Committee

Dr. Muhammad Bilal

(Supervisor)

Dr. Muhammad Arshad

(Co-supervisor)

Dr. Arshid Pervez

(Committee member)

Dr. Ahson Jabbar Shaikh

(Committee member)

17/12/2021 Ph.D Defense 67

Acknowledgements

Dr. Muhammad Arfan (SNS, Dept. of Chemistry, NUST)

Dr. Khurram Yaqoob (IESE, Dept. of Env. Sci., NUST)

Dr. Mazhar Iqbal (Env. Sci. Quaid e Azam University)

Dr. Muhammad Saifullah Awan (NCP, Quaid e Azam University)

Dr. Sohail Anjum Shahzad (Chemistry Dept. CUI ATD)

Dr. Ajmal Khan (University of Nizwa, Oman)

Dr. Tayyab Ashfaq Butt (University of Hails, KSA)

Prof. Dr. Pingxiao Wu (South China University of Technology, China)

17/12/2021 Ph.D Defense 68

Acknowledgements

Dr. Muhammad Irshad Dr. Qaisar Mahmood (T.I.)

Chairman HoD

Thanks to the subject teaching respectable teachers during PhD course work

All DAC and faculty member of ES Department

Lab technologists, and Lab fellows

I am thankful to my parents, uncle, wife, kids and sister for the

prayers, motivation and encouragement

17/12/2021 Ph.D Defense 69

References
Aliabadi, R. S. and N. O. Mahmoodi (2018). "Synthesis and characterization of polypyrrole, polyaniline nanoparticles and their nanocomposite for removal of azo dyes; sunset yellow and
Congo red." Journal of cleaner production 179: 235-245.

Chen, B., et al. (2018). "From Large Scale Synthesis to Lighting Device Applications of Ternary I-III-VI Semiconductor Nanocrystals: The Inspiring Greener Material Emitters." The journal of
physical chemistry letters.

Deligiannakis, Y. (2018). "Nanomaterials for Environmental Solar Energy Technologies: Applications & Limitations." KONA Powder and Particle Journal: 2018004.

Devi, L. G. and B. Anitha (2018). "Exploration of vectorial charge transfer mechanism in TiO2/SrTiO3 composite under UV light illumination for the degradation of 4-Nitrophenol: A comparative
study with TiO2 and SrTiO3." Surfaces and Interfaces 11: 48-56.

Gamallo, M., et al. (2018). "6 Textile Wastewater Treatment by Advanced Oxidation Processes." Life Cycle Assessment of Wastewater Treatment: 5.

Gottlieb, A., et al. (2003). "The toxicity of textile reactive azo dyes after hydrolysis and decolourisation." Journal of Biotechnology 101(1): 49-5

Goutam, S. P., et al. (2018). "Green synthesis of TiO2 nanoparticles using leaf extract of Jatropha curcas L. for photocatalytic degradation of tannery wastewater." Chemical engineering journal
336: 386-396.

Gunti, S., et al. (2018). "Nanostructured photocatalysis in the visible spectrum for the decontamination of air and water." International Materials Reviews 63(4): 257-282.

Hamad, H., et al. (2018). "Electrocatalytic degradation and minimization of specific energy consumption of synthetic azo dye from wastewater by anodic oxidation process with an emphasis on
enhancing economic efficiency and reaction mechanism." Ecotoxicology and environmental safety 148: 501-512.

Huang, J., Lv, T., Huang, Q., Deng, Z., Chen, J., Liu, Z., & Wang, G. (2020). Effect of Rh valence state and doping concentration on the structure and photocatalytic H2 evolution in (Nb, Rh)
codoped TiO2 nanorods. Nanoscale.

Matějová, L., et al. (2018). "TiO2 and nitrogen doped TiO2 prepared by different methods; on the (micro) structure and photocatalytic activity in CO2 REDUCTION AND N2O decomposition."
Journal of Nanoscience and Nanotechnology 18(1): 688-698.

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References
Mendes, C., et al. (2018). "Biodegradation study of azo dye Direct Orange 39 by Saccharomyces cerevisiae in a vertical bioreactor." Exploring Microorganisms: Recent Advances in Applied Microbiology: 45.

Miyoshi, A., et al. (2018). "Water Splitting on Rutile TiO2‐Based Photocatalysts." Chemistry–A European Journal.

Ngoepe, N. M., Hato, M. J., Modibane, K. D., & Hintsho‐Mbita, N. C. (2020). Biogenic Synthesis of Metal Oxide Nanoparticle Semiconductors for Wastewater Treatment. Photocatalysts in Advanced Oxidation
Processes for Wastewater Treatment, 1-31.
Nie, Y.-C., et al. (2018). "Photocatalytic degradation of organic pollutants coupled with simultaneous photocatalytic H2 evolution over graphene quantum dots/Mn-N-TiO2/g-C3N4 composite catalysts:
Performance and mechanism." Applied Catalysis B: Environmental 227: 312-321.

Niinimäki, K. and L. Hassi (2011). "Emerging design strategies in sustainable production and consumption of textiles and clothing." Journal of cleaner production 19(16): 1876-1883.

Puvaneswari, N., et al. (2006). "Toxicity assessment and microbial degradation of azo dyes."

Safardoust-Hojaghan, H. and M. Salavati-Niasari (2017). "Degradation of methylene blue as a pollutant with N-doped graphene quantum dot/titanium dioxide nanocomposite." Journal of cleaner production 148:
31-36.

Shan, Y., et al. (2018). "Dual effect of polypyrrole doping on cadmium sulfide for enhanced photocatalytic activity and robust photostability." Journal of Materials Science 53(3): 2065-2076.

Shivaramu, N. J., Coetsee, E., Roos, W. D., Nagabhushana, K. R., & Swart, H. C. (2020). Charge carrier trapping processes in un-doped and BaAl2O4: Eu3+ nanophosphor for thermoluminescent dosimeter
applications. Journal of Physics D: Applied Physics, 53(47), 475305.

Tour, J. M., et al. (2018). Methods of producing graphene quantum dots from coal and coke, Google Patents.

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production 172: 1986-1997.

Yang, T., et al. (2018). "Enhanced photocatalytic ozonation degradation of organic pollutants by ZnO modified TiO2 nanocomposites." Applied Catalysis B: Environmental 221: 223-234.

Ye, Jie, et al. "Efficient photoelectron capture by Ni decoration in Methanosarcina barkeri-CdS biohybrids for enhanced photocatalytic CO2-to-CH4 conversion." Iscience 23.7 (2020): 101287.

Zhao, C., Ran, F., Dai, L., Li, C., Zheng, C., & Si, C. (2020). Cellulose-assisted construction of high surface area Z-scheme C-doped g-C3N4/WO3 for improved tetracycline degradation. Carbohydrate Polymers,
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Thank you
 Overall Performance with Physico-chemical Properties

Crystallite size SEM (particle size Bandgap

Photocatalyst RB5 decolorization (%)
(nm) nm) (eV)

TiO2-300 36.85 97-150 3.19 32.8

0.1Fe-TiO2-300 7.31 30-40 2.99 73.5
20N-TiO2-300 7.38 20-30 2.95 77.3
0.1Fe-20N-TiO2-300 8.05 40-80 2.92 82.6
GQD-0.1Fe-TiO2-300 5.32 20-50 2.94 85.3
GQD-20N-TiO2-300 7.37 20-55 2.91 92.9
GQD-0.1Fe-20N-TiO2-300 5.37 10-25 2.85 99.9

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X-ray Diffraction Analysis

FWHM β Crystallite size

Photocatalyst
(radian) (nm)
TiO2 300 0.0040 36.85
0.1Fe-TiO2-300 0.0276 7.31
20N-TiO2-300 0.0279 7.38
0.1Fe-20N-TiO2-300 0.0201 8.05
GQD-0.1Fe-TiO2-300 0.0201 5.32
GQD-20N-TiO2-300 0.0203 7.37
GQD-0.1Fe-20N-TiO2-300 0.0184 5.37

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 Types of Semiconductors
- Low bandgap energy
- Stable
- Unsuitable CB position Zhao, et al. (2020)
CB
CdS
Splitting energy
CdSe eV 1.23
WO3 SrTiO3

NaTaO3
TiO2
TiO2

VB - Suitable CB and VB position

- Low bandgap energy
- Stable
- Suitable CB and VB position
- Wide bandgap
Ye, et al. (2020) - Unstable  photocorrosion
Huang et al. (2020)

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 Dye, a colored substance
 Dyes are organic compounds of natural or synthetic origin

• Absorb visible light selectively in the range 400–700 nm

• Capable of dying various materials (fabrics, paper, leather,

wood, plastic, food, cosmetics).

RB5 (double azo dye)

A-N=N-B A-NH2 + B-NH2

Gamallo et al. (2018). Amines
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 CO2 + H2O
+ Degraded products
•O2− +H2O
h+
RB5
HO2 + OH−
e−
O2 e−
H+
2 •OH
RB5

CO2 + H2O
+ Degraded products

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 Statistical analysis

 One-way ANOVA

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 Objective 3

1.2 Optimization studies Fe doped TiO2:

1.2.1 Effect of Photocatalyst Dose 1.2.2 Effect of pH
100 100
RB5 decolorization (%)

RB5 decolorization (%)

80 80

60 60

40 40

20 20
0
0
0.25 0.5 1 2 4 8
2 4 6 8 10 12
Photocatalysts Dose (mg ml-1) pH
1.2.3 Effect of initial RB5 concentration
100

RB5 decolorization (%) 80

60

40

20

0
10 20 30 40 50 60 100
Initial Dye concentration (mg L-1)
Figure 1.3 Optimization studies Fe doped TiO2: Effect of Photocatalysts dose ; reaction pH and initial RB5 concentration
Reaction Conditions: Dye Conc. 30mgL-1, reaction temperature
17/12/2021 °C, photocatalyst dose 1gL-1, pH 6.2, illumination 500w halogen lamp
Ph.D22Defense 79
4.7 Comparison of photocatalytic performance
RB5 T GQD-T NT GQD-NT FeT GQD-FeT FeNT 1GQD-FeNT

100

80
% RB5 Decoorization
% RB5 Decoorization

60

40

20

0
0 10 20 30 40 50 60 70 80 90 100 110 120
Time (min)

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4.5.1 Recycling of the photocatalyst

100 TiO₂-300 0.1Fe-TiO₂-300 GQD-0.1Fe-TiO₂-300

RB5 decolorization (%)

80

60

40

20

0
C1 C2 C3 C4
Number of cycles

Figure ‎3.99 Recycling studies for TiO2-300, 0.1Fe-TiO2-300 and GQD-0.1Fe-TiO2-300

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4.5.2 Recycling of the photocatalyst
TiO₂-300 20N-TiO₂-300 GQD-20N-TiO₂-300
100

RB5 decolorization (%)

80

60

40

20

0
C1 C2 C3 C4
Number of cycles

Figure ‎3.99 Recycling studies for TiO2-300, 20N-TiO2-300 and GQD-20N-TiO2-300

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Objective 3
3.2.1 Comparison of related performance of different doped material

30 min 60 min 90 min

100

RB5 decolorization (%) 80

60

40

20

0
RB5 T FeT NT FeNT GQDs-T GQDs-FeNT
Photocatalysts

Figure 3.5 Effect of different doped material and blanks on % RB5 Removal in 30 minutes of irradiation

17/12/2021
Reaction Conditions: Dye Conc. 30mgL-1, reaction temperature 22 °C,
Ph.D Defense
photocatalyst dose 1gL-1, pH 6.2, illumination 500w halogen lamp 83
 Synthesis of Photocatalysts

Metal/nonmetal doped TiO2 GQDs decorated TiO2

(0.2-5 wt % GQD loading and 300°C calcination)

22

Fe-TiO2 9
9
(0.01-5 wt %)
(200, 300 and 400°C) 22 GQDs-TiO2 9
GQDs-Fe-TiO2

N-TiO2
5
(5-30 mol%)
(200, 300 and 400°C) GQDs-N-TiO2 8
Fe-N-TiO2
0.1Fe-20N-TiO2
84 (200, 300 and 400°C)

GQDs-Fe-N-TiO2
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 Sol gel synthesis
Solution A Solution B

Addition
Titania precursor + with Absolute ethanol, glacial
absolute ethanol vigorous acetic acid and DI D. water
stirring

Addition of
Transparent colloid
metal, nonmetal
and GQDs
Aging till formation of
xerogel

Raw photocatalyst
powder

Ground to fine powder

Photocatalyst
and calcination

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 -4

-3 Fe-TiO2 N-TiO2 Fe-N-TiO2

RB5 Degraded products

-2
Energy vs NHE

-1
GQDs
0
2.94 eV
2.92 eV
1 2.95 eV

2 2.81 eV

4 Degraded products RB5

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Functional Group Analysis

GQD-0.1Fe-TiO2-300

0.1Fe-TiO2-300
T (%)

TiO2-300

500 1000 1500 2000 2500 3000 3500 4000

Wavenumber (cm-1)

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Functional Group Analysis

GQD-20N-TiO2-300

20N-TiO2-300
T (%)

TiO2-300

500 1000 1500 2000 2500 3000 3500 4000

Wavenumber (cm-1)

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