Introduction
• The presence of pharmaceuticals in the environment is a new
challenge for drinking water, wastewater, and water reuse
treatment systems.
• Non-steroidal anti-inflammatory drugs (NSAIDs) are a special
group of pharmaceuticals that are widely used and
frequently detected in hospital effluents, surface waters, STP
effluents as well as soil matric.
• Among various semiconductors, TiO2 is by far the most
suitable photocatalyst for environmental applications due to
its biological and chemical inertness, strong oxidizing power,
cost-effectiveness, environmentally benign nature, etc.
Continued…
• Due to a wide band-gap of TiO2 only a small fraction of
UV can be utilized for photo-degradation. Modification
techniques have been used to overcome this, such as
metal doping, non-metal doping, semiconductor
coupling.
• Non-metal doping of TiO2 by incorporation of nonmetals
such as nitrogen, carbon, sulfur and fluorine has been
considered an effective method for extending the
spectral response of TiO2 to visible light.
• The N,S co-doped nanosheets exhibit higher photo-
catalytic activity under visible light (>400 nm) than N–S–
TiO2 nanoparticles for the photo-catalytic decomposition
of 4-CP in water.
Results and Discussion
• Characterization of Catalysts:
1. TEM studies were used to observe the particle size,
crystallinity and structure of the synthesized N,S-TiO2
nanoparticles and nanosheets. The images should spheroid
morphology and mean particle diameter were between 5
and 10 nm.
2. The XDR pattern of TiO2 sample show that the diffraction
pattern of hydrothermal TiO2 nanosheet is similar to the of
the sol-gel TiO2 nanoparticles.
3. The peak intensities of N,S-TiO2 Nanosheets were sharper
and stronger as compared to the nanoparticles, indicating
the formation of larger crystals and higher crystallinity.
Methodology
Preparation of Catalyst (N,S co-doped TiO2;
Sol gel and Hydrothermal Method)
Characterization of Catalyst (FTIR, TEM,
BET, XRAD)
Photo-catalytic activity (via decomposition
of NSAID drugs under simulated solar
irradiation)
1. Results compared with un-
doped samples, Degussa P25
2. Effect of pH, pharmaceutical
conc., catalyst loading,
reaction time were
investigated
Continued…
• According to the UV-Vis spectra, the N,S-TiO2 nanosheets had
enhanced absorbance at wavelength above 500nm. Its probably
related to the synergistic effect of nitrogen and sulfur co-doping on
the electronic structure of TiO2.
• BET surface area of the S1 sample(nanoparticles) is approximately
twice the size of the S2 sample(nanosheets), nanoparticles have
higher surface to volume ratio than nanosheets.
• Moreover, FT-IR spectra shows broad absorption peak around 3400
cm-1 and the band at 1630 cm-1 can be assigned to the stretching
vibration and bending vibration of surface adsorbed water and the
hydroxyl groups.
Catalytic Screening
Screening experiments were performed to assess the relative catalytic
activity of doped and un-doped TiO2 samples with 5 mg/L initial IBP
and NPX concentrations under simulated solar irradiation.
Results show that N,S co-doped TiO2 samples (S1 and S2) exhibit higher
Photoactivity than the un-doped samples(S3andS4)and Degussa
P25. The S1 catalyst showed highest photoactivity and yielded
about 85% and 99.36% conversion of IBP and NPX, respectively. Low
percentages of degradation were observed in un-doped catalysts.
• Effect of Phytolysis and adsorption
Photolysis experiments were performed at pH 6 with 5 mg /L
initial concentration of IBP and NPX for 90 min under simulated
solar irradiation. Photolysis of IBP and NPX was 10 AND 20 %
respectively.
The adsorption capacity of S1, S2, S3, S4 and Degussa P25 was
0.019, 0.033, 0.004, 0.012 and 0.035 mg/g, respectively. For all
catalysts the adsorption removal reached its maximum after 30
min and then it remained almost constant to 90 min.
• Effect of Catalyst Loading
Results shows that the maximum conversions of IBP for S1 and S2
were 85% and 71% at a catalyst loading of 5.0 and 2.0 g L−1,
respectively.
The effect of catalyst loading is more pronounced in early stages
of the reaction (20–30 min) especially for the S2 catalyst.
• Effect of initial drug concentration:
The conversion level increased with increasing IBP
concentration up to 5 mg L−1and after that it decreased
in both catalysts. The decrease in conversion level was
stronger for the S2 catalyst.
• Effect of pH
The pH of the reaction solution has a significant effect on
the efficiency of the photocatalytic processes by
affecting the surface charge and the state of ionization of
the compound.
The role of pH in the photocatalytic conversion was
studied in the pH range 3-9 at a constant IBP
concentration(5mg/L).
• The final(i.e.after 90 min irradiation) conversion level of IBP for
the S1 catalyst was 80%,92%,and 82.5% at pH values of 3, 5
and 6,respectively.
• The conversion level decreased drastically and no removal was
observed at pH 9. For S2 catalyst the conversion level is the
same at about 64% regardless of the initial pH range 5 to 9.
• Effect of Anions
Photocatalytic degradation of organic pollutants in deionized
water may differ from that in real water that contains various
organic and inorganic compounds.
• The conversion level decreased by 6%, 2.5%, and 5.5% in the
presence of CO2−3, HCO−3 and Cl−, respectively, for the S1
photocatalyst and decreased by 9% and 5.6% for the S2
photocatalyst.
• Mineralization Study
The N,S-TiO2 nanoparticles and N,S-TiO2 nanosheets possess
higher mineralization than Degusa-P25 due to higher adsorption
of visible light.
Conclusion
• The N,S- TiO2 nanoparticles had a high surface-to-volume ratio,
which provided numerous surface active sites.
• N,S -TiO2 nanoparticles showed the highest photocatalytic
potential at pH 5 while the efficiency of N,S co-doped TiO2
nanosheets was independent of pH in the range 5-9. The high
photo catalyst activity of the doped sample was related to the
synergistic effect of Nitrogen and Sulfur.
• The N,S-TiO2(particle or sheet) dramatically enhanced activity,
this is a noteworthy alternative for treating pharmaceutical-
contaminated waters.
