Synthesis of Ag-TiO2-Reduced Graphene oxide

hybrid composites as photocatalyst for

degradation of dye

Supervisor Presented By
Dr. Dhanesh Tiwary Shivam Sahu
14053009
 Introduction

 Industrial waste pollute a substantial part of the water

resources.
 Dyes encompass a chief part of industrial water
effluents
 Removal of the dyes is very essential since it is
carcinogenic and has a hazardous effect on mankind.
 Only 45-47 % dyestuffs has been reported
biodegradable .
 A set of techniques called Advanced oxidation processes which
has been developed to treat dye-contaminant wastewater
effluents .

 In this technology semiconductor with suitable band gap energy

are used as a photo catalyst.

 the photo catalytic activity depends on the ability of the catalyst

to create electron–hole pairs, which generate free radicals
 Titanium dioxide(TiO2)
 TiO2 is widely used as photocatalyst because of its following
properties :
Nontoxicity
High photo-activity
Photo- and chemical stability

 High band gap energy (3.2 eV) absorbs the radiation only in
the UV region
 Diverse research activities have focused on shifting the titania
band gap to lower values.
 Graphene

 Graphene is a single-layer, two-dimensional carbonaceous

material.

 Due to its fascinating electronic, mechanical and thermal

properties , it has been widely applied in various areas.

 As a result of high specific area , excellent transparency, high

chemical stability, it can be used for photocatalyst carrier .

 Thus Gr based photocatalyst has been enjoying great research

interest.
 AgNPs(Silver nanoparticles)
 AgNPs is used as photocatalyst because of its following
properties :
Optical properties
Catalytic properties
 Localized surface plasmon resonance (LSPR) phenomenon
which enables them to have strong and broad absorption in the
visible region of the solar spectrum.

 Their extremely large surface area permits the coordination of

a vast number of ligands.
 Materials and Methods
• Synthesis of Graphene Oxide: Reduced graphene oxide (rGO) was
prepared through Hummers’ method.
 Commercially obtained graphite powder taken in a mixture of
H2SO4, NaNO3, and KMnO4.
After completion of the reaction, H2O2 was added to the
reaction vessel.
The rGO was filtered and washed twice with 1 M HCl and twice
with DI water. The rGO separated in the form of a dry, brown
powder.
•Binary Composite Synthesis (TiO2/r-GO):
 TiO2 (2g) was sonicated in 80 ml Water Ethanol Mixture (3:1 ratio) for 2 hours.
Graphene oxide (0.05g) was sonicated in 40 ml Water Ethanol Mixture (3:1 ratio) for 2
hours and added to TiO2 suspension and further sonicated for half and hour.
The materials were sealed in a teflon beaker and set at 120o C for 24 hours.
The product was centrifuged and washed thrice with water ethanol mixture.
Final product was dried at 80o C for 12 hours.

Ag nanoparticle addition
• 60 ml solution of 3 mmol silver nitrate solution was taken in beaker.
•To it added 0.5 g TiO2-rGO composite.
•The mixture was kept in microwave at 180 W, for 3 min.
•The product was centrifuged and washed with water thrice.
•It was dried in oven at 80o C for 12 hours.
Characterization(XRD)
Peak of Graphene oxide (GO) was
observed at 11.5o which was not
observed in TiO2-rGO.
• No diffraction patterns from carbon
species were observed, which resulted
from the shielding of main characteristic
peak of rGO at 24.5o by the main peak of
anatase TiO2 at 25.3o.
• The peaks of 25.3o, 37.0o, 48.0o, 53.9o,
55.6o, 62.7o, 68.8o, 70.5o and 75.0o can
be indexed to (101), (004), (200), (105),
(211), (204), (116), (220) and (215)
crystal planes of anatase TiO2
respectively.
•Diffraction peaks at 27.8o, 36.6o, and
41.4owere also observed, which were
assigned to the (110), (101), and (111)
faces of rutile TiO2.
•Three additional peaks of 44.0o, 64.6o
and 77.8o were found in TiO2-rGO-Ag
samples which were related to metallic
Ag (200), (220) and (311) planes.
SEM

Flakes of GO were seen on which TiO2 nanoparticles were

seen in binary composite along with the Ag nanoparticles
loaded in ternary composites. TiO2 particles were clearly
observed as well dispersed and intertwined on rGO. Ag
nanoparticles were uniformly dispersed over TiO2-rGO
composite.
TEM  The sizes of Ag nanoparticles
were also calculated to be in
range of 20-30 nm.
 The obtained composite
showed the two-dimensional
sheet structure with micron
range which creases after the
hydrothermal reduction.
 The coexistence of TiO2 and
Ag NPs was confirmed in the
form of dark regions which
were clearly visible.
Energy-dispersive X-ray spectroscopy (EDX )

The percentage of Ag metal atoms was calculated using this analysis. The
ternary composites shows a very small percent of Ag metal atoms in the
composite i.e. 0.02%
Studying the photocatalytic activity of the nanocomposite
by degradation of Acid Red dye (0.5g/L catalyst
concentration)
 Wavenumber Bond
cm-1

3400 O-H streching

vibrations

1720 C=O streching

1610 OH streching of
water molecule

1200 C-OH streching

FTIR investigation of the nanocomposite 1100 C-O streching

before (Black) and after the degradation
680 Ti-O-Ti bond
studies (Red) indication no change in
composite during the degradation process,
hereby confirming its catalytic nature.
Thank you