CHALCOGENIDES

PHOTOCATALYTIC ABILITY OF
CHALCOGENIDES
WHAT ARE CHALCOGENIDES?

• A chalcogenide is a chemical
compound consisting of at least one
chalcogen anion and at least one
more electropositive element.
Although all group 16 elements of
the periodic table are defined as
chalcogens, the term chalcogenide is
more commonly reserved for
sulfides, selenides, and tellurides,
 PROPERTIES OF
CHALCOGENIDES..
IR
transparenc
y

Electr
o Photo
chalcogenide
cataly cataly
st st

themoelect
rics
CHALCOGENIDES AS
PHOTOCATALYSTS

.HER-WATER SPLITTING

PHOTO DEGRADATION OF
ORGANIC POLUTANTS
 Steps in HER photocatalysis
2D Transition-Metal-Dichalcogenide-Nanosheet-Based
Composites for Photocatalytic and Electrocatalytic
Hydrogen Evolution Reactions

Photoexcitation

Reduction half

Recombination
Lu.et.al.,Adv. Mater. 2016, 28, 1917
 Requirements of an HER
photocatalyst
Semiconductor photocatalysts
for water oxidation: current
status and
challenges
• Minimum band gap
of 1.23eV
• Band gap >2eV is
often required
• Eg<3eV for efficient
utilizaton of solar
energy
• CB should be
positioned more
T. Fan, et.al.,, Phys. Chem. Chem. Phys.,
-ve than E of HER 2014
the bottom level of the conduction band has to be
more negative than the reduction potential of H+/H2 (0 vs. NHE
(normal hydrogen electrode)), and the top level of the valence
band has to be more positive than the oxidation potential of
O2/H2O (1.23V vs. NHE).
 .

•
One-pot Synthesis of CdS Nanocrystals
Hybridized with Single-Layer Transition-Metal
Dichalcogenide Nanosheets for Efficient
Photocatalytic Hydrogen Evolution†

Chen et.al Angew. Chem. Int. Ed. 2015 , 127,

,1226
SYNTHESIS ROUTE-ONE POT WET
CHEMICAL METHOD
To Oleyl
amine+OA+ODE,
addCdO

heat upto 300deg

,purge with N2

inject(NH4)2WS4/NH4)
2MoS4.heat for 2hrs
• Synthesis and characterization of
composite visible light active
photocatalysts MoS2-g-C3N4 with
enhanced hydrogen evolution
activity

Lei et.al.,In t e r n a t i o n a l j ournal o f

hydrogen energy 3 8 ( 2 0 1 3) 6 9 6 0
 SYNTHESIS ROUTE
Heat cynamide in
alumina combustion
boat at 550deg=g-
C3N4
•
Ammonium
molybdate+thiourea+
water-
autoclave220deg,24hr
s=layered MOS2
Add MOS2 soln
dropwise to (g-
C3N4+WATER)
Stirring,ultrasonic
dispersion,heating
under N2 gas at
 Synthesis of Few-Layer MoS2 Nanosheet-
Coated TiO2 Nanobelt Heterostructures
for Enhanced Photocatalytic Activities

Zhou.et.at.,Small 2013, 9, No. 1,

140
 SYNTHESIS ROUTE
TiO2+NaOH

Autoclave

Fitered,washed
with hcl=H2Ti3O7
Sodium
molybdate+acetamid
e+TiO2 belt
autoclave
TMD-Based Multicomponent
Photocatalysts

• hybridize photocatalysts with

other nanomaterials for the
preparation of multicomponent
catalysts for further improving
the charge separation and
transport.
MoS2/Graphene Cocatalyst for
Efficient Photocatalytic H-2
Evolution under Visible Light
Irradiation

Chang et.al.,AcsnanoVolXXX
 SYNTHESIS ROUTE

Sodium molybdate+L-cysteine-
AUTOCLAVEat 453 K for 24hrs

Add RGO+CdCl2 at 353

Polyvinylpyrolidine+argon gas

Thiogycolic acid+NaOH+Na2S

ANNEALING at 673K,2hrs
 Photocatalytic Activities of
ARTiCLE Copper Doped Cadmium
Sulfide Microspheres
Prepared by a Facile
Ultrasonic
Spray-Pyrolysis Method

doi:10.3390/molecules21060735

Su et.al.Molecules 2016, 21, 735

SYNTHESIS ROUTE
• Cadmium
nitrate,thiourea+w
ater

• Add optimum
amount of copper
nitrate

• 1+2 to ultrasonic
nebulizer
 Challenges that TMD’S pose before
us….
• achieving well-defined size, interface, and
controllable thickness and morphology of
TMDs

• critical for realizing efficient hole–electron

separation and migration in photocatalytic
reactions.
Eco-friendly synthesis of metal dichalcogenides
nanosheets and their environmental remediation
potential driven by visible light

• Ashish.et.al.,Scientific reports
5,15718,2015
TERNARY CHALCOGENIDES AS
PHOTOCATALYSTS
 Effect of different solvent on the photocatalytic
activity of ZnIn2S4forselective oxidation of aromatic
alcohols to aromatic aldehydes undervisible light
irradiation
L. Su et al. Applied Surface Science 384 (2016)
161
 SYNTHESIS ROUTE

Precursors:ZnSO4,thioacetamide,I
nCl3.4H2O

Stirring in ethanol soln in teflon

liner

AUTOCLAVE at 160deg for

12hrs
 Efficient photocatalytic hydrogen
ARTICLE
production under visible
light over a novel W-based ternary
chalcogenide
photocatalyst prepared by a hydrothermal
process

Cu2WS4
Jing et.al I n t e r n a t i o n a l j ournal o f
hydrogen energy 3 5 ( 2 0 1 0 ) 8 5 2 1
SYNTHESS ROUTE-hydrothermal
Na2WO4+CuCl+thioac
etamide

Magnetic stirring in
ethanol-water mixture

Autoclave at 200deg
 Self-assembled cabbage-likeNaInS2
ARTICLE
microstructures with efficient visible
light photocatalytic performance

Y.Gao etal.JournalofSolidStateChemistry203(2013)44
Synthesis Route-
HYDROTHERMAL

Soln1:InNO3+WATER

Soln2:S+NaOH+water at
100deg
Mix both .REFLUX IN
AUTOCLAVE at 180deg
 To start with…???
RGO-TMD composites show excellent
photocatalytic activities..Boron niride-
white graphite ,a suitable subtitute for
graphene or not?

= ???
• BN powder+IPA-heat in RB for 24hrs
• ,50deg, with magnetic stirring
• 20hrs ultrasonication

• Soln made to stand for days,supernatent centrifuged

• Wash ppt with acetone
• Dry at 60 deg overnight

• H-BNNS +HBF4 in RB-heat at 50 deg for 8hrs under magnetic

stirring,centrifuge ppt,wash with water,dry
Ball milled h-BN: An efficient holes
transfer promoter to enhance the
photocatalytic performance of TiO2

• TiO2 + zirconia balls of 3 different sizes

• Add h-BN +H2O

• Bal mil for 180 min at 550rpm

 High yield synthesis of novel boron nitride
submicro-boxes and their
photocatalytic application under visible light
irradiation

• KBH4+NH4F+Zn powder-autoclave
• At 450 deg for 30hrs

• Crude prduct cooled,washed wih HCL and dried

• SnCl2 +BNMB+=water –heat at 100deg for5 hrs.cool and

dry

Catal. Sci. Technol., 2011, 1, 1159–1165

Enhanced photocatalytic activity and anti-
photocorrosion of AgI nanostructures by
coupling with graphene-analogue boron nitride
nanosheets

• BN +WATER-sonicate for 30min

• Add AgNO3 +KI stir in the dark

• Centrifuge and collect the sediments

• Wash wth distilled water

• Heat in furnace at 80 dg for 8hrs