INDIAN INSTITUTE OF TECHNOLOGY KHARAGPUR

DEPARTMENT OF METALLURGICAL AND

MATERIALS ENGINNERING

PRESENTED BY
K VASU
ADVANCES IN GRAPHENE BASED
SEMICONDUCTOR PHOTOCATALYSTS
FOR SOLAR ENERGY CONVERSION
i. INTRODUCTION

 Solar Energy conversion by photo catalysis has been

promising Technology for a sustainable future.
 We can sort out the Environmental problems like
 global warming
 fossil fuel depletion
 pollution
GRAPHITE OXIDE
 Graphite oxide is a compound of carbon, oxygen and
hydrogen, by treating with strong oxidizers and acids for
resolving extra metals.
 The structure and properties of graphite oxide depends on
the particular synthesis method and degree of oxidation.
 The bulk material spontaneously disperses in basic
solutions to yield monomolecular sheets, known as
graphene oxide by analogy to graphene.
 Used in membranes, thin films, composite materials.
HUMMER’S METHOD
 Hummers' method is a chemical process that can be used to generate 
graphite oxide through the addition of potassium permanganate to a solution
of graphite, sodium nitrate, and sulfuric acid.
 It is also able to be revised in the creation of a one-molecule-thick version of
the substance known as graphene oxide.
GRAPHENE
 An allotrope of carbon consisting of one atom thick 2-D
sp2 –hybridized carbon packed into a hexagonal crystal
lattice with Exceptional properties.
PROPERTIES OF GRAPHENE

 High carrier mobility at room temperature (10000 cm2

V-1 s-1)
 A large theoretical specific surface area (2630 m2 g-1)
 Good optical transparency (97.7%)
 High young’s modulus (1 TPa)
 Excellent thermal conductivity (3000-5000 W m-1 K-1)
 Reservoir for photo generated electrons
APPLICATION OF GRAPHENE

 STORAGE AND ENERGY CONVERSION

 NANOELECTRONICS

 OPTOELECTRONICS

 SENSORS TO BIO APPLICATION

TECHNIQUES FOR GRAPHENE SYNTHESIS
 Bottom-up method:
heat treatment of the mixture of citric acid (CA)
and tannic acid (TA) with different weight ratios

 Top – down method:

The top-down method breaks down precursors like
graphite into layers that are atom thick. This method
simply converts graphite to graphene via mechanical
exfoliation, liquid-phase exfoliation (LPE), electrochemical
exfoliation, and chemical oxidation-reduction.
MECHANISM OF SEMICONDUCTOR
PHOTOCATALYSTS
 Electrons excited from valance band to conduction band
 Charge carriers that migrate to the surface of
photocatalysts
 Participate in surface oxidation
reduction reaction with the
absorbed reactants
 The recombination
of charge carriers(90% in 10 ns)
PREPARATION OF GRAPHENE BASED
SEMICONDUCTOR PHOTOCATALYSTS
 The preparation is of particular importance when building
uniform and efficient graphene based photocatalysts.
 Metal oxide
 Metal sulphide
 Metallate / graphene
composite
 Metal Nano particles (LSPR)
SYNTHESIS OF GRAPHENE BASED METAL
OXIDE PHOTOCATALYSTS
 A series of metal oxide semiconductors shows promising
photocatalytic application. (TiO2, ZnO2, Fe2O3, NiO, MnO2 )
 Many preparation protocols have been developed to fabricate
TiO2 /graphene composite photocatalysts.
FUNCTIONS OF GRAPHENE FOR
PHOTOCATALYTIC ACTIVITY ENHANCEMENT

 Fundamental science to construct graphene based

semiconductor photocatalysts with higher photoactivities.

Enhanced adsorptivity for reactants

Extended light absorption range
Photon-absorber

Electron transfer mediator

ENHANCED ADSORPTIVITY FOR
REACTANTS
 Surface adsorption is prerequisite for photocatalytic
processes.
 Graphene/ rod-shaped TiO2 nanocomposite samples with
high BET surface area exhibit higher photocatalytic
performance towards degradation of methyl orange(MO)
than P25.
 Enhanced physical adsorption of molecules, owing to the
higher BET surface, contributes to the photoactivity
improvement.
EXTENDED LIGHT ABSORPTION RANGE
 Photocatalysis is initiated by photoexcitation.
 Graphene is able to extend the light absorption range of
semiconductors.
 The surface carbon doping effect of Graphene often leads
to the light absorption edge extension of TiO2 from the
ultraviolet range to visible range.
 Thus making the TiO2/ Graphene composite is visible light
–responsive photocatalyst.
 The extension of the light absorption range of
CdS/graphene system is equal to TiO2/Graphene because
of band gap narrowing.
PHOTON ABSORBER
 Large scale density functional calculations on the model of the
graphene/TiO2 (110) interface.
 Along with wavelength dependent photo current study, shows
possible role of Graphene as a photosenstizer for TiO2.
 ZnS/GR nanocomposites as an organic dye like macromolecular
“photosensitizer” for ZnS.
 ZnS/GR nanocomposites exibits visible light photoactivity
towards epoxidation of alkanes under ambient condition.
 Graphene also exhibits strong near-infrared (NIR) absorbance
was applied for NIR photothermal therapy for cancer.
ELECTRON TRANSFER MEDIATOR
 EF of graphene is -0.08 V versus NHE, which is more
positive then ECB of most semiconductor.
 Photogenerated electrons will spontaneously transfer from
semiconductors to graphene nanosheets when come into
contact. So it was accepted as ETM.
 In an ideal system, the quantum yield which indicates the
efficiency of the photocatalytic process,

 KCT – RATE OF CHARGE TRANFER

 KR- RATE OF RECOMBINATION
MATERIALS ENGINEERING TOWARDS IMPROVING THE
ELECTRON TRANSFER EFFICIENCY IN GRAPHENE
BASED PHOTOCATALYSTS
 Chemically bonded TiO2/graphene through the Ti-C bond,
Which provide a good spatial condition for charge
transport from TiO2 to Graphene.
 Improve the transfer efficiency of photogenerated charge
carriers will increase by metal ions (Ca2+,Cr3+,Mn2+, Fe2+,
Co2+,Ni2+,Cu2+ and Zn2+) as “mediators” into their
interfacial layer matrix.
 The interfacial mediators can also drive the balance
between the positive effect of graphene on retarding the
recombination of electron-hole pair from semiconductor
and negative “shielding effect” of graphene.
 The interfacial electron transfer mediator was stepped
from metal ions to noble metal palladium(Pd).
SUMMARY AND PERSPECTIVES
 Graphene-based semiconductor photocatalysts as the next
generation artificial photosynthesis systems with higher
performance.
 The band-gap opening of graphene (GNR)could open a
wide scope for photocatalytic application.
 Doping graphene with nitrogen has been proved to be an
effective method for material engineering.
 Materials engineering should aim to enhance the
morphology control, light absorption, improve the mass
transportation, and increase the accessible surface area.
SUMMARY AND PERSPECTIVES

 More charge carriers can be generated by incident

photons, which will increase the apparent quantum
efficiency of photocatalysts.
 The advent of robust graphene is sure to make graphene
semiconductor composite photocatalysts promising
candidates for solar energy storage and conversion.
REFERENCES
 https://pubs.rsc.org/en/content/articlelanding/2015/nr/c5nr03338a
 https://onlinelibrary.wiley.com/doi/10.1002/anie.201411096
 https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6271203/
 https://www.atriainnovation.com/en/graphene-characteristics-and-
applications/
 PPT - Graphene -based nanocomposite photocatalyst PowerPoint Presentation
- ID:2405791 (slideserve.com)
 Photocatalyst - Green Millennium Inc
 Crystals | Free Full-Text | Advances in the Applications of Graphene-Based
Nanocomposites in Clean Energy Materials | HTML (mdpi.com)
 3D Nanoporous Graphene Based Single-Atom Electrocatalysts for Energy
Conversion and Storage | Accounts of Materials Research (acs.org)
 Design, modification and application of semiconductor photocatalysts -
ScienceDirect
 Graphene: Status and Prospects | Science
 Nanotoxicity of Graphene and Graphene Oxide | Chemical Research in
Toxicology (acs.org)
 Graphene in Photocatalysis: A Review - Li - 2016 - Small - Wiley Online Library
 Graphene plasmonics | Nature Photonics
 Synthesis and photocatalytic activity of nano-sized iron oxides – ScienceDirect
 Photocatalytic activity of metal oxides—The role of holes and OH radicals -
ScienceDirect
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