STUDIES ON

EFFECT OF PERVOSKITE ON PHOTOCATALYSIS

A Project Work
Submitted By
ROJALIN PATTNAIK
ROLL NO-19MCH009
Under the guidance of
Dr.Purnendu Parhi

DEPARTMENT OF CHEMISTRY
Ravenshaw University
Cuttack-753003
 Certificate
This is to ceritify that the project work entitled ,”STUDIES ON EFFECT
OF PERVOSKITE ON PHOTOCATALYSIS” being submitted to
Ravenshaw university ,cuttack in partial fulfilment of the
requirements for the completion of project work in MSc,embodies
the project work done by Miss Rojalin Pattnaik (roll no-19MCH009)
under my supervision at Ravenshaw university,cuttack.

Dr.Purnendu Parhi Prof.Smurti Prava Das

(Supervisor) HOD ,Chemistry
Ravenshaw University Ravenshaw Univesity
 DECLARATION
I hereby declare that the project work entitled “STUDIES ON EFFECT
OF PERVOSKITE ON PHOTOCATALYSIS “ embodied in this synopsis has
been carried out at the department of Chemistry,Ravenshaw
University,cuttack,Odisha,India under the supervision of
Dr.Purnendu Parhi.In keeping with the general practice of reporting
scientific observation ,due acknowledgement has been made
wherever the work is based on the finding of other
investigatiors .The author is responsible for purely unintentional
oversights and errors ,which could be traced herein .

Name-ROJALIN PATTNAIK
Roll no-19MCH009
Date-
Signature Signature
(Supervisor),Chemistry

Ravenshaw University
 ACKNOWLEDGEMENTS
During my research tenure at Ravenshaw University along with
journey of studying Master degree,I ran into many intresting and
helpful people who played different role and contributed in unique
and variable ways in my professional as well as personal
development.The least I could do is express my sincere and deep
sense of gratitude of my supervisor Dr.Purnendu Parhi for his
insightful advice and allowing me to think and work creatively in the
laboratory for the research work .I will never forget his encouraging
words and patience when my motivation was low.
I would also like to thank all the
faculty members of the Chemistry department,Prof Smruti Prava
Das,Dr.Jaya Prakash Das,Dr.Sabita Nayak,Dr.Seetaram
Mohapatra,Dr.K.S.V Varadwaj,Dr.Bairagi charan Malik,Dr. Rasmi
Rekha senapathy.
I am very much thankful to my
parents for their support and encouragement throughout my study.I
am also thankful to my friends for their encouragement,support and
valuable contribution for the completion of my project work.

Name-Rojalin Pattnaik
Roll no-19MCH009
Dept.of Chemistry
Ravenshaw University
 CONTENTS
1. INTRODUCTION-
-> Photocatalysis
->Types of photocatalysis
->Advancement in photocatalysis research
->Catalysts used in photocatalytic reaction
->Pervoskite based photocatalyst
2.PERVOSKITE BASED PHOTOCATALYST
->Structure of Pervoskite
->Types of Pervoskite
->Why we choose Pervoskite as photocatalyst
->Use of pervoskite based photocatalyst
3.DISADVANTAGES OF PERVOSKITE BASED PHOTOCATALYST
AND FUTURE ASPECTS
4.CONCLUSION
5.REFERENCE
1.INTRODUCTION-:
Environmental sustainability and the development of alternative and
renewable energy supplies represent two of our current society .The
increase of human activities related to hazardous greenhouse gases
emission ,have been recognized as the major driver of the present
global climate change issues .To prevent these issues we use
renewable energy source like solar power energy .The solar energy
employment can increase the world safety and humans sustainability
by decreasing pollution ,lowering the risk of mitigating climate
change and reducing such a dangerous dependence on fossile fuels .
From this perspective photocatalysis is
considered one of the main routes for an efficient utilization of solar
light energy .Photocatalysis is mainly defined as the catalysis of a
“photochemical reaction at a solid surface “or in other words it is a
process in which light energy is used to drive pairs of chemical
reaction ,both oxidation and reduction occurs simultaneously for the
photocatalyst to operate sustainably .
Advantages of photocatalysis-
This technology possesses several advantages including
environmental protection ,complete degradation of pollutants and
no secondary pollution .
History-
Early mentions of photocatalysis (1911–1938)
The earliest mention of photocatalysis dates back to 1911,
when German chemist Dr. Alexander Eibner integrated the concept
in his research of the illumination of zinc oxide (ZnO) on the
bleaching of the dark blue pigment, Prussian blue. Around this time,
Bruner and Kozak published an article discussing the deterioration of
oxalic acid in the presence of uranyl salts under illumination, while in
1913, Landau published an article explaining the phenomenon of
photocatalysis. Their contributions led to the development
of actinometric measurements, measurements that provide the basis
of determining photon flux in photochemical reactions. After a brief
stint of lack of research on photocatalysis, in 1921, Baly et al. used
ferric hydroxides and colloidal uranium salts as catalysts for the
creation of formaldehyde under light in the visible
spectrum. However, it wasn't until 1938, when Doodeve and
Kitchener discovered that TiO2, a highly-stable and non-toxic oxide,
in the presence of oxygen, could act as a photosensitizer for
bleaching dyes, as ultraviolet light absorbed by TiO2 led to the
production of active oxygen species on its surface, resulting in the
blotching of organic chemicals via photooxidation. This would
actually mark the first observation of the fundamental characteristics
of heterogeneous photocatalysis.
Advancements in photocatalysis research (1964–1981, present)
Research in photocatalysis subsided for over 25 years due to lack of
interest and absence of practical applications. However, in 1964, V.N.
Filimonov investigated isopropanol photooxidation from ZnO and
TiO2;[2][7] at around the same time, Kato and Mashio, Doerffler and
Hauffe, and Ikekawa et al. (1965) explored oxidation/photooxidation
of carbon dioxide and organic solvents from ZnO radiance.[2][8][9][10] A
few years later, in 1970, Formenti et al. and Tanaka and Blyholde
observed the oxidation of various alkenes and the photocatalytic
decay of nitrous oxide (N2O), respectively.
However, a breakthrough in photocatalysis research occurred in
1972, when Akira Fujishima and Kenichi Honda discovered
electrochemical photolysis of water occurring between connected
TiO2 and platinum electrodes, in which ultraviolet light was absorbed
by the former electrode, and electrons would flow from the
TiO2 electrode (anode; site of oxidation reaction) to the platinum
electrode (cathode; site of reduction reaction);
with hydrogen production occurring at the cathode. This was one of
the first instances in which hydrogen production could come from a
clean and cost-effective source, as the majority of hydrogen
production back then came – and still today comes – from natural
gas reforming and gasification. Fujishima's and Honda's findings have
led to other advancements in photocatalysis; in 1977, Nozik
discovered that the incorporation of a noble metal in the
electrochemical photolysis process, such as platinum and gold,
among others, could increase photoactivity, and that an external
potential wasn't required. Future research conducted by Wagner and
Somorjai (1980) and Sakata and Kawai (1981) delineated the
production of hydrogen on the surface of strontium titanate (SrTiO3)
via photogeneration, and the generation of hydrogen and methane
from the illumination of TiO2 and PtO2 in ethanol, respectively.
Research and development in photocatalysis, especially in
electrochemical photolysis of water, continues today, but so far,
nothing has been developed for commercial purposes. In 2017, Chu
et al. assessed the future of electrochemical photolysis of water,
discussing its major challenge of developing a cost-effective, energy-
efficient photoelectrochemical (PEC) tandem cell, which would,
“mimic natural photosynthesis.”
->Types of photocatalysis
1.Homogeneous photocatalysis
In homogeneous photocatalysis, the reactants and the
photocatalysts exist in the same phase. The most commonly used
homogeneous photocatalysts include ozone and photo-
Fenton systems (Fe+ and Fe+/H2O2). The reactive species is the •OH
which is used for different purposes. The mechanism of hydroxyl
radical production by ozone can follow two paths.
O3 + hν → O2 + O(1D)
O(1D) + H2O → •OH + •OH
O(1D) + H2O → H2O2
H2O2 + hν → •OH + •OH
Similarly, the Fenton system produces hydroxyl radicals by the
following mechanism[19]
Fe2+ + H2O2→ HO• + Fe3+ + OH−
Fe3+ + H2O2→ Fe2+ + HO•2 + H+
Fe2+ + HO• → Fe3+ + OH−
In photo-Fenton type processes, additional sources of OH radicals
should be considered: through photolysis of H2O2, and through
reduction of Fe3+ ions under UV light:
H2O2 + hν → HO• + HO•
Fe3+ + H2O + hν → Fe2+ + HO• + H+
The efficiency of Fenton type processes is influenced by several
operating parameters like concentration of hydrogen peroxide, pH
and intensity of UV. The main advantage of this process is the ability
of using sunlight with light sensitivity up to 450 nm, thus avoiding the
high costs of UV lamps and electrical energy. These reactions have
been proven more efficient than the other photocatalysis but the
disadvantages of the process are the low pH values which are
required, since iron precipitates at higher pH values and the fact that
iron has to be removed after treatment.
2.Heterogeneous photocatalysis
Heterogeneous catalysis has the catalyst in a different phase from
the reactants. Heterogeneous photocatalysis is a discipline which
includes a large variety of reactions: mild or total oxidations,
dehydrogenation, hydrogen transfer, 18O2–16O2 and deuterium-alkane
isotopic exchange, metal deposition, water detoxification, gaseous
pollutant removal, etc.
Most common heterogeneous photocatalysts are transition metal
oxides and semiconductors, which have unique characteristics.
Unlike the metals which have a continum of electronic states,
semiconductors possess a void energy region where no energy levels
are available to promote recombination of an electron and hole
produced by photoactivation in the solid. The void region, which
extends from the top of the filled valence band to the bottom of the
vacant conduction band, is called the band gap. When a photon with
energy equal to or greater than the materials band gap is absorbed
by the semiconductor, an electron is excited from the valence band
to the conduction band, generating a positive hole in the valence
band. Such a photogenerated electron-hole pair is termed
an exciton. The excited electron and hole can recombine and release
the energy gained from the excitation of the electron as heat.
Exciton recombination is undesirable and higher levels lead to an
inefficient photocatalyst. For this reason efforts to develop functional
photocatalysts often emphasize extending exciton lifetime,
improving electron-hole separation using diverse approaches that
often rely on structural features such as phase hetero-junctions
(e.g. anatase-rutile interfaces), noble-metal nanoparticles, silicon
nanowires and substitutional cation doping. The ultimate goal of
photocatalyst design is to facilitate reactions between the excited
electrons with oxidants to produce reduced products, and/or
reactions between the generated holes with reductants to produce
oxidized products. Due to the generation of positive holes and
electrons, oxidation-reduction reactions take place at the surface of
semiconductors.
In one mechanism of the oxidative reaction, the positive holes react
with the moisture present on the surface and produce a hydroxyl
radical. The reaction starts by photo-induced exciton generation in
the metal oxide surface (MO stands for metal oxide):
MO + hν → MO (H+ + e−)
Oxidative reactions due to photocatalytic effect:
H+ + H2O → H+ + •OH
 2 H+ + 2 H2O → 2 H+ + H2O2
H2O2→ 2 •OH
Reductive reactions due to photocatalytic effect:
e− + O2 → •O2−
•O2− + H2O + H+ → H2O2 + O2
H2O2 → 2 •OH
Ultimately, the hydroxyl radicals are generated in both the reactions.
These hydroxyl radicals are very oxidative in nature and non selective
with redox potential of (E0 = +3.06 V)
Photocatalysis has long been studied for clean energy and
environmental applications. Over the past two decades, the number
of applications based on photocatalysis has increased sharply, while
a wide range of materials systems have been developed [1–4].
Photocatalysis has been of particular interest in the production of
hydrogen from water using solar energy [5]. Further, conversion of
CO2 to hydrocarbons (fuels) is also of significant interest, as it is a
solution to reduce CO2 emissions across the globe [6,7]. Apart from
the clean energy generation, photocatalysis has several promising
applications in the environmental field. Some of the applications
include degradation of volatile organic compounds (VOC) for water
treatment [8], germicide and antimicrobial action [9–11], de-
coloration of industrial dyes [12–14], nitrogen fixation in agriculture
[15], and removal of NOx/SOx air pollutants [16–19]. These
applications have driven the development of variety of materials
systems which are suitable for specific applications.
->DIFFERENT TYPES OF PHOTOCATALYST-:
Metal like Ag,Au,Fe,Pt,ZnO,are used as photocatalyst,which enhance
photocatalatic activity. Also TiO2-based materials are the most
studied for photocatalytic applications, ternary and other complex
oxide systems have been increasingly explored as photocatalysts.
Among the various classes of materials studied, perovskites-based
photocatalysts have unique photophysical properties and offer
distinct advantages.
->PERVOSKITE BASED PHOTOCATALYST-:
Pervoskite is also used as a good photocatalyst as it
possesses photophysical as well as photochemical properties.
Perovskites are the class of compounds presenting the
general formula ABO3. Generally, in this crystal structure, the A site
is occupied by the larger cation, while the B site is occupied by the
smaller cation. Perovskites are one of the most important families of
materials exhibiting properties suitable for numerous technological
applications [20]. Perovskite compounds such as PbZrO3, BaTiO3,
PbTiO3 are most commonly used piezoelectric compounds [21].
BiFeO3 thin films show multiferroic behavior [22], while compounds
such as SrTiO3 have shown excellent photocatalytic properties
[23,24]. The origin of such properties lies in the crystal structure of
perovskites. The perovskite crystal structure has corner connected
BO6 octahedral and 12 oxygen coordinated A cations, located in
between the eight BO6 octahedral . The perfect structure of the
octahedral connection results in a cubic lattice. However, depending
on the ionic radii and electronegativity of the A and B site cations,
tilting of the octahedral takes place, which gives rise to lower
symmetry structures. As seen from the crystal structure, B site
cations are strongly bonded with the oxygen (or any other anion)
while, A site cations have relatively weaker interactions with oxygen.
Depending on the type of the cations occupying the lattice sites,
these interactions could be altered to yield the different perovskite
crystal geometries.

->STRUCTURE OF PERVOSKITE-:
Perovskite-type oxides, originated from CaTiO3,
are a family of oxides having the general formula ABO3 (where A is a
rare or alkaline earth metal and B is a first row transition metal),
wherein cations with a large ionic radius coordinate to 12 oxygen
atoms and occupy A-sites and cations with a smaller ionic radius are
six-coordinate and occupy B-sites (Fig-1 )[12]
 (Fig 1;structure of ABO3 pervoskite)

Photocatalysts are semiconductor with a band gap between 1.4 and

3.8 eV [12]. The type, structure and morphology of photocatalysts as
well as an effective electric field inducing the separation of
photogenerated electron-hole pairs at the interface of the individual
semiconductors reduces the probability of electron-hole
recombination, are very important properties determining the
degradation of organic pollutants. Since in 1953 Parravano reported
that NaNbO3, KNbO3, and LaFeO3 can be used for CO oxidation, the
application of perovskite oxides to heterogeneous photocatalysis
increased .Since in 1953 Parravano reported that NaNbO3, KNbO3,
and LaFeO3 can be used for CO Oxidation, the application of
perovskite oxides to heterogeneous photocatalysis increased .
As was mentioned above, an ideal perovskite has cubic crystal
structure (space Group, Pm 3m, corner-sharing network of BO6
octahedra, with the B ion in its center, the A Ion positioned on a
dodecahedral site in the middle of the cube), However, the real
perovskite ABO3 exhibited lattice distortion to varying degrees
(octahedra are tilted Around its center), thereby resulting in the
transformation of crystal phases in the following Sequences:
orthogonal, rhombohedral, tetragonal, monoclinic, and triclinic
phase, Depending on the details of the octahedral rotations.
Moreover, it is well known that, rotations of the oxygen octahedral
has important Impact on crystal field and thus changes the dipole
and electronic band structures, thereby Influencing the behaviors of
photogenerated charge carriers, including excitation, transfer, And
redox reaction, in whole photocatalytic process . This is due to the
fact that the octahedral rotations influence the B–O bond length and
B–O–B angle due to the shift of the Oxygen ions from the edges of
the cubic perovskite structure .
The structure, size and potential applications of perovskite oxides
materials are strongly influenced by the synthesis process; therefore
a lot of research is aimed both at its Processing and application. The
development of innovative processing methods through Chemistry
permits one to lower the preparation temperature and to improve
homogeneity and reproducibility of the products for the synthesis of
ultrafine and chemically pure Powders of mixed-metal oxides. Most
of the perovskite photocatalysts are still prepared by conventional
solid state reactions where particles are typically on a micron scale,
which limits their commercial applications due to lower light
absorption in the visible region and short lifetimes of the excited
states . As an alternative route, several methods have been reported
for the synthesis of perovskite oxides, such as: combustion
synthesis , sol-gel method , thermal decomposition of bimetallic
compound , sonochemical method , microemulsion method ,
polymerisable complex method , the polyvinyl alcohol (PVA) route ,
electrospinning method , coprecipitation method , microwave-
assisted method . Among the various methods, hydrothermal
method is a facile dominant tool for the synthesis of anisotropic
nanoscale material. Significant advantages of this method are
controlled size, low temperature growth, cost effectiveness and less
complicated . AVO3 oxides were reported for most of the divalent
elements as A-cation . For alkali-Earth elements (except Mg) their
structures are threedimensional frameworks consisting of Corner-
shared, regular or slightly distorted, VO6 octahedral. Among them,
extensive attention Was focused on silver vanadium oxides
nanomaterials due to their potential applications in
Photocatalysis.For vanadium oxides the unique hybridized valence
bands (V 3d, O 2p, and Ag 4d orbitals) lead to a narrow band gap and
highly dispersed valence bands. For, There are many evidences for
the photocatalytic activity of LaFeO3, But, there are a few reports
about photoactivity of remaining AFeO3 photocatalysts, so
Investigation of iron-based rare earth perovskites and impact of
particular rare earth metal On electronic and photocatalytic
properties of ferrites is necessary. Perovskite alkaline earth Stannate
with ASnO3 (A = Ca, Sr and Ba) general formulae has very interesting
properties. Among them, SrSnO3 has been applied as a photocatalyst
material . This Effective photocatalytic activity can be attributed to
the spatial structure of SrSnO3, in which The three-dimensional
network of corner- sharing SnO6 octahedra can help charge carriers
to Move more easily and the octahedral tilting distortion has a
positive effect on local charge Separation.
Because of the structural features, designing of perovskite-type
oxides gives a possibility to Use almost 90% of the metallic natural
elements of the Periodic Table and offer the way to Correlate solid
state chemistry to photocatalytic properties. Table 1 presents list of
selected Groups of perovskite oxides, which can be used as a
potential photoactive nanomaterials, Taking into account their band
gap energy and crystal structure. Many of them are still Unexamined
during photocatalytic processes.
->TYPES OF PERVOSKITE-
Pervoskite is mainly classified into three
types.A.Simple perovskite,B.double perovskite,C.Mixed perovskite.
->Again simple pervoskite is classified into 3 types,
a.ABO3 types
b.layered structure pervoskite
c.hybrid organic and inorganic pervoskite

a.AB03 Types- The perovskite oxides (ABO3) are originated from

CaTiO3 and are widely studied for various photocatalytic applications
owing to their high stability, structural tunability, and excellent
photocatalytic activity. The mineral form of CaTiO3 was discovered
by a German scientist, Gustav Rose in the Ural mountains in 1839,
and it was termed as “perovskite” in tribute to a renowned Russian
mineralogist Count Lev Aleksevich von Perovski.17 Currently, several
perovskites have been found, and they constitute a broad class of
materials with ABO3 type structure. Inthe ABO3 crystal,the size
ofA2+ isgreaterthan B4+
andoxygenexistsasO2−;additionally,severaloftheelementsof the
periodic table can be adjusted at A and B-sites resulting in a huge
family of such materials.18 The availability of these
differentsitesallowstheresearcherstoreplaceordopedifferent
elementsandtofabricatenewmaterialswithhighphotocatalytic activity.
An ideal ABO3 perovskite holds cubic symmetry as
showninFigure2a,wheretheA-cationsare12-foldcoordinated and lies
at the center of the cube, whereas the B-cations are coordinated
with 6 oxygen anions in an octahedral fashion

structure of ABO3
type pervoskite
ABO3 pervoskite such as LaNiO3 ,NaNiO3,BaBiO3 etc are used as
photocatalyst and also help in degradation in methylene blue

b.Layered structure pervoskite - In layered perovskite structure, the

network arrangement of octahedrons has boosted the mobility
charge carriers with high quantum yield efficiency . Hua et al. have
been synthesized N-doped La2Ti2O7 decorated on graphene sheets
through the attachment of Ti-N bond, Ti-C bond, and oxynitrides. The
composite material shows high photocatalytic activity for the
decomposition of bisphenol A under visible light irradiation and
degrades 81% within 300 minute. The mixing of N 2p states and O 2p
states extend optical adsorption characteristics of the composite.
Again, the presence of graphene enhances the ability for the charge
separation and transformation that enhance catalytic activity [30].
Heterojunction formation by the combination of oxygen vacant
bismuth tungstate nanosheets (BWO-OV) and oxygen-enriched
graphitic carbon nitride (OCN) show high photocatalytic efficiency for
tetracycline degradation. This 3D Z-scheme heterojunction built an
electric field that accelerates the interfacial charge transfer. Under
light irradiation, electrons are excited from Bi 4p orbital to Bi 6p
orbital and form an electric field that reduce recombination rate of
charge carriers [31]. Bi2WO6 has been grown vertically on Ta3N5
nanofibers to prepare visible light active Bi2WO6/Ta3N5Z-scheme
heterojunction photocatalyst.This type pervoskite is used as
photocatalyst in pollutant degradation.
c.Hybrid organic-inorganic pervoskite –
The general formula of hybrid organic–inorganic perovskites is ABX3
where A, B, X represent an organic cation, an inorganic metal and a
halogen element respectively. Such types of hybride perovskites
show much affectivity in photocatalytic application due to fast
electron and hole mobility, high absorption coefficient, suitable
bandgap, reduced rate of electron-hole recombination [33, 34]. This
type of perovskite is also termed as revolutionized photovoltaics due
to their 25.2% power conversion efficiency [35]. The perovskite show
excellent properties for dye degradation, hydrogen evolution, CO2 to
CO, photo-polymerization reduction through photocatalytic pathway
[35, 36]. Lead free methylammoniumiodobismuthate perovskite
((CH3NH3)3Bi2I9) shows high degradation efficiency for RhB, MB,
reactive blue under visible light irradiation. The presence of carbon
atom in the catalyst play several role for good catalytic activity of the
sample like it increases surface acidity, decrease electron-hole
recombination rate, broaden visible light absorption capability. In the
degradation mechanism, photo-generated holes follow one electron
oxidation step for the production of hydroxyl radicals. These hydroxyl
radicals are mainly responsible for the decomposition of the
chromophoric dye structure to organic acid and alcohols [34].
Narrow band gap (2 eV) characteristics cesium bismuth iodide
(Cs3Bi2I9) has been anchored with UV100–TiO2 nanoparticles to
increase visible light absorption capacity [1]. Organic-inorganic
hybrid bromide perovskite shows good photocatalytic activity in
aqueous media by the formation of composite with MOF.
Nanocomposite MAPbBr3@ZIF-8 (MA represent methyl amine, ZIF-8
represent zeoliticimidazolate framework) show excellent stability in
aqueous media and visible light activity for the decomposition of
organic pollutants. In-situ hydroxyl radicals are formed from the
composite materials and take an important role for the degradation
of methyl orange under visible or sunlight irradiation [37]. Graphitic
carbon nitride (GCN) and cesium lead halide perovskite (CsPbBrCl2)
based type-II heterojuntion catalyst degrade Eosin B under visible
light irradiation. 30 mg GCN content GCN-CsPbBrCl2 composite
material show 94% Eosin B degradation efficiency in 120 min. The CB
of CsPbBrCl2 is more negative than GCN and VB of GCN is more
positive than other. This type of position favours the separation of
electron and hole for the creation of ROS at the surface of the
composite material. The adsorbed dye molecule at the catalyst
surface easily degrades to the non-toxic substance by the reaction
with ROS.

(STRUCTERE OF Hybrid organic-inorganic pervoskite)

B.Double pervoskite- Compounds with general formula A2B2O6
belong to the double perovskites and they have similar crystal
structures to simple perovskites. Double perovskites have the basic
framework of corner connected BO6 octahedra and A cations
enclosed within, however, the connectivity of the octahedra may
differ from structure to structure. Double perovskites could
accommodate different cations at the A or/and B sites, taking a
general form AA'BB'O6. Accommodation of different cations at the A
and B sites alters the photophysical properties of the compound
significantly. Among the binary oxides, only a few compounds are
known to have band gap values in the visible region (narrow gap),
e.g., Fe2O3, WO6, CuO, Bi2O3. However, these materials suffer from
insufficient CB potential for hydrogen evolution. Some of the
materials also suffer from poor stability and low mobility of
photoexcited charges. On the other hand, many of the binary oxides
are known to be efficient photocatalysts, however only activated by
UV radiation (wide gap). Complex compounds offer a possibility of
combining the elements from ‘narrow gap’ and ‘wide gap’ binary
compounds to exploit the properties of both types of oxides, and
thus are potentially useful as visible light photocatalysts. The
following section reviews photocatalytic properties of double
perovskites which are visible light active.Sr2FeNbO6,La2FeTiO6 etc
are double pervoskites used for the degradation.

(FORMATION OF DOUBLE PEROVOSKITE)

C.Mixed Oxide Pervoskite-
 Mixture of oxides and nitrides or oxides
and sulphides has been developed to engineer the band structure of
the oxide photocatalysts suitable for the visible light absorption.
Oxynitride and oxysulphide photocatalysts offer distinctive
advantages over their doped counterparts. Earlier reports on
oxynitrides have revealed that replacing oxygen by nitrogen at lattice
sites, in a stoichiometric manner, narrows the band gap of the oxide,
by pushing the VBM into the band gap [129]. Such a modification
does not produce native point defects, which would otherwise be
introduced in the case of N doping. Stoichiometric incorporation of
nitrogen also avoids the localized states induced by N doping and
reduces the possible electron-hole recombination. Similar
composition containing mixtures of sulfur and oxygen i.e.,
oxysulfides, has been developed for photocatalysts.
Oxynitride compounds such as CaNbO2N,
SrNbO2N, BaNbO2N, and LaNbON2 belong to the perovskite type
crystal structures [131]. Photocatalytic hydrogen evolution has been
reported under visible light from methanol solution. SrNbO2N (Eg 1.8
eV) has been investigated in detail, where the photoelectrode of
SrNbO2N on a transparent conducting surface shows water oxidation
reaction under no external bias [132]. Tantalum counterparts of
these compounds were developed and utilized in the Z scheme
photocatalysis. Compounds such as CaTaO2N and BaTaO2N were
loaded with Pt co-catalyst and coupled with pt/WO3 for Z scheme
water splitting [133]. A solid solution of BaTaO2N and BaZrO3 was
formulated for hydrogen and oxygen evolution, which showed
improved performance compared with the individual photocatalysts
under visible light [134]. LaTiOxNy is another perovskite type
compound which shows high photocurrent density under visible light
[135]. Apart from the double perovskites belonging to the general
formula AA'BB'O6, there are a several other compounds that show
crystal structures close to the perovskite type structure, however
such compounds are not included in current review.

(Structure of mixed oxide pervoskites)

->WHY WE CHOOSE PERVOSKITE AS PHOTOCATALYST-:

Tanaka Et al. have detailed the advantages of perovskite
photocatalysts [56]:
They are formed from a wide variety of compositional and
constituent elements, but their essential, basic structures are similar.
1. Their bulk structures can be characterized well, and their surface
properties can be Fairly well extrapolated from the knowledge of
their well-defined bulk structures.
2. Their valency, stoichiometry, and vacancy can be varied widely.
3. Much information on their physical and solid-state chemical
properties has been Accumulated.
Also we know that the photocatalytic activity depends upon electron
transport a across semiconductor-electrolyte interface and is
affected by every factor like surface states, surface band structure
(depletion region induced electric field), and band bending, that
affect the Electron transfer. the band gap values to enable visible-
light absorption and band Edge potentials to suit the needs of
specific photocatalytic reactions makes perovskites a good
Photocatalyst .Again distortion in lattice affects the Electron
transport,ie photocatalytic activities of perovskite. It is found that
Some groups of perovskite materials such as titanate perovskites [57-
65],Tantalate perovskites [66-67], vanadium- and niobium-based
perovskites [73-78], and ferrite Perovskites [79-84] have shown
visible-light activity.
Several Researchs have done research on Application of perovskite
in different fields. Shi et al reviewed a ABO3-based photocatalysts for
water splitting.They summarized Different modification strategies
based on fundamental principle and process of Photocatalysis and on
the crystal structure and chemical component of perovskites [14].
Zhu Et al reviewed the preparation, characterization, and application
of perovskite oxides in Heterogeneous catalysis. Catalytic
performances of samples with different morphologies for Gas, solid,
and liquid-phase reactions have been overviewed [85].Kanhere
worked on visible light activite photocatalytic perovskite and decided
perovskite into two groups,1.Simple ABO3 type perovskite complex
perovskites (double, layered,etc)[86]
Now Researchers have been taking place how photocatalytic
properties of perovskite vary with changing reaction conditions and
Synthesis method. By changing or adjusting the reaction conditions
we can obtain perovskits with desired structure and physicochemical
property,while characterization gives the possibility to explore and
understand the textural structures and properties of the synthesized
photocatalysts.
There are various photocatalytic applications of perovskites like
application in solar cell, its anti bacterial activity,photocatalytic
splitting of water,photocatalytic degredation of organic dyes
etc.figure shows the Effect of pervoskite on photocatalysis.
 (Figure showing effect on pervoskite on photocatalysis)
Here we are doing a review on “Effect of pervoskite on
photocatalyst”.
->USE OF PERVOSKITE AS PHOTOCATALYST-:
Pervoskite plays a remarkable role
and have been used in the past few decade .In the particular section
the recent and pioneering reports on the utilization of pervoskite in
photocatalytic application such as organic pollutant degradation ,H2
energy ,CO2 reduction ,N2 fixation and a correlation is made for the
future roadmap pervoskite in these field .The subsections contain
information of different classes of pervoskite and how it is used for
making progress in photocatalytic applications.
A:Simple pervoskite with visible light response
1-> Titanate Perovskites
Titanate perovskites have been studied for photocatalytic
applications for a long time. Most of the titanate perovskites have
band gap energy (Eg) value more than 3.0 eV, however they show
excellent photocatalytic properties under UV radiation [1]. Using
these titanates as host materials, doping is widely used to alter the
optical properties and induce visible light absorption. TiO2 (anatase)
has a band gap of 3.2–3.4 eV and its CB potential is −0.3 to −0.6 eV
above the water reduction level [38]. Certain perovskite
titanateshave CB energies more negative than TiO2, making them
more suitable candidates for hydrogen generation. Titanates also
offer good photostability and corrosion resistance in aqueous
solutions. In this section, a detailed review of MTiO3 (M = Sr, Ba, Ca,
Mn, Co, Fe, Pb, Cd, Ni) systems is presented.
->SrTiO3-:
SrTiO3 is a simple cubic (Pm3m, a = 3.9 Å) perovskite with an indirect
band gap of 3.25 eV [39]. When loaded with a co-catalyst such as Rh
or NiOx, SrTiO3 shows stoichiometric water splitting under UV
radiation [40] and has been studied extensively for developing visible
light water splitting catalysts. Doping of the Ti site with Mn, Ru, Rh,
and Ir was of significant interest in early days [41]. It is found that
these dopants induce mid-gap states in the band gap allowing visible
light absorption [42]. Mn and Ru doping are found useful for O2
evolution, while dopants like Ru, Rh, and Ir are suitable for H2
evolution [41]. Rh-doped SrTiO3 thin films also shows cathodic
photocurrent from overall water splitting under visible light, where
7% Rh doped SrTiO3 showed 0.18% incident photo-to-electron
conversion efficiency (IPEC) under 420 nm irradiation [43]. Using Rh-
doped SrTiO3 as a H2 evolving photocatalyst, various Z scheme
systems have been developed. In a significant demonstration, a
novel electron mediator [Co(bpy)3]3+/2+ was used for Rh-doped
SrTiO3 with BiVO4 photocatalyst. Such a system showed a solar
energy conversion efficiency of 0.06% under daylight [44]. Efforts in Z
scheme photocatalysis have also been targeted towards eliminating
the need for electron mediators by preparing composite
photocatalysts. In such systems, electrons from an O2 evolving
photocatalyst recombine with holes from a H2 evolving
photocatalyst at the interface of the composite. The quality of the
interface and the band alignment of the two semiconductors are
important factors for the successful realization of mediator-free type
Z schemes.
2. BaTiO3
Like SrTiO3, Rh doping in BaTiO3 has been carried out and a quantum
yield of 0.5% under 420 nm was reported [52]. Being a hydrogen
evolving catalyst, this material has also been used as Z scheme with
Pt/WO3 for overall water splitting [52]
3. CaTiO3
Calcium titanate is one of the common perovskite minerals with a
band gap of 3.6 eV. Cu doping in CaTiO3 is widely studied and visible
light-driven photocatalytic water decomposition has been reported
[53]. Cu doping not only induces visible light absorption, but also
enhances hydrogen evolution under UV radiation when NiOx co-
catalyst is used. Studies of such doped systems, where dopants
enhance the photocatalytic activity host materials are important to
design efficient photocatalysts. Detrimental effects of doping on the
properties such as electron-hole recombination, electron/hole
effective mass, and reduced crystallinity should be studied and
reported in detail. These studies are useful to gain insights on the
photocatalytic activities of the doped systems. Co-doping of Ag and
La at CaTiO3 has been done to narrow the band gap and induce
visible light absorption [54]. DFT studies also indicate that like
SrTiO3, TiO2-terminated CaTiO3 surfaces possess the capability of
visible light absorption [55]. Along with alkali titanates, several
transition metal titanates show promise for visible light
photocatalysis. Figure 8 shows the empirically estimated band
diagram of the MTiO3 systems with respect to water oxidation and
reduction levels.
4.CoTiO3
CoTiO3 has a band gap in the visible region (Eg 2.28 eV). Recently this
compound has been investigated for photocatalytic O2 evolution
reaction without any co-catalyst [57]. A yield of 64 μmol·g−1·h−1
was obtained under visible light. CoTiO3 and TiO2 composites have
been studied for 2-propanol mineralization, however it is worth
noting that the band positions of CoTiO3 are not suitable for
transferring photoexcited charges to TiO2, offering no significant
advantage [58].
5. NiTiO3
NiTiO3 has a reported band gap of around 2.16 eV and its light
absorption spectra show peaks in visible region corresponding to
crystal field splitting [59]. NiTiO3 nanorods have been employed for
degradation of nitrobenzene under visible light [59].
6. FeTiO3
FeTiO3 has a band gap of 2.8 eV and thus it absorbs visible light.
Composites of FeTiO3 and TiO2 are studied for the degradation of 2-
propenol under visible light. In such composites, TiO2 acts as hole
capturing phase, thereby separating the electron-hole recombination
[60].
.7. CdTiO3
CdTiO3 (Eg 2.8 eV) nanofibers were synthesized and studied for the
photodegradation of rhodamine 6G (R6G) dye [61].
8. PbTiO3
PbTiO3 has a band gap of 2.75 eV and has been investigated for
visible light photocatalysis. Core-shell particles of nano-TiO2 (shell)
and micro-PbTiO3 (core) were studied for effective charge separation
and photocatalytic performance [62]. It is worth noting that PbTiO3
is ferroelectric in nature while TiO2 is dielectric. It is shown that the
ferroelectric behavior helps electron-hole separation at the interface
of two particles.
9. MnTiO3
Further, F doped MnTiO3 shows improved separation of charges and
degrades rhodamine B under visible light [63]. Photocatalytic activity
of MnTiO3 perovskite nanodiscs for the removal of organic
pollutants.Here MnTiO3 was synthesized by hydrothermal
method,with particle of thickness 16nm, diameter 291 nm . The
photocatalytic degradation of 89.7%, 80.4%, 79.4%,79.4% was
observed for MB,RhB,MO and CR under Xenon lamp
b.Vanadium and Niobium Based Perovskites
Similar to tantalum (Ta)-based photocatalysts, Vanadium,Niobium
(Nb)-based photocatalysts show good photocatalytic activity under
UV irradiation.
1. KNbO3 and NaNbO3
Both KNbO3 (Eg 3.14 eV) and NaNbO3 (Eg 3.08 eV) have band gap
values in the UV-responsive region, however suitable modifications
of the band structure have resulted in visible light photocatalysis
[89]. N-doped NaNbO3 is a known visible light photocatalyst for the
degradation of 2-propanol [90]. Nitrogen doping in KNbO3 has been
studied for water splitting as well as organic pollutant degradation
[91]. First principles calculations predict that co-doping of La and Bi
would induce visible light response in NaNbO3 [92]. Recent work on
ferroelectric perovskites of KNbO3-BaNiNbO3 shows that the solid
solution of these compounds could absorb six times more light and
shows fifty times more photocurrent than others [93]. Although
photocatalytic properties are not known, this is an attractive
candidate for visible light driven photocatalyst.
2. AgNbO3
Replacing an A site alkali metal by silver reduces the band gap of the
perovskite and AgNbO3 has a band gap of around 2.7 eV. Studies
have shown that the photocatalytic activity of AgNbO3 strongly
depends on the shape of the particles: polyhedron-shaped particles
are favorable for O2 evolution reactions [94]. Further, La doping was
found to enhanced the hotocatalytic performance by 12-fold for
gaseous 2-propenol degradation [95].
3. AgVO3
AgVO3 exists in two types of crystal structures, viz. α-AgVO3 (Eg 2.5
eV) and β-AgVO3 (Eg 2.3 eV) [96]. Both phases are photocatalytically
active. However, β-AgVO3 shows better photocatalytic performance
than the α-phase. The CB potential of AgVO3 is not sufficient for H2
evolution, but it is suitable for the degradation of volatile organic
compounds (VOCs) and O2 evolution. β-AgVO3 nanowires show
excellent photocatalytic performance in the degradation of Rh B
[97]. Composites of AgBr-AgVO3 were reported to display
respectable efficiency for Rh B degradation [98], while Ag-loaded
AgVO3 has shown good performance for degradation of bisphenol
[99].
.4. CuNbO3
CuNbO3 crystallizes in the monoclinic structure and has a band gap
of 2.0 eV. It is an intrinsic p-type semiconductor and has shown 5%
efficiency for photon to electron conversion when used as a
photocathode. Being a stable material under irradiation, more
investigations should be carried out on this material [100]. Tantalum,
niobium, and vanadium belong to the same group in the periodic
table. Perovskite compounds of these elements show decreasing
band gap and CB potential values. This trend is attributed to the 3 d,
4 d and 5 d orbital energies in V, Nb and Ta, respectively.
c. Ferrite Perovskites
Most of the ferrite perovskites have their native band gaps in the
visible region. Hematite and other iron oxide compounds have
known shortcomings such as short exciton diffusion length, low
electron conductivity, and lower conduction band edge potential
[101]. However certain ferrite-based perovskites have shown good
photocatalytic activities, circumventing the shortcomings seen in
binary iron oxides.
1. LaFeO3
LaFeO3 (Eg 2.1 eV) has been explored for degradation of pollutants
as well as hydrogen evolution under visible light. Sol-gel synthesized
LaFeO3 loaded with Pt co-catalyst showed high yield of hydrogen
evolution (3,315 μmol·h−1·g−1, in the presence of ethanol) under
400 W tungsten light source [68]. Another study on this phase
demonstrates high yield of H2 and O2 (1290 μmol and 640 μmol
after three hours, respectively), without any co-catalyst loading
[102]. Further, Thirumalairajan et al. showed shape dependent
photocatalytic activity of LaFeO3 for Rh B dye under visible light
(>400 nm) [103]. Doping of Mn in LaFeO3 has also been studied and
it shows higher photocatalytic activity [104]. Lanthanum ferrite has
demonstrated excellent photocatalytic activity under visible
irradiation; however, studies on the fundamental photophysical
properties are lacking the literature. Understanding the reasons why
LaFeO3 is a better photocatalyst that Fe2O3, in terms of comparative
electronic properties such as electron-hole separation, mobility,
photoexcited lifetimes etc. is important for further development in
ferrite-based photocatalyst. Photocatalytic property of perovskite
LaFeO3 synthesized by sol-gelprocess and vacuum microwave
calcination. 2016 [88].It’s photocatalysis activity was studied by
applying it for degradation of methyl orange and methylene blue. It
was found that vaccum microwave calcination (low
temperature,short duration) has superior photodegradation
efficiency compared to particles prepaired conventionall calcination
method. The MB and MO dye solution in presence of LaFeO3
becomes colourless in 240 min under visible light irradiation.[88]

2. BiFeO3
BiFeO3 is a known ferroelectric material with a band gap of 2.3 eV.
Recent studies have shown that BiFeO3 could be used as a visible
light photocatalyst [105]. The ferroelectric properties of BiFeO3
could be utilized to enhance the electron-hole separation and
improve the photocatalytic activity. Figure 10 shows the effect of
polarization on the band bending of BiFeO3 particles. Band bending
affects the separation of electrons and holes in the space charge
region and thus affects the photocatalytic activity. Gd-doped BiFeO3
show enhanced photocatalytic degradation for rhodamine B
degradation attributed to its ferromagnetic behavior [106]. Ca
doping in BiFeO3 leads to improved performance for photocatalytic
degradation of Congo Red dye [107]. In another study, cations such
as Y, Mg and Al were doped in BiFeO3 and their photocatalytic
performance was evaluated by degradation of Rh B under 400 nm
radiation. The degradation performance was limited to C/C0 of 0.8
within three hours [108]. The study of the effects of ferroelectric
behavior on photocatalytic performance is a relatively new topic and
it generally shows impressive activity for the degradation of organic
pollutants, however, more experimental evidence and understanding
are needed to establish a correlation between ferroelectric behavior
and photocatalytic activity. Further studies on the stability and
toxicity of bismuth-based materials should be carried out for
realizing their practical applications. It is further noted that the tilting
of octahedra in the perovskite crystal structure significantly affects
its electronic properties. Nevertheless, the effect of tilting of
octahedra on the photophysical properties such as electron-hole
separation, electron transport, delocalization of charges has not been
studied in detail. Such studies will prove useful in establishing the
importance of perovskites in the field of photocatalysis.

D. Other Perovskite Systems -:

Among the other perovskite photocatalysts, compounds of bismuth,
cobalt, nickel, and antimony (occupying B sites) have band gap values
in the visible region. Pentavalent bismuth perovskites are known to
be active photocatalysts under visible light radiation. Perovskites
such as LiBiO3 (Eg 1.63 eV), NaBiO3 (Eg 2.53 eV), KBiO3 (Eg 2.04 eV),
and AgBiO3 (Eg 2.5 eV) have all been investigated for degradation of
organic pollutants [112]. NaBiO3 shows better photocatalytic
performance for phenol and methylene blue (MB) degradation as
compared to other Bi5+ containing perovskites as well as P25-TiO2
[112]. NaBiO3 is also reported to have higher photocatalytic activity
than N-doped TiO2 photocatalyst [113]. NaBiO3 and BiOCl
composites have been studied for enhanced electron-hole
separation and subsequent photocatalysis [114]. AgBiO3 was shown
to be effective in restricting the growth of Microcystis aeruginosa
under simulated solar light [115]. This study shows that AgBiO3 with
band gap energy around 2.5 eV could be a potential algaecide under
natural light. DFT studies show that NaBiO3 has a strong band
dispersion arising from Na 3s and O 2p hybridized orbitals, which
contributes to the higher photocatalytic activity [112]. LaCoO3 has a
band gap value of 2.7 eV and oxygen deficient LaCoO3 (LaCoO3-δ)
has been studied for MO degradation (>400 nm) [116]. Other
compounds such as LaNiO3 has been studied for MO degradation
using wavelengths greater than 400 nm [117]. Cu doping in LaNiO3
has been studied for improved H2 evolution [118]. Ilmenite type
AgSbO3 has an absorption edge onset at 480 nm, and it has been
demonstrated for O2 evolution under sacrificial agent as well as
degradation of MB, RhB, and 4-chlorophenol [119]. Further, solid
solution of LaCrO3 and Na0.5La0.5TiO3 was developed for hydrogen
evolution [120]. Recently, Gd2Ti2O7/GdCrO3 composite was
reported as photocatalyst p-n junction photocatalyst [71]. The study
shows that GdCrO3 has a band gap of 2.5 eV and is responsible for
the visible light absorption [72].
E. Complex Perovskite Materials
1. Double Perovskites
Compounds with general formula A2B2O6 belong to the double
perovskites and they have similar crystal structures to simple
perovskites. Double perovskites have the basic framework of corner
connected BO6 octahedra and A cations enclosed within, however,
the connectivity of the octahedra may differ from structure to
structure. Double perovskites could accommodate different cations
at the A or/and B sites, taking a general form AA'BB'O6.
Accommodation of different cations at the A and B sites alters the
photophysical properties of the compound significantly. Among the
binary oxides, only a few compounds are known to have band gap
values in the visible region (narrow gap), e.g., Fe2O3, WO6, CuO,
Bi2O3. However, these materials suffer from insufficient CB potential
for hydrogen evolution. Some of the materials also suffer from poor
stability and low mobility of photoexcited charges. On the other
hand, many of the binary oxides are known to be efficient
photocatalysts, however only activated by UV radiation (wide gap).
Complex compounds offer a possibility of combining the elements
from ‘narrow gap’ and ‘wide gap’ binary compounds to exploit the
properties of both types of oxides, and thus are potentially useful as
visible light photocatalysts. The following section reviews
photocatalytic properties of double perovskites which are visible
light active.
2. Sr2FeNbO6
Sr2FeNbO6 has a cubic crystal structure and a band gap of 2.06 eV. In
its pristine form, it is a known photocatalyst, while 7% Ti doping at Fe
site has shown two time enhancement of the hydrogen generation in
methanol solution. A total of 28.5 µmol·h−1 and 650 µmol·h−1 were
reported in presence of sacrificial agents and with 0.2% Pt as co-
catalyst [121]. W doping in Sr2FeNbO6 has also been studied and
demonstrated enhancement to hydrogen evolution under visible
radiation [122].
3.La2FeTiO6
Hu et al. reported higher photocatalytic activity for La2FeTiO6 than
for LaFeO3 for degradation of p-chlorophenol under visible light
irradiation [123].
4.1.3. Other Double Perovskites
Rare earth and bismuth-based double perovskites were studied for
visible light photocatalysis. Compounds with general formula
Ba2RBiO6, (R = La, Ce, Pr, Nd, Sm, Eu, Gd, Dy), were prepared and
their photocatalytic activity was studied for MB degradation [124].
Authors found rare earth cation dependent photocatalytic
performance, where compounds such as Ba2EuBiO6, Ba2SmBiO6,
and Ba2CeBiO6 showed high photocatalytic activity. Complex
perovskites such as CaCu3Ti4O12 have also been studied for their
photocatalytic performance. CaCu3Ti4O12 was found to possess an
indirect band gap of 1.27 eV and Pt-loaded CaCu3Ti4O12 shows
degradation of MO under radiation greater than 420 nm [125].
Photophysical properties of certain double perovskite compounds
have been reported, however, more efforts are needed to
investigate photocatalytic properties of these materials. Compounds
such as Ba2CoWO6, Ba2NiWO6, Sr2CoWO6 and Sr2NiWO6 are stable
perovskites compounds for O2 evolution using sacrificial agents
[126]. Certain tantalum-based compounds have been studied for
degradation of organic compounds. N-doped K2Ta2O6 is known to
absorb visible light up to 600 nm and degrade formaldehyde under
visible light [127]. Our group demonstrated that Bi doping in
Na2Ta2O6 causes visible light absorption and degradation of MB
[128]. Although some work has been done with double perovskites
as photocatalysts, understanding of their fundamental properties is
limited. More work is needed to discover their advantages as visible
light photocatalyst and develop novel materials systems.
E.Mixed oxide pervoskite-
Mixture of oxides and nitrides or oxides and sulphides has been
developed to engineer the band structure of the oxide
photocatalysts suitable for the visible light absorption. Oxynitride
and oxysulphide photocatalysts offer distinctive advantages over
their doped counterparts. Earlier reports on oxynitrides have
revealed that replacing oxygen by nitrogen at lattice sites, in a
stoichiometric manner, narrows the band gap of the oxide, by
pushing the VBM into the band gap [129]. Such a modification does
not produce native point defects, which would otherwise be
introduced in the case of N doping. Stoichiometric incorporation of
nitrogen also avoids the localized states induced by N doping and
reduces the possible electron-hole recombination. Similar
composition containing mixtures of sulfur and oxygen i.e.,
oxysulfides, has been developed for photocatalysts. Mixed oxysulfide
perovskites of Sm2Ti2S2O5 (Eg 2.0 eV) is known for water oxidation
and reduction reaction for oxygen and hydrogen evolution,
respectively in presence of sacrificial agents under low photon
energy wavelengths of 650 nm. The band structure of this phase
reveals that the presence of sulphur narrows the band gap and
enables visible light absorption [130]. Oxynitride compounds such as
CaNbO2N, SrNbO2N, BaNbO2N, and LaNbON2 belong to the
perovskite type crystal structures [131]. Photocatalytic hydrogen
evolution has been reported under visible light from methanol
solution. SrNbO2N (Eg 1.8 eV) has been investigated in detail, where
the photoelectrode of SrNbO2N on a transparent conducting surface
shows water oxidation reaction under no external bias [132].
Tantalum counterparts of these compounds were developed and
utilized in the Z scheme photocatalysis. Compounds such as
CaTaO2N and BaTaO2N were loaded with Pt co-catalyst and coupled
with pt/WO3 for Z scheme water splitting [133]. A solid solution of
BaTaO2N and BaZrO3 was formulated for hydrogen and oxygen
evolution, which showed improved performance compared with the
individual photocatalysts under visible light [134]. LaTiOxNy is
another perovskite type compound which shows high photocurrent
density under visible light [135].

Photocatalytic properties of CoOx-loaded nano-crystalline perovskite

oxynitrides ABO2N (A ¼ Ca, Sr, Ba, La; B ¼ Nb, Ta) 2015[90]. Florian
Oehler prepared a highly crystalline niobium and tantalum based
oxyniyride perovskite by hydrothermal method. During Synthesis the
temperature was maintained 740°C for CaNbO2N and 1000°C for
BaTaO2N and particle size was found to be 27-146 nm. CoOx as co-
catalyst was located on the oxynitride particles resulting in a strong
increase of the photocatalytic activity upto 30% methyl orange
degradation within 3hours for SrNbO2N.CoOx. Photocatalytic methyl
orange degradation was performed by 50µM aq. solution of Methyl
Orange, 200mg/Lit catalyst for 3hrs ,with Xenon lamp (300-420nm)
[90] .
*Also metal halide pervoskite plays an important role in
photocatalytic applications. The recent renaissance in ABX3 hybrid
perovskite semiconductors has revolutionized photovoltaics,
enabling solutionprocessable solar cells that have now reached
23.3% power conversion efficiency.10−13 In addition to the
exceptional photovoltaic performance,

(reaction of metal halide pervoskite based photocatalyst)

Hybrid perovskite systems have also demonstrated breakthroughs in
piezoelectrics, high-gain photodetectors,light-emitting diodes,lasers
and transistors. The excellent photovoltaic and optoelectronic
performance is attributed to beneficial optoelectronic properties,
such as, strong light absorption, long charge-carrier lifetimes and
long charge-carrier diffusion lengths. Our previous work also
reported low trap densities and small surface recombination
velocities, leading to a noticeable enhancement of the
photogenerated carrier lifetime and mobility.Thus, given the
beneficial properties for photovoltaic applications, they also should
be of interest in photocatalytic applications. Here we report a cost-
effective, highly efficient and easy-toprocess photocatalytic system
centering on ABX3 Pb-halide perovskite nanocrystals (NCs) for direct
C−C bond formation reactions. To demonstrate their photocatalytic
characteristics, we explore a model reaction, α-alkylation of
aldehydes, a widely employed valuable chemical transformation.
Particularly, we demonstrate that APbBr3 NCs can directly
photocatalyze the α-alkylation reaction with high yield and without
N2-sparging. By slight modification of the reaction conditions, we
show that our photocatalytic system can selectively catalyze other
important chemical reactions, such as, sp3 C-couplings and alkyl-
halide reductions. The perovskite photocatalyst studied here are a
versatile material system easily prepared from earth-abundant
elements and low-cost starting materials.10 The as-prepared NCs are
not only stable in common organic solvents (Figures S1−5), but also
are effective in photocatalysis with a TON of over 52,000 for
αalkylation, 3 orders of magnitude higher than precious Ir or Ru
catalysts. As a result, the perovskite photocatalyst are much more
economical than Ir/Ru (2-order cost lower), rendering them as new
promising candidates for broad application in organic synthesis. The
exploration of the perovskites’ photocatalytic characteristics for
organic synthesis was inspired by a simple one-pot reaction. After
mixing of the readily available starting materials in an open vial, a
one-pot perovskite emissive suspension was formed due to the
solvents’ emulsion/deemulsion effect.28 To the resulting suspension
organic substrates 2-bromoacetophenone 1a, and octanal 2a are
added at room temperature. Upon blue-LED illumination, several
products are generated, including dehalogenated acetophenone 3a
(yield 76%), sp3 C-coupling product 4a (8%), and α-alkylation product
5a (7%). Next, we explore the photocatalytic selectivity toward the
desired product.

3.DISADVANTAGES OF PERVOSKITE BASED PHOTOCATALYST AND

FUTURE ASPECTS-:
➢ Pervoskite is useful in photocatalytic applications like in solar
cell,organic pollutant degradation,etc.but some pervoskite like
metal halide pervoskite,organic and inorganic metal based
pervoskite are very toxic to environment. So we should use eco
friendly metal pervoskite.
-> Lead-based Pervoskites have shown very promising performances
in photocatalytic processes, but due to the high and well-known
toxicity of Pb, for both the ecosystem and environment, it should be
replaced with more eco-friend elements.
-> Generally, germanium- and tin-based perovskite systems showed
rapid oxidation and uncontrolled crystallization, resulting in poorly
efficiency. Bismuth antimony-based MHPs showed promising results,
with stability comparable to lead-based MHPs [85]. However,
appropriate efficiencies, due to the unsuitable band gaps, have not
reached the traditional standards. Thus, a better understanding of
photogenerated carrier dynamics at the interfaces needs to be
addressed, in order to effectively improve the performance,
➢ Again the efficiency of perovskites upon certain dye are low ,so
some co-catalyst should be added or some improvements should be
done to make it more efficient.
More emphasis should be given to make the perovskite photocatally
active under visible light.
->More specifically, several methods have been tested in order to
enhance environmental stability in relation to target photocatalytic
reactions, including CO2 reduction, H2 evolution, organic matter
photodecomposition or organic transformations. The relative HOIPs
(hybrid organic inorganic perovskite) sensitivity to degradation by
polar molecules can be addressed by using low-polarity solvents for
CO2 reduction, such as ethyl acetate or acetonitrile, creating stable
photocatalytic reaction conditions. Further enhanced stability can be
achieved by combining HOIPs with graphene or graphitic carbon
nitrile, by passivation through the interaction between the surface
groups. In addition,the compositions withTiO2 or transition
structures can help to speed up the charge separation, by acting as
reaction sites to improve the overall stability [216]. Morphology
modification, and substitution of halogens in the HOIPs or the ions in
the A- and B-sites’ structure, have also been proven as suitable
approaches to enhancing the stability toward decomposition In the
same way,low-polarity solvents may be employed in photocatalytic
organic synthesis.
➢ It’s recyclability and stability under natural environment defines
it’s lifetime,i.e upto how long it will survive and able to degrade the
organic pollutants.

4.CONCLUSIONS->
From the above studies we can conclude that
perovskites have good photolytic property and they have band gap in
the range 1.4-3.8eV .here we have studied photocatalysis of CsPbX3,
LFeO3, CaNbO3N, BaTaO2N, CsPbI3, MnTiO3 zinc doped Co1-
xZn1.5FeO3, LaFeO3 nano perovskite. A large number of perovskite-
based compounds (over 80) have been studied for visible light driven
photocatalytic applications. Perovskite structures offer abundant
scope in designing novel compounds based on A and B site
occupancy, which gives rise to a wide range of materials systems
with unique properties. Among these compounds, photocatalysts
with pristine band gaps in the visible region such as LaFeO3, PrFeO3,
NaBiO3, and AgBiO3 (Table 2) show promising photocatalytic
performance under visible radiation (>400 nm). Although there are
reports on the photocatalytic activity of these compounds, detailed
studies on these materials are limited. M iteRGO-NiO composite
against various organic pollutants like Eosine B, MO, MB, RB5, RhB,
MV, MG, AB1, CR even in visible light. More efforts are needed to
understand the structure-property relations in such ferrites and
bismuth based compounds and improve their photocatalytic activity.
Among the wide band gap semiconductors, SrTiO3- and NaTaO3-
based photocatalysts are the most investigated systems. The
strategy of doping foreign elements in wide band gap photocatalysts
is widely used to induce visible light absorption and subsequently to
enable photocatalytic activity. Nonetheless, very limited knowledge
is available on the adverse effect of dopants on the photophysical
properties of the compounds (e.g., if the benefit derived from
dopant-induced visible light activity is overweighed by a loss of UV
light activity). This should be properly investigated in the future.
Appropriate dopants which retain the beneficial properties of the
host materials while inducing visible light responses should be
identified. Research work on complex perovskites show that these
compounds offer distinct advantages as compared with simple
perovskites.The results found were very impressive. So further
researches should be done both photocatalytic activity of perovskites
and its practical applications in future.
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