ChemCatChem - 2020 - Som - Advances in Nanomaterial Based Water Treatment Approaches For Photocatalytic Degradation of

Reviews
ChemCatChem doi.org/10.1002/cctc.201902081
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3 Advances in Nanomaterial-based Water Treatment
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Approaches for Photocatalytic Degradation of Water
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8 Ipsita Som+,[a] Mouni Roy+,[a, b] and Rajnarayan Saha*[a]
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ChemCatChem 2020, 12, 3409 – 3433 3409 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Reviews
1 Demand of pure drinking water is increasing day by day in line design of efficient photocatalysts. The oxidation rates and
2 with both a growing population and global industrialization. degradation efficiency of photocatalysts are governed by some
3 Studies in the past few decades on the application of advanced basic parameters, like organic pollutant concentration, photo-
4 oxidation processes (AOP) for the treatment of wastewater catalyst concentration, pH, reaction temperature, light intensity,
5 containing perilous organic pollutants, are promising when irradiation time, inorganic ions, oxidants, and these are also
6 compared to conventional water treatment methods. In case of discussed. Titania and titania based materials have many
7 *
AOP, generation of powerful oxidant radicals ( OH, HOO ) is
*
attractive properties (nontoxicity, less costly, advanced optical
8 crucial for the purpose of degradation. Several processes for the properties, high stability) towards photo degradation process.
9 in-situ generation of such highly reactive oxidants have been Several studies have been reported investigating the intermedi-
10 discussed. This Review highlights the literature reports on the ates produced during degradation process as well as the final
11 degradation of various organic pollutants (dyes, pharmaceut- degraded product, which might be toxic and/or hazardous to
12 icals, pesticides, herbicides, insecticides) by means of photo- the human as well as to the environment. This review
13 catalysis. A number of scientific investigations have been assimilates elaborate study on the mechanism of photocatalytic
14 performed, which elucidate suitable properties (band gap degradation of various organic pollutants.
15 energy, carrier transport, crystallinity etc.) for the deliberate
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1. Introduction into the environment, can also impose toxicity.[8,9] Some
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pharmaceutical compounds may cause long-term, irreversible
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The demand of safe and drinkable water is huge due to changes to the genome of micro-organisms.[10] Furthermore,
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exponential growth of population and global industrialization. some pharmaceuticals are endocrine disrupting compounds
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Contamination of ground water and surface water by industrial (EDCs) and beta-blocker causing adverse effects on the human
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effluents, dyes, fertilizers, pesticides and herbicides as well as endocrine system.[11,12,13] Increasing water pollution leads to not
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pharmaceutical wastes which comes from various type of only worsening water quality, but also imparts adverse effect
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industries like textile, fertilizer, pharmaceutical, petrochemical on aquatic ecosystem, human health, economic advancement
25
etc. and also from domestic activities, leads to daily colossal and social inflation.[14] Removal of pollutant contaminations
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water pollution.[1] Furthermore, the runaway water from agricul- from water to make it potable, is a big challenge. Biological
27
tural land contains a huge quantity of pesticides, insecticides, treatment is one conventional wastewater treatment technique.
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fertilizers, which are used for increasing crop quality and yield, Biological treatment is based on bacteria, nematodes, or other
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but also contribute to water pollution. This chemically contami- small organisms which are employed to break down organic
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nated water, if consumed, may lead to serious immediate wastes using normal cellular processes.[15] Some other techni-
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diseases like dysentery, typhoid, diarrhea, hepatitis, skin rash, ques are physio-chemical in nature like- adsorption, chemical
32
etc., while their prolonged intake is very noxious to human oxidation, coagulation, flocculation, flotation, electrochemical
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health.[2,3] Organic compounds used for coloring the textiles decomposition, membrane processes comprise of nanofiltra-
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have also been known to cause a serious health and environ- tion, reverse osmosis etc.[16] Certain chemicals (such as ozone,
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mental hazard. The excess dyestuff that does not bind to the hydrogen peroxide, Fenton reagent, NaOCl, etc.) are used in
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fibers during the coloring process is discharged into the some cases to degrade the organic contaminants in the water.
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environment producing serious environmental pollution. The The advantages of these methods are less investment, low
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existence of these untreated dyes in surface and subsurface energy consumption, simple and easy maintenance.[17] But these
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water even at very low concentrations lead to toxic effect on treatment techniques have some limitations as for example
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humans, aquatic lives and can initiate a lot of water borne they can only transfer the non- biodegradable component into
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diseases as for example hemorrhage, dermatitis, ulceration of sludge leading to formation of secondary waste product which
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skin, nausea, mucous membrane, perforation of nasal septum further required costly disposal or regeneration method.[18] In
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and severe irritation of respiratory tract.[4,5,6,7] Now-a-days the this regard advanced oxidation process (AOP), first proposed in
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pharmaceuticals and pharmaceuticals residues are considered the 1980s, has emerged as an effective route for water
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as emerging pollutants in water bodies. The waste from the purification.[19] The term ‘Advanced’ in advanced oxidation
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pharmaceutical industries and hospitals, which are dumped processes rely on the in-situ formation of powerful hydroxyl
47
radicals (.OH) in sufficient quantity to oxidize recalcitrant toxic
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[a] I. Som,+ Dr. M. Roy,+ Prof. R. Saha organic pollutants by attacking them non-selectively and
49
Department of Chemistry efficaciously. AOP can even leads to complete mineralization of
50 National Institute of Technology pollutants i. e. transformation of toxic pollutant into small
51 Durgapur 713209 (India)
E-mail: rajnarayan.saha@ch.nitdgp.ac.in molecules like carbon-di-oxide and water, generating less
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rnsahanitd@gmail.com sludge.[20] AOP can be categorized in two type’s viz homoge-
53 [b] Dr. M. Roy+ nous and heterogeneous photocatalytic oxidation. The hetero-
54 Department of Chemistry
Banasthali University geneous photocatalyst finds major application than homoge-
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Banasthali, Rajasthan 304022 (India) neous photocatalyst due to non-toxic, cheap, easy separation,
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[+] Both authors contributed equally to this manuscript recyclable property.[21] Thus, advanced oxidation process follow-
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ChemCatChem 2020, 12, 3409 – 3433 www.chemcatchem.org 3410 © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Reviews
ing heterogeneous photocatalysis proved to be more advanta- than the components alone which can be explained on the
1
geous than other methods.[22,23] basis of reduction of charge carrier (holes and electrons)
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Besides, there is a need for proper identification of recombination when the LaFeO3/TiO2 nanocomposite is irradi-
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intermediates as well as products, formed during such photo- ated under visible light.[29]
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catalytic degradation. Generation of Hazardous intermediates, Schünemann et al., applied advanced oxidation process for
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or polyaromatic and/or aromatic products after treatment the selective benzyl alcohol oxidation to benzaldehyde under
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process is unacceptable as it may even increase the level of visible light illumination using prepared inorganic halide
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toxicity of the treated water rather than making it pollutant- perovskites-TiO2 composite material, CsPbBr3/TiO2. This catalyst
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free. This requirement can be solved by studying the successive shows very good selectivity towards benzaldehyde (< 99 % at
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aliquots, while the degradation process, using several chroma- 50 % conversion).[30]
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tographic techniques like GC-MS,[24] HPLC,[25] LC–MS,[26] UPLC-
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MS[27] etc. Therefore, chromatographic monitoring of such
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photocatalytic process enables us to judge the effectiveness of
13 2. Different method involved in the generation
the heterogeneous photocatalyst towards pollutant degrada-
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tion into non-toxic open chain compounds or mineralized of oxidant radicals
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products. This provides us with the knowledge of the suitability
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and future perspective of the designed photocatalyst in dealing It is clear from the above discussions that in-situ formation of
17 *
with real life wastewater treatment purposes. sufficient amount of powerful oxidant radicals like OH and
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There are several literature reports depicting the utility of HOO radicals, specifically OH radicals is a crucial factor for
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AOP in degradation of pollutants. Pirila et al. studied TiO2 P25 degradation of organic pollutants in wastewater. The following
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based photocatalytic degradation of four organic industrial section demonstrates the mechanistic approach for the produc-
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pollutants such p-coumaric acid (agro-industrial wastewater), tion of those indispensable radicals. The discussions are broadly
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bisphenol A, phthalic anhydride (plasticizers) and diuron classified into two types of approaches as: non-photochemical
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(herbicide), in two different batch photoreactors employing and photochemical methods.
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advanced oxidation processes under UV A irradiation.[28] It was
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found that Diuron was removed most efficiently in Teflon
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reactor with 98 % degradation within 45 min consuming least 2.1. Non-photochemical method
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energy. Here, Bisphenol A (BPA) was reported to be the most
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difficult to eliminate by photocatalysis among all the studied In this method hydroxyl radicals are generated without using
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pollutants. any additional electromagnetic source of energy. In the
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Kumar et al. showed better photocatalytic activity for the following section few non-photochemical methods have been
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degradation of methyl orange (MO) in aqueous solutions using reported for wastewater treatment.
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LaFeO3/TiO2 nanocomposites under visible light irradiations for
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180 min. It was reported that LaFeO3/TiO2 composite shows
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nearly 90 % decomposition of MO while pure LaFeO3 nano-
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particles shows 83 % decomposition under similar conditions.
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The result shows enhanced reactivity of nanocomposites, rather
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39 Ipsita Som is pursuing Ph.D. at National Chemistry, Banasthali University, India. She
Institute of Technology, Durgapur, India. She has eleven international publications and one
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earned her Master’s in Technology from the book chapter. Dr. Roy has also completed
41 National Institute of Technology, Durgapur, Sponsored DST SERB-NPDF Project (No. PDF/
42 West Bengal, India. She is working on the 2017/000390) on Nano porous Transition
43 chemical and photochemical degradation of Metal Based Semiconductors towards Catalysis
44 organic contaminants and identification of and in Electrochemical. Applications, as the
45 intermediates. sole PI.
46 Prof. Rajnarayan Saha has more than 18 years
47 of research experience in the field of Environ-
Dr. Mouni Roy has earned her PhD degree and
48 mental Chemistry and Water and Wastewater
performed her thesis work in CSIR-CGCRI,
Treatment. He earned his Ph.D. degree at the
49 Kolkata, West Bengal, India. Her thesis work
Indian Institute of Technology, Mumbai (IITB).
50 was focused on synthesis of cost-effective
He did his Masters in Technology as well as in
51 mesoporous transitional metal oxide semi-
science at IITB and Burdwan University. In
conductors for application in water remedia-
52 addition to the doctoral program, many
tion. She has been attached to the Depart-
53 M.Tech students are pursuing of their Dis-
ment of Chemistry, National Institute of
54 sertation work under him. He has published
Technology, Durgapur, India, as a National
more than 35 research papers in different
55 Post-doctoral Fellow. Recently she joined as
renowned international and national journals.
56 Assistant Professor in the Department of
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Reviews
2.1.1. Fenton’s process undergo effective oxidation of organic pollutants in

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wastewater.[35] The typical reaction is mentioned below.
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The Fenton’s reaction was first discovered by H. J. Fenton
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(1894) where there is a combined usage of Fe2 + and H2O2. It is
.
2O3 þ H2 O2 ! 2 OH þ 3O2 (8)
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observed that the oxidative potential of H2O2 (E = 1.776 V) is
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increased, when Fe2 + is used as a catalyst under acidic Pisarenko et al. targeted reutilization of water by removing
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conditions. The reactions involved in Fenton processes are organic water contaminants using ozone and ozone/peroxide
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oxidation process at pilot scale. The group studied mitigation of
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Fe2þ þ H2 O2 ! Fe3þ þ 2 OH þ OH
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(1) organic contaminant [tris(2-carboxyethyl)phosphine and N,N-
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Diethyl-meta-toluamide]and formation of N-nitrosodimeth-
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OH þ H2 O2 ! O2 H þ H2 O (2) ylamine in drinking water. The data from experiment indicate
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that the addition of hydrogen peroxide make the greater OH
12 Fe2þ þ OH ! Fe3þ þ OH
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(3) exposure in surface water treatment which lead to beneficial for
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the oxidation of the recalcitrant compounds, such as tris(2-
Fe3þ þ O2 H ! Fe2þ þ O2 þ Hþ
.
14 (4)
carboxyethyl)phosphine and N,N-Diethyl-meta-toluamide.[36]
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16 OH þ OH ! H2 O2 (5)
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Organic pollutant þ OH ! Degraded products (6) 2.2. Photochemical method
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In general, the photochemical process-based degradation
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Youssef et al. studied the degradation of methyl orange in methods involve the usage of photons and obey the following
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aqueous solution by Fenton’s reaction under different exper- mechanistic approach.
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imental conditions, including, dosages of H2O2 and Fe2 +, differ- Initially, light of suitable wavelength is adsorbed by the
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ent dye concentration at different pH of reaction media. More catalyst. The electron originated from the valence band of the
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than 97.8 % of degradation efficiency was achieved within photocatalyst promoted to its conduction band forming
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15 min of reaction at pH of 2.79.[31] electron-hole pairs. Hence the photogenerated electron-hole
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charge carriers migrate towards the surface, the highly oxidative
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holes in the valence band are trapped by the surface adsorbed
28 *
2.1.2. Ozonation water molecules to generate hydroxyl radicals ( OH), while
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electrons are scavenged by the adsorbed molecular oxygen to
30 * *
Ozone is a powerful oxidative agent that degrades organic yield reactive superoxide radical anion (O2 ). The O2 radical
31
pollutants. Ozone produces the oxidative *OH radicals in anion on further reaction with water molecule produces power-
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ful oxidants, OH and HOO radicals.[37] These radicals efficiently
* * *
wastewater. The resulting OH radicals surrounded by organic
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pollutants may leads to degradation of pollutants. The typical degrade organic pollutants in aqueous media.[38] Furthermore,
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reaction mechanism involved in ozonation was reported as[32] the enhanced sensitization effect between the dyes and the
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semiconductor may also favor the degradation efficiency. In this
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3O3 þ OH þ Hþ ! 2 OH þ 4O2
.
(7) process the chromophore groups present in the dye molecule
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absorbs photons from light source causing the electron on the
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Sharma et al. investigated ozonation process for decoloriza- highest occupied molecular orbital (HOMO) of dye molecules to
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tion and/or degradation of reactive red 135 dye. It was excited to the lowest unoccupied molecular orbitals (LUMO).
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concluded that 99.99 % decolorization of Reactive Red 135 This excited dye molecule then release electrons which are then
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(RR135) could be obtained in each case when initial dye injected to the conduction band of the semiconductor leaving
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concentrations was 500, 1000 and 1500 mg/L after reaction cationic dye radical. The adsorbed molecular oxygen would
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time of 48, 55 and 67 min, respectively.[33] capture the electrons in the conduction band of semiconductor
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Tehrani-Bagha et al. investigated the ozonation processes to degrade the dye molecule.[39] The mechanistic approach of
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for decolorization and degradation of an anthraquinone dye, heterogeneous photocatalytic oxidation process is shown in
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Reactive Blue 19. The effect of operational parameters such as Figure 1.
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ozone dosage, pH, dye concentration and the electrolytes, on Here are the discussions in relation to such photochemical
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decolorization process was also studied. The COD and TOC sources used for water remediation purpose.
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removals were observed to be 55 % and 17 %, respectively.[34]
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2.2.1. UV light assisted photocatalysis
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2.1.3. Peroxide mediated ozonation
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UV light falls in the energy region of 10–400 nm. Many works
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The combination of hydrogen peroxide with ozone produces regarding photocatalytic degradation using transition metal
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more effective system compared to sole ozonation process. In oxide/UV system has been reported. Few of them are discussed
56 *
this case rapid generation of OH radicals results, which below.
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Reviews
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23 Figure 1. Mechanistic view of photo-induced degradation process..
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Dewidar et al. reported that the photocatalytic effect of ZnO the core-shell ZnFe2O4@ZnO nanophotocatalyst exhibit better
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particles combined with UV light was capable to degrade photocatalytic activity than pure ZnO.[43]
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phenol. COD reduction percentage of phenol depends on pH,
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initial concentration, air superficial velocity, catalyst loading.
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The solid liquid mass transfer was studied to understand, 2.2.2. Visible light assisted photocatalysis
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optimize, control and design the photocatalytic reactor. The
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maximum COD reduction was found at pH 2, catalyst loading of Generally, less than 5 % of UV energy reach on the surface of
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1.5 g/L, initial phenol concentration of 25 ppm, and air super- the earth out of the total UV energy released from the sun,
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ficial velocity of 2.51 cm/s.[40] only. This UV energy is insufficient to acquire efficient photo-
35
Saeed et al. prepared titanium oxide supported palladium catalytic degradation of organic pollutants. Besides, UV energy
36
(TiO2/Pd) and titanium oxide supported platinum (TiO2/Pt) and is costly and hazardous to human and animal health. Visible
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used as photocatalyst for degradation study of methyl violet light, however, covers a significant part of the solar spectrum. A
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dye. It was concluded that TiO2/Pt degraded 62 % dye while visible light active photocatalyst, therefore, is always required
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TiO2/Pd degraded about 47 % dye in aqueous medium under for practical application and economical purpose. Most of the
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the same experimental conditions (time 20 min).[41] semiconductor can easily absorb the lower energy visible light
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Herrera et al. evaluated photocatalytic activity of iron oxide efficiently. In this section, photocatalytic degradation process
42
(IO) nanoparticles functionalized with TiO2 for photocatalytic under visible light or UV/VIS system has been discussed.
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degradation of phenol under UV light irradiation. Iron oxide (IO) Sood et al. synthesized TiO2 nanoparticles doped with
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nanoparticles were synthesized by co-precipitation method different molar concentration of bismuth following sol-gel
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followed by encapsulating in a polysiloxane matrix which was method. It was reported that the incorporation of Bi3 + ions in
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then finally functionalized with TiO2of different dosage (sample the TiO2 lattice give enhancement in the photocatalytic
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A: 0.1 g TiO2 and B: 0.3 g TiO2) at 25 °C. The synthesized degradation rate of the Alizarin Red S dye under visible light
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amorphous shaped nanomaterial (IO TiO2 B) contributes a region. The degradation efficiency was dependent upon several
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high photodegradation percentage of phenol with low concen- factors e. g. the doping concentration of Bi3 + ion and the dose
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tration (0.2 g/L) of IO TiO2 B nanomaterials under UV of the prepared catalyst. TiO2 doped with a 1 % Bi3 + ion doping
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irradiation.[42] concentration and the best photocatalytic degradation efficien-
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Shao et al. prepared the ZnFe2O4@ZnO nanophotocatalysts cies for the dye was at the dose of 0.1 g/L. The optimum
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with improved photocatalytic activity by solvothermal method. degradation efficiency of dye was more than 80 % within
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The photocatalytic degradation of Methylene Blue (MB) was 90 min of reaction time.[44]
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accomplished under UV irradiation. It has been reported that Shakira et al. reported photodegradation of paracetamol drug
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solution under visible light irradiation by ZnO and La doped ZnO
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Reviews
by taking various concentration. It has been monitored that 3 % La which increases the degradation rate of organic pollutants. This
1
doped ZnO nanoparticles exhibited highest photocatalytic activity process is known as the photo-Fenton processes.[51] The
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with 80 % degradation of Paracetamol drug in 180 min. However, reaction mechanisms are as follows.
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La doped ZnO nanoparticles show better activities as compared to
4
pure ZnO nanoparticles.[45] Fe2þ þ H2 O2 þ hn ! Fe3þ þ OH þ OH
.
(9)
5
Mohammadia et al., (2016) prepared Zn doped, Cu doped
6 Fe3þ þ H2 O2 þ hn ! Fe2þ þ O2 H þ Hþ
.
and Zn Cu co-doped WO3 nanoparticles by precipitation and (10)
7
co-precipitation methods. The prepared catalyst exhibited good
8
photocatalytic degradation of gentamicin under UV and visible In this reaction mechanism when Fe2 + coupled with H2O2 is
9
light irradiation. The photocatalytic efficiency of WO3 nano- irradiated with light homolytic and heterolytic cleavage of
10 *
particles for gentamicin degradation (irradiation time: 90 min; hydrogen peroxide occurs simultaneously generating OH
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radical and O2H radical respectively. Here, E0(Fe2 + /Fe3 +) =
*
pH: 9) under UV light is higher than visible light while
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gentamicin degradation by Zn Cu co-doped WO3 nanoparticles 0.77 V and E0 (H2O2/H2O) = 1.776 V. So, Fe2 + is oxidized in
13
were high compared to pure samples.[46] presence of H2O2 and highly oxidative OH radical to Fe3 + by
*
14
Patel et al. prepared TiO2, N-doped TiO2, V-doped TiO2, and rejecting one electron.[52]
15
V N-codoped TiO2 thin films and studied their photocatalytic Lagori et al. reported the photo-Fenton degradation of
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activities on methylene blue, chlorophenol and nitrophenol. It Rhodamine B toper form a preliminary in vitro test on the
17
was observed that the codoped TiO2 gave the highest photo- possible use of two different laser wavelengths, 405 and
18
catalytic activity in comparison to the mono-doped and 532 nm.[53]
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undoped TiO2 because of high visible light absorption and Roy et al. prepared mesoporous cube shaped hematite (α-
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possible reduction in the recombination of photo-generated Fe2O3) particles using FeCl3 as an Fe3 + precursor and 1-butyl-3-
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charges.[47] methylimidazolium bromide (ionic liquid) as a soft template in
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Sharmila et al. synthesized porous and spongy iron nano- the presence of different alkali metal (lithium, sodium and
23
particles by using Eucalyptus Globulus leaves which acts as potassium) acetates, under hydrothermal conditions at 150 °C/
24
photocatalyst to study the photodegradation of Rhodamine B 4 h followed by calcination at 350 °C. They studied the catalytic
25
dye under both UV light and sunlight. The optimum condition degradation of methylene blue (MB), a toxic water pollutant,
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(pH = 2.4, catalyst dosage = 30 ml, residence time = 3 hours) using the mesoporous cube shaped hematite (α-Fe2O3) particles
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exhibited about 79 % and 35 % dye removal efficiency under UV via heterogeneous photo-Fenton process. The experiment
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source and solar irradiation, respectively. Green synthesis shows that the percentage of dye removal for Fe2O3-Li, Fe2O3-
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method of preparation of iron nanoparticles using Eucalyptus Na and Fe2O3-K catalysts was 48 %, 90 % and 78 %, respectively.
30
globulus leaves was proved to be an useful catalyst for dye The Fe2O3-Na catalyst assisted the formation of small fragments
31
degradation.[48] of open chain compounds as final degraded products.[54]
32
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2.2.3. Gamma radiation induced photocatalysis 2.2.5. Microwave irradiation induced photocatalysis
35
36
Apart from UV and visible light sources, environmental Recently microwave (MW) irradiation has acquired a great deal
37
pollution can be minimized by utilizing gamma irradiation of attention towards wastewater treatment applications. The
38
sources. The chemical usage in treatment of industrial waste- environmental application of MW is based on the. rapid and
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water can be effectively reduced when conventional treatment selective heating property of MW. It can be applied alone or has
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is combined with gamma (ionizing) radiation. The reuse of been used coupled with oxidants and catalysts or coupled with
41
irradiated sludge suggests economic and/or environmental AOP like Fenton process, UV (photolysis) or photocatalysis (UV/
42
benefit in terms of recycling in agriculture.[49] titanium dioxide, TiO2).[55,56,57] Various MW absorbing materials
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Shaoqing et al. investigated gamma radiation induced with high surface area and a wide range of pore size
44
catalytic degradation of p-nitrophenol (PNP), a pollutant and distribution has been developed for enhancing the degradation
45
raw material in chemical industry for the manufacture of of organic pollutants under MW.[58] When a MW-absorbing
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pesticides, herbicides etc. in the presence of titanium dioxide material is used, for example activated carbon (AC), hot-spots
47
(TiO2) nanoparticles in aqueous solution. An efficient removal are formed on the surface of the AC; thus, selective heating is
48
was found for the degradation of PNP. Several intermediates as produced causing spur in the molecular rotation and finally
49
for example hydroquinone, benzoquinone, 4-nitropyrogallol, decreases the activation energy.[59]
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and 4-nitrocatechol were identified by HPLC and LCMS.[50] Ju et al. investigated degradation of Malachite green (MG)
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using TiO2 under microwave irradiation. The satisfactory results
52
indicated that MG was decomposed in 3 min with the
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2.2.4. Photo Fenton Process corresponding TOC removal efficiency of 85 %. Further studies
54
regarding the intermediates formed during the degradation
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If UV radiation is coupled with the usage of hydrogen peroxide revealed formation of four kind of N-demethylation intermedi-
56
and Fe2 + or Fe3 + ions, more hydroxyl radicals are produced ate and two types of newly detected reaction products.[60]
57
Reviews
3. Controlling factors for designing port to the reactive sites. This makes pollutant degradation
1
photocatalyst process easier.[67] Ghazzal et al. investigated Photocatalytic
2
degradation of Rhodamine 6G on mesoporous titania films.[68]
3
Therefore, high porosity and surface area of titania incriminate
4
The generation of oxidative hydroxyl radical is very important in higher contact surface to the Rhodamine 6G and then enhance
5
the degradation process of pollutants present in aqueous the photocatalytic degradation rate.[69]
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media. However, the role of heterogeneous catalyst also has Integration of graphitic materials (reduced Graphene Oxide)
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marked influence in degradation process. The presence of a has been proved to be effective for enhancement of the
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suitable heterogeneous photon energy exploiting catalyst in transport of charge carriers in semiconductor photocatalysts.
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the reaction media not only enhances the production of greater Furthermore, inhibition of hole-electron recombination is
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amount of hydroxyl radicals but also provides surface for another crucial criteria for better photocatalytic performance.
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undergoing degradation process efficiently. Thus in this scenar- Constructing heterojunction, the interface between two layers
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io the designing of photocatalyst plays a dominant role. The or regions of dissimilar crystalline semiconductors is a useful
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various controlling factors, like band gap energy, carrier trans- approach to enact this goal. Overall, there are various
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port, crystallinity, surface area and chemical stability, for design- heterojunction photocatalysts, including: p-p heterojunction, n-
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ing photocatalytic materials has been discussed below. n heterojunction, n-p heterojunction, z-scheme heterojunction
16
semiconductor photocatalyst. Among these n-p heterojunction
17
photocatalyst has some advantages e. g. 1) faster charge trans-
18
3.1. Band Gap Energy ference to photocatalyst; 2) operative charge separation; 3)
19
enhances photocatalytic degradation by rejecting other nano-
20
As discussed earlier in the mechanism section the generation of particle induced local inharmonious reduction and oxidation
21
charge carriers is the most important phenomenon in the reactions; and (4) improves lifetime of charge carriers by
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photocatalytic reactions. When the energetic photons illumi- delaying recombination.
23
nate the photocatalyst the electron from the valence band Li et al. fabricated ZnO/CdS nano-heterostructure with
24
migrate the energy interval present in the semiconductor and flower-like morphology by a facile two-step precipitation
25
reaches the conduction band. This energy interval or bandgap method and studied the photocatalytic degradation of Rhod-
26
energy (Eg) is an important structural feature of a amine B (RhB) under simulated sunlight. The degradation of
27
photocatalyst.[61] Small Eg signifies easier low energy expendi- RhB was about 50 % at 120 mints by using ZnO nanoparticle
28
ture and photo activation. Research is going on for preparation solely. The photodegradation was enhanced about 100 % after
29
of narrow band gap photocatalyst till date. However, fast 90 mints light irradiation for ZnO/CdS nano-heterostructure.
30
recombination of photogenerated charge carriers may occur This can be attributed due to the fact of inhibition of electron-
31
due to very narrow bandgap of photocatalyst. The balance hole pair recombination by a charge transfer process in
32
between these two ambiguous phenomena can lead to the ZnO CdS heterostructured. The band alignment of ZnO/CdS
33
generation of optimized photocatalyst.[62] nano heterostructure is also responsible for the enhanced
34
Ahmed et al. investigated the efficiencies of various photo- photocatalytic degradation of RhB.[70]
35
catalysts ZnO (Eg = 3.37 eV) TiO2 anatase (Eg = 3.20 eV) Fe2O3 Zhang et al., synthesized nanoscale ZnO/TiO2 coupled oxide
36
(Eg = 2.20 eV) and CdS (Eg = 2.40 eV) for the degradation photocatalyst by a two-step method, the homogeneous
37
purpose of Acid Red 18 under UV light illumination. ZnO hydrolysis and low temperature crystallization. The photo-
38
showed the highest degradation over TiO2 anatase catalyst. catalytic activity of coupled oxides was examined towards the
39
Remarkably, the narrow band gap of Fe2O3 and CdS have degradation of methyl orange (MO) as a model compound.[71] It
40
negligible activity on Acid Red 18 decolorization.[61] was concluded from the experiment that the ZnO/TiO2 showed
41
better photocatalytic activity compared to pure phase ZnO or
42
anatase TiO2, and even higher than that of the Degussa P25
43
3.2. Carrier transport TiO2. It was explained on the basis of the presence of the
44
intimately bonded ZnO/TiO2 surface heterostructure, which
45
Photocatalytic reaction actually takes place at the semiconduc- promotes the separation of the photogenerated electrons and
46
tor surface. Thus, spontaneous migration of photogenerated holes. Thus, it decreases the electron-hole pair recombination
47
charge carriers from the interior bulk to the surface is one of rate.[72]
48
the essential criteria for improved photocatalytic performance Wen et al. fabricated BiOI/CeO2 p–n junction photocatalysts
49
of a photocatalyst.[63,64] In case of mesoporous photocatalyst the and studied the photocatalytic degradation of methylene
50
nanosized channel walls promote faster electron migration orange and Bisphenol A, refractory pollutant under visible light
51
from bulk to the surface, resulting in efficient degradation of irradiation. Samples with the Bi/Ce molar ratios 1 : 1 exhibited
52
organic pollutants adsorbed on the surface of the the highest photo activity and it can be contemplated that BiOI
53
photocatalyst.[65,66] Mesoporosity is one of the crucial factors for can broaden the visible-light absorption region of CeO2. Thus,
54
efficient photocatalytic degradation of pollutants. Introduction improvement of the transfer rate of electron-hole pairs by
55
of mesoporosity in photocatalytic material lead to greater forming a p-n junction occurs. The optimum removal efficiency
56
specific surface area for pollutants adsorption and mass trans- of Methylene orange and Bisphenol A was 94.20 % at pH 9.5.[73]
57
Reviews
Recently one-dimensional (1D) nanostructures (nanowires, hole and electron.[78] So, it is mandatory to keep a reduced
1
nanotubes, nanobelts and nanoribbons) provide a significant number of defects in the photocatalytic material for enhanced
2
benefit towards heterogeneous photocatalyst due to their photocatalytic degradation performance.
3
interesting physical properties, unique geometric character- Tayade et al. prepared nanocrystalline TiO2 followed by
4
istics. Firstly, the 1D geometry promotes fast and long-distance controlled hydrolysis of titanium tetra isopropoxide. The
5
electron transport. Secondly, 1D nanostructures possesses anatase phase was transformed to rutile phase by thermal
6
larger specific surface area and pore volume as compared with treatment at 1023 K for 11 h. Comparison between the photo-
7
analogous bulk materials. Thirdly, the light absorption and catalytic activity of the anatase and rutile phases of nanocrystal-
8
scattering are considerably enhanced, based on the high line TiO2 was investigated for the degradation of acetophenone,
9
length-to-diameter ratio for the 1D nanostructures. Fourthly, nitrobenzene, methylene blue and malachite green present in
10
shortened diffusion distance for minority carriers. [74] Therefore, aqueous solutions. The better photocatalytic activity of the
11
it has provided a matter of immense interest to investigate the anatase TiO2 than rutile TiO2 may be for less number of defects
12
potential applications of 1D-based nanocomposites in the field formed in anatase phase of TiO2 which prohibit the chance of
13
of heterogeneous photocatalysis. hole-electron recombination.[79]
14
Bae et al. reported the synthesis of 1D-ZnO nanotubes Gao et al. synthesized high crystallinity TiO2 nanocrystals
15
which is grown through a Ga-catalyzed vapor transport method with tunable anatase/rutile ratios by low temperature dissolu-
16
at low temperature. The photocatalytic degradation of an tion-reprecipitation process and solvothermal treatment com-
17
azobenzene-containing polymer PAZO solution and rhodamine posite method.[80] It can be seen from the experiment that the
18
B (RhB) on ZnO nanotubes was studied. It was concluded that photocatalytic activity of the pure anatase sample is higher
19
the photoactivity of the 1D-ZnO nanotubes is much higher than than that of the pure rutile and the majority of the anatase-
20
the ZnO thin films and ZnO nanowires. The strong connection rutile mixed phase TiO2samples (the rutile content > 20 %).
21
between the 1D-ZnO nanotube and the substrate facilitated the Therefore, the photocatalytic activities are decreased with
22
transport of electrons which enhance their photocatalytic increasing rutile content. This is because of the faster recombi-
23
properties.[75] nation rate of the photo induced charges in rutile relative to
24
Zhag et al. designed 2D/2D BiOBr/CDS/g-C3N4 Z-scheme anatase.[81] However, the 20 % rutile-TiO2 sample exhibits the
25
heterojunction photocatalyst with carbon dots as solid state highest photocatalytic activity. The recombination of photo-
26
electron mediator and studied the photodegradation of cipro- induced charges can be inhibited since the electrons can easily
27
floxacin and tetracycline under visible and near infrared light transfer from the conduction band of anatase to that of rutile
28
irradiation. This resultant BiOBr/CDS/g-C3N4 hybrid exhibits due to the conduction band level of anatase is higher than that
29
excellent photodegradation activity than their pure counterpart. of rutile.
30
The degradation efficiency of ciprofloxacin and tetracycline by Štengl et al. prepared pure brookite phase of titania by
31
this composite is about 74 % and 82.7 % respectively. This is due hydrothermal synthesis of titanium peroxo-complex in the
32
to BiOBr/CDS/g-C3N4 possess remarkable interfacial charge presence of glycolic acid at 220 °C. The photocatalytic activity of
33
transfer ability and capable to broaden solar light absorption brookite phase was evaluated using orange II dye in aqueous
34
range owing to the short charge transport distance.[76] solution under UV radiation. The photocatalytic activity of the
35
Li et al. fabricated an efficient binary Bi2Fe4O9/Bi2WO6 Z- brookite phase calcined to 800 °C in air was higher than
36
scheme heterojunction through a facile hydrothermal route. nanocrystalline unheated brookite powder. The brookite crystal-
37
The obtained Bi2Fe4O9/Bi2WO6 displays 100 % of RhB photo- linity increases with increasing temperature of annealing (in
38
degradation by Bi2Fe4O9 (7 %)/Bi2WO6 within 90 min, which is interval 100–800 °C). Hence, the photocatalytic activity in-
39
much higher than that by pure Bi2Fe4O9 and Bi2WO6. The creases. Furthermore, decrease in photocatalytic activity at
40
effective photo induced carrier separation, the broadened temperatures above 800 °C is due to the increase rutile phase.[82]
41
photo absorption range, high oxidation capacity of hole and
42
the high reduction power of electron are in charge of the
43
elevated catalytic activity because of the formed Z-scheme 3.4. Surface area
44
system.[77]
45
Surface area of photocatalyst is a pivotal factor for improving
46
the rate of photocatalytic degradation processes.[83] Thus,
47
3.3. Crystallinity increasing the surface area results in better adsorption of the
48
organic pollutants on the surface of the photocatalyst. Meso-
49
Crystallinity can be defined as the degree of structural order in porous semiconductors of high surface area and improved
50
a solid. The photocatalytic degradation process prominently porosity (optimum pore size and pore volume) provides more
51
depends on the phase of the photocatalyst material and its surface reactive sites for adsorption and diffusion of reactant
52
crystallinity. Nanocrystalline TiO2 has anatase and rutile crystal molecule which accelerate the photocatalytic activity.[84]
53
phase, although these two crystalline phases do not respond at Roy et al. synthesized porous cobalt oxide (Co3O4) nanorod
54
the same extent towards photocatalytic degradation of organic and nanosheet-like (70–100 nm) particles followed by a facile
55
pollutants. It is to be noted that density of defect increases with hydrothermal method at 150 °C for 2–5 h and 12–24 h,
56
increasing crystallinity. Defect act as recombination centers for respectively and showed the degradation of Chicago Sky Blue
57
Reviews
6B, a azo dye used in the food, paper and textile industries. The 4. Optimized Factors influencing the
1
2
adsorption of Chicago Sky Blue 6B on the catalytic surface was photocatalytic degradation
higher in case of synthesized sample for 5 h compared to 2 h
3
treated sample which may be due to the higher BET surface
4
area (112 m2 g 1), pore volume (0.5 cm3 g 1)and pore diameter The oxidation rates and efficiency of the photocatalytic
5
(7.4 nm ) which improved the catalytic efficiency.[85] reactions are dependent on some of operational parameters
6
Yu et al. synthesized template free mesoporous which are the driving force of photodegradation of the organic
7
Fe2O3possessing high surface area of 111 m2/g, narrow pore molecule.[89,90,91,92]
8
diameter of 4.4 nm and pore volume of 0.179 cm3 g 1, used as
9
an adsorbent to treat wastewater contaminated by toxic azo
10
dye, Congo red. The studies exhibited that Fe2O3 with high 4.1. Effect of organic pollutant concentration
11
surface area possesses favorable adsorptive properties than the
12
commercial metal oxide powders with low surface area.[86] Organic pollutant concentration is a crucial factor for improved
13
Flores et al. fabricated ZnO nanostructures of different photocatalytic degradation rate. Basically, the percentage
14
morphologies (hexagonal disks, dumbbell-shaped, rice-like, degradation decreases with increasing amount of organic
15
rods) through ultrasound-assisted hydrolysis of zinc acetate at pollutants concentration.[93] More organic substrates are ad-
16
room temperature. The photocatalytic activity of the ZnO sorbed on the surface of the photocatalyst, as the concentration
17
nanostructures was investigated by monitoring methylene blue of organic pollutants increases reducing the number of active
18
(MB) decomposition rates under ultraviolet (365 nm, 10 W) sites available on the surface for the photons to be adsorbed.
19
radiation. ZnO nanostructure having rice-shaped morphology Therefore, significant amount of UV is absorbed by the organic
20
grown at pH 9 exhibited highest photocatalytic degradation pollutants rather than the photocatalyst. So, the formation of
21
rate towards MB decomposition compared to other morphol- hydroxyl radicals (·OH, primary oxidant) is hampered resulting in
22
ogy. Complete MB degradation was observed after 240 minutes less degradation percentage.[94]
23
of UV exposure for the ZnO nanostructure having rice-shaped Santhosh et al. prepared bare 3D-TiO2, magnetic 3D-TiO2
24
morphology. Interestingly, for the same duration of UV and magnetic 3D-TiO2@Hierarchical Porous Graphene Aerogels
25
exposure, the ZnO nanostructures hexagonal disks, dumbbell- (HPGA) nanocomposite:(m3D-T-HPGA NC) by solvothermal proc-
26
shaped and rods show 91.6, 73.4, and 64.7 % MB degradation, ess and studied the effect of initial pollutants concentration on
27
respectively. It can be explained on the basis of the fact that photocatalytic degradation of the two toxic pollutants, Cr(VI)
28
ZnO nanostructure having rice-like morphology possess highest and bisphenol A (BPA). As the initial Cr(VI) concentration
29
specific surface area (18.88 m2/g) among all the three increases from 25 mg L 1 to 50 mg L 1 there is a decrease in the
30
morphology.[87] degradation of Cr(VI) ions from 60 to 45 % in 220 min
31
respectively due to less availability of electron hole pairs. So,
32
there will be a decrease in the degradation process. Similarly,
33
3.5. Chemical stability the degradation of BPA was drop off from 70 to 55 % when
34
concentration of BPA increases from 25 mg L 1 to 50 mg L 1.[95]
35
Chemical stability, durability and reusability of a photocatalyst Nahar et al. also studied the effect of initial Rhodamine B
36
in a reaction medium is another important factor for implemen- (RhB) concentration ranging from 5 to 20 mg/L, on it’s photo-
37
tation of a catalyst as efficient material capable of improved catalytic degradation using prepared Ag nanoparticles (NPs)
38
activity towards wastewater treatment. A photocatalyst which is loaded Ag2SO3 (AgSS) photocatalyst. The dye removal efficiency
39
chemically stable in reaction medium can be further used for of AgSS decreases with increasing concentration of RhB. The
40
reusability purpose which proved the catalyst as commercially highest degradation percentage (99 %) was conquered by using
41
beneficial. Moreover, the durability of the photocatalyst in the an initial concentration of 5 mg/L after irradiation period of
42
reaction medium discards the chances of producing secondary 120 min and the lowest final degradation (1 %) was attained for
43
sludge/pollutant which makes it useful in terms of environ- 20 mg/L.[96]
44
mental perspective.
45
Dong et al. investigated the photodegradation activity for
46
rhodamine B, methylene blue and methyl orange organic dyes 4.2. Effect of photocatalyst concentration
47
under UV-visible light using highly efficient Ag-based photo-
48
catalyst Ag2Nb4O11. Furthermore, the cycle operation of the It is reported earlier that photocatalyst dosage has both positive
49
degradation of Rhodamine B was carried out which reveal that and negative impact on the photodecomposition rate. Gen-
50
the photocatalytic ability of the Ag2Nb4O11 sample was not erally, the photodegradation of organic pollutants increases
51
noticeably lost after 40 recycles over a 1400 min reaction. The with increasing photocatalyst dosage.[97,98,99] With increasing
52
removal rate is 75 % after a 35 min reaction during the 40th and catalyst concentration number of active sites increases on the
53
last cycle. The cycling ability (40 times) as well as recovery photocatalyst surface which cause an enhancement in the
54
generation of number of OH radicals.[100,101] Reduction of
*
characteristics imply that the Ag2Nb4O11 photocatalyst has
55
excellent durability, stability, and regeneration ability.[88] degradation efficiency of organic pollutants occur at higher
56
concentration of photocatalyst loading. The photocatalyst act
57
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as a obstacle for the incident UV irradiation and diminish its 4.4. Reaction temperature
1
arrival to some particles at higher catalyst loading. one more
2
feasible reason is the agglomeration of the catalyst nano- Reaction temperature should be properly maintained for
3
particles that aided by their high surface energy and surface improved photocatalytic performance. Generally, the rate of
4
area. Furthermore, the effective surface area of the catalyst photocatalytic degradation of organic molecules gradually
5
decreases which can lead to the reduction in the degradation increases as the temperature is elevated. The bubbles produced
6
efficiency. Hence, optimum photocatalyst concentration need in the solution indicate the formation of free radicals with
7
to be maintained for better photocatalytic performance. enhancement of reaction temperature. However, electron-hole
8
Abdellahet al.[102] studied the effect of TiO2 dosage on the recombination in photocatalyst can also be overruled with the
9
percentage degradation of Methylene blue (MB) dye under UV increase in reaction temperature.[107] The increasing temperature
10
irradiation. The effect of TiO2 loading on the degradation of MB may accelerate the oxidation rate of organic molecules at the
11
was investigated within the range of 0.5–2 g/L under distinct interface.
12
experimental conditions. It can be seen that the percentage Mozia et al. investigated that as reaction temperature
13
removal increased with the increase in TiO2 loading with a increases the photodegradation rate constant increases in case
14
maximum of 1 g TiO2 /L. Beyond that, the removal percentage of acid red 18. The increase in solution temperature from 313 to
15
decreased with increase in the TiO2 dosage. 323 K increased the reaction rate from 11 to 13 %.[108]
16
Yunus et al. studied the effect of N- S co-doped TiO2 loading Hu et al. reported the temperature effect ranging from 38 to
17
on the percentage degradation of phenol under UV irradiation. 100 °C on the photocatalytic degradation of methyl orange dye
18
The amount of N, S co-doped TiO2was varied as 1 g/L, 2 g/L and using prepared anatase-TiO2 hydrosol as photocatalyst under
19
3 g/L. It was seen that 3 g/L of photocatalyst loading has the UV-VIS light Irradiation. It was seen that the temperature
20
100.0 % photodegradation performance within 4.5 h irradiation influences the reaction rate. The rate constants increased by
21
time whereas1 g/L and 2 g/L of photocatalyst dosage resulted about 6 times from 3.52 × 10 4to 2.17 × 10 3 min 1by adjusting
22
in 69.9 % and 96.2 % degradation of phenol, respectively.[103] the temperature from 38 to 100 °C.[109]
23
24
25
4.3. Effect of pH 4.5. Effect of Light Intensity and Irradiation Time
26
27
pH of solution plays a vital role upon photodegradation of Both light intensity and time of irradiation affect the organic
28
organic molecule, as variation of pH of the solution changes the pollutants degradation. Photocatalyst absorbs the light with an
29
surface charge of photocatalyst.[104] energy equal to or more than band gap energy. This causes the
30
Photocatalyst surface becomes positively charged at lower movement of electrons from valence band to conduction band
31
pH of solution. Therefore, the anionic dye due to its’ strong by leaving holes in the valance band. Generally, the photo-
32
Lewis base character is adsorbed on the surface of photocatalytic degradation rate increases with increasing intensity of
33
catalyst easily. The surface of photocatalyst becomes predom- radiation as well as increase of irradiation time.[110] However,
34
inantly negatively charged when the pH of the solution effect of irradiation time on photocatalytic degradation of
35
increases. The increased adsorption of cationic molecules takes organic pollutants depends on light intensity. Percentage
36
place at higher pH value. The optimum pH of solution has to be degradation of organic pollutants can be enhanced by using
37
fixed for the different organic molecules. solar energy compared to artificial light at the same irradiation
38
Bubacz et al.[105] showed that the rate of photocatalytic time.[111] Formation of photogenerated charge carriers (hole-
39
degradation of methylene blue, a cationic dye and phenol electron) become facile at high intensity of radiation along with
40
increases with increase in pH. The best results in case of high irradiation time, which leads to increase the photocatalytic
41
solutions of phenol were acquired at pH = 6.5. The influence of degradation rate of organic contaminants present in waste-
42
pH on methylene blue dye decolorization is as follows: pH = 9 > water. The hole-electron pair separation encounters with
43
pH = 5.8 > pH = 3. It is clear that the highest degree of photo- recombination at lower light intensity, reduces the formation of
44
catalytic degradation of methylene blue was obtained in the free radicals and, thus, causes reduction in the degradation of
45
basic solution (above 96 % after 6 h of UV radiation). the organic molecules.
46
Chen et al.[106] reported the effect of pH in the reaction Chanathaworn et al. studied the degradation of the Rhod-
47
medium on the percentage degradation of crystal violet (CV) amine B dye by altering the irradiation intensity of black light
48
dye by using TiO2 as photocatalyst under UV irradiation. The lamp in the range of 0–114 W/m2. The percentage of decoloriza-
49
photodegradation rate of the CV dye was found to increase tion efficiency was 42.1 and 87.8 when exposure to black light
50
with the increase in the pH. It was found that the cationic CV intensities of 23 W/m2 and 114 W/m2, respectively, for 90 mi-
51
dye was difficult to adsorb onto the TiO2 surface at low pH, as a nutes. It was also found that the percentage of decolorization
52
result the photodegradation process of CV remained very slow. efficiency reached at 90 % after 120 minutes exposure in
53
presence of black light, of intensity 114 W/m2. The results
54
indicated that an increase in the irradiation intensity along with
55
irradiation time of black light enhanced the dye degradation.[111]
56
57
Reviews
Liu et al. studied the experiment under three various light .

H2 O2 þ 2 ! OH þ OH þ O2
1
intensities (1.24 mW/cm2, 2.04 mW/m2, 3.15 mW/m2) and the
2
fact of degradation of Acid Yellow 17 increases with increasing .
H2 O2 þ v 2 OH
3
light intensity was established.[112]
4 . .
Pardeshi et al. investigated the effect of light irradiation H2 O2 þ eCB OH þ OH
5
time on the photocatalytic degradation of phenol in aqueous
6
zinc oxide suspension using visible light from sun and 1000 W Degradation of the organic pollutants occurs at a faster rate
7
xenon lamp separately. The photodegradation of phenol in with increase of H2O2 concentration.[119] Here, photolysis of H2O2
8 *
sunlight was found to increase with increase in irradiation time as well as trapping of electrons by H2O2cangenerate OH
9
leading to 100 % degradation within 8 h. However, when radicals. Thus, recombination of hole-electron pairs is somewhat
10 *
sunlight was replaced by 1000 W xenon lamp, there was inhibited providing more chance of the formation of OH radical
11
maximum 47 % photo degradation within 9 h. So, in terms of and O2 on the surface of the photocatalyst. While, beyond the
12
light irradiation time it was proved that zinc oxide is an optimum concentration ofH2O2 increase in H2O2level decreases
13
effective photocatalyst in sunlight as compare to artificial visible the degradation rate of dye due to quenching of OH radical by
*
14
light.[113] H2O2.[120]
15
Antonopouli showed the effect of oxidants like hydrogen
16
peroxide and persulfate ion on the degradation of DEET (N,N-
17
4.6. Effect of inorganic ions dimethyl-m-toluamide), a representative emerging micro-pollu-
18
tant by using Degussa P25 TiO2 as photocatalyst. It was
19
Sometimes various inorganic ions as for example magnesium, reported that degradation of DEET increases with increasing
20
iron, zinc, copper, bicarbonate, phosphate, nitrate, sulphate and S2O82 concentration up to a certain level which conforms to
21
chloride present in wastewater can affect the photocatalytic the optimum concentration under the experimental conditions
22
degradation rate of the organic pollutants. This can be studied. The enhancement in degradation rate can be explained
23
explained on the basis of adsorption of these inorganic ions on the capability of persulfate to act as an electron acceptor,
24
onto the surface of photocatalyst leaving behind a reduced inhibiting the charge recombination along with the production
25 *
number of surface-active site for adsorption of organic of very strong oxidants HO radicals. Conversely, addition of
26
pollutants which decrease the rate of photocatalytic degrada- high concentrations of H2O2 induces a marked decrease to the
27
tion of organic pollutants.[114] Moreover, some of the cations reaction rate of degradation of H2O2.[121]
28
such as copper, iron and phosphate decrease the photo- In the above discussions it is clear that heterogeneous
29
degradation efficiency if they are present at certain concen- catalyst assisted photocatalytic degradation of different types of
30
trations, whereas, calcium, magnesium and zinc have little organic pollutants depends on several factors. Organic pollu-
31
effect on the photodegradation of organic compounds because tants eluted from several industries, contaminating water
32
these cations have maximum oxidation states limiting inhibitory sources, can be effectively degraded by maintaining such
33
effect on the degradation process.[115] optimized conditions. To investigate elaborately on this arena,
34
Gao et al. showed the effects of various inorganic ions several studies has been performed to dig-into the reality of the
35
(cations and anions) on the photocatalytic degradation of toxicity effect of the intermediates produced during degrada-
36
carbamazepine, pharmaceuticals and personal care products, tion process as well as the final degraded product. This requires
37
over the visible light driven BiOCl photocatalyst. The half-life of an elaborate study on the photocatalytic degradation mecha-
38
carbamazepine became 11.83, 12.28, and 154.44 min upon nism of organic pollutants. In this context, titania nanomaterials
39
addition of HCO3 (50 mg/L), Cl (200 mg/L) and NO3 (100 mg/ proved to be quite convincing candidate for the desired
40
L) respectively. The addition of inorganic anions exhibited a process. Semiconductor, nontoxic, inexpensive titania nano-
41
negative effect on photocatalytic degradation of carbamaze- materials are extremely stable in the reaction medium and can
42
pine with the order of inhibition effects of HCO3 > Cl > NO3 exploit UV light efficiently for the photocatalytic degradation
43
which may be due to the quenching effects of hydroxyl radicals purpose. Suitable modifications on the synthesis procedure can
44
or holes that ultimately decreases the photocatalytic degrada- tune these nanomaterials towards much more efficiency. Hence,
45
tion of carbamazepine.[116] several research groups concentrated on the use of TiO2
46
nanomaterials towards degradation of organic pollutants
47
present in wastewater which has been discussed in the
48
4.7. Effect of oxidants following section.
49
50
The electron-hole recombination in photocatalyst can be
51
reduced by adding some irreversible electron acceptors such as 5. Photocatalytic degradation mechanism
52
H2O2, (NH4)2S2O8, KBrO3, and K2S2O8 to the reaction
53
mixture.[117,118] H2O2 is used for enhancing the photocatalytic Yang et al. proposed a photocatalytic degradation mechanism
54
activity of prepared photocatalyst in most cases. (Figure 2) of Rhodamine B using TiO2 film on a capillary column
55
The mechanism in which H2O2 attains the photocatalytic under UV light radiation.[122] Rhodamine B degraded by some
56
degradation is given as follows: following steps. At first de-ethylation occur by attacking the
57
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3
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13
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21
22
23
24
25
26
27
28
29
30
31
32
Figure 2. Proposed degradation mechanism of Rhodamine B.[122]
33
34
35
36
OH radicals into the N CH2 bond of NCH2CH3 group lead to dimethylamino) methyl benzylone, most common intermediate
*
37
the formation of mono de-ethylated (a) and di de-ethylated in all the three reaction. Therefore, the production of benzoic
38
products (b).Then product (c) is obtained by eliminating acid, p-(dimethylamino)-benzoic acid, and p-dimethyl amino-
39
{(C2H5)2NH} group from compound (b). Moreover, the product phenol occur due to the attack by hydroxyl radicals on 4-(N,N-
40
(e) is formed due to the decarboxylation of compound (c). dimethyl amino) methyl benzylone. The relevant intermediates
41
Moreover, hydroxyl radical attacks the double bond by which a are further degraded by the breaking of the aromatic cyclic
42
ring opening reaction takes place producing some intermediate group in the molecular structure, and some fatty acidic
43
compounds which then further mineralized to CO2 and water. compounds of low molecular weight formed. This is probably
44
The degradation intermediates were identified by positive ion due to the strong oxidation power of the hydroxyl radicals
45
mood mass spectra generated in the photocatalytic reaction system. some acidic
46
Gao et al. proposed the photocatalytic degradation mecha- intermediates are also formed which is proved by gradual
47
nism (Figure 3) of malachite green by using a novel biomimetic decrease of pH value which are further degraded to the final
48
photocatalyst named HMS-FePcS (hexagonal mesoporous sili- mineralized products of water and carbon dioxide.
49
cas-iron sulfophthalocyanine).[123] There are two main photo- Zuo et al. proposed a photocatalytic degradation mecha-
50
catalytic degradation pathway which are demethylation reac- nism (Figure 4) of methylene blue (MB) dye using TiO2
51
tions, that took place on the amino group, and the formation of impregnated diatomite as photocatalyst.[124] The initial step is
52
activated [MG-OH]* by the attack of hydroxyl radicals on the the cleavage of the C S +=C functional group in MB, which is
53
central carbon atoms producing the intermediates (a). in direct coulombic interaction with the surface of TiO2/
54
diatomite by OH radicals. Hence, conversion of C S +=C to C S
*
The formation of activated [MG-OH]* occurs because of the
55 *
breaking of the C C bond between the central carbon atoms (=O) C takes place by attacking OH radicals with the
56
and N,N-dimethylaminobenzyl and the formation of 4-(N,N- production of product (a).The passage from C S +=C to C S
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27 Figure 3. Proposed degradation pathway of malachite green over the novel HMS-FePcS catalyst under visible light.[123]
28
29
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(=O) C involves the conservation of the double bond con- structure of the amino triphenylmethane producing inter-
31
jugation, which activates the opening of the central aromatic mediates (a) and (b) shown in Figure 5.
32
ring containing both heteroatom, S and N which lead to the (iii) The pathways of photocatalytic degradation of the CV: In
33
formation of (b) and (c). Then finally mineralization can take accordance with previous reports[126,127] most N-de-alkyla-
34
place via the formation of compound (d) from (b) and tion processes are took place by the generation of a
35
compound (c). nitrogen-centered radical and destruction of dye chromo-
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Liaoa et al. prepared Bi2WO6 via hydrothermal method and phore structures is proceeded by the formation of a
37
showed its’ photocatalytic degradation pathway (Figure 5) of carbon-centered radical. The photocatalytic pathway is
38
crystal violet (CV) dye along with identification of depicted in below figure. At first the CV dye molecule is
39
intermediates.[125] Generally, the degradation of CV occurs adsorbed. Then, OH radicals attack through the conju-
*
40
through two main step (i) N-de-methylation and (ii) Oxidative gated structure of the CV chromophore lead to the
41
degradation. They are briefly discussed below. formation of a carbon-centered radical. After that carbon-
42
(i) N-de-methylation: The N-de-methylation of the CV dye centered radical was attacked subsequently by molecular
43 *
occurred necessarily through the attack of the OH species oxygen leading ultimately to the formation of (a) and (b).
44
towards the N,N-dimethyl group on the CV molecule The (a) can also be adsorbed on the Bi2WO6 particle surface
45 *
producing the intermediates ( N-de-methylated CV species) and be carried out in comparable events ( OH radical
46
as major products which are shown in the right hand side attraction and hydrolysis or deprotonation, attack, and/or
47 *
of the picture. Most of the OH radicals are formed either oxygen attack) to form a di-N-de-methylated derivative, (c),
48
directly from the reaction between the holes and surface- and the same process occur from (b) to (d). The N-de-
49 *
adsorbed H2O or OH . The CV approached the negatively methylation process persists until complete formation of
50
charged surface of Bi2WO6 particle via the positively the N-de-methylated (g) and (i) take place. All the
51
charged dimethylamine group. The concentration of the intermediates were further degraded to produce different
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intermediates are examined by the HPLC-PDA-ESI/MS. compounds which are finally mineralized and result in
53
(ii) Oxidative degradation of the CV: The degradation of the CO32 and NO3 .[128]
54 *
CV dye may occur through attack of the OH radicals on Comparelli et al. reported the photocatalytic degradation of
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the central carbon of the CV through the conjugated methyl-red dye under UV light illumination in the presence of
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nanosized TiO2 and ZnO. Several intermediate by-products were
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These intermediates are further degraded to produce smaller

1
aromatic intermediates containing a six and a five-atom ring
2
phthalide which are oxidized to yield smaller fragments e. g.
3
phthalic acid, fumaric acid, succinic acid, malonic acid, maleic
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acid. Low molecular weight acids e. g. oxalic acid, formic acid,
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acetic acid, decompose to yield carbon dioxide by decarbon-
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ylation. Decarbonylation of these acids takes place via the
7
photo-Kolbe reaction.[132]
8
9
R-COO þ hþ ! R0 þ CO2
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Jallouli et al. reported the photocatalytic degradation of a
12
well-known pharmaceutical compound, ibuprofen (IBU) in
13
municipal water, ultrapure water, and pharmaceutical industry
14
wastewaters using TiO2photocatalyst under UV-LED system.[133]
15
The proposed degradation mechanism is shown below (Fig-
16 *
ure 8). The OH radical generated from TiO2 oxidize the
17
ibuprofen molecule producing hydroxy IBU (a) decarboxylation
18
of IBU produces intermediate (b) which is further oxidized by
19 *
OH radical to produce (d). On the other hand decarboxylation
20
occurs as a result of intermediate (c) produce which further
21
degraded to intermediate (e) when depropylation occur. Finally,
22
the aromatic ring of intermediate (e) is opened and mineralized
23
to carbon-di-oxide and water.
24
Yang et al. reported photocatalytic oxidation of paracetamol
25
including identification of intermediates and mechanisms using
26
TiO2 as photocatalyst under UV light.[134] It is clear that the
27
reaction mechanism (Figure 9) can proceed in three pathways
28
(1,2 and 3) as a result of ortho, meta and para hydroxylated
29
paracetamol with respect to OH group of paracetamol (a,b
30 Figure 4. Photocatalytic degradation pathway of MB.[124] *
and c) is produced by addition of OH onto the aromatic ring.
31
Among the three products, product b is the dominant one
32 *
because it exhibited the highest concentration. Addition of OH
33
recognized by HPLC-MS, showing that two different mecha- radical at ortho position with respect to the to the OH group
34
nisms (Figure 6) were operative during the photocatalytic of paracetamol is preferable. This may be attributed by the
35
oxidation.[129] The first mechanism is basically demethylation of nearby OH, stronger electron-donor group than the opposite-
36
N(CH3)2 group attached to the benzene ring producing NHCOCH3 in the benzene ring of paracetamol which make the
37 *
intermediates a and b. The second mechanism involve the ortho position more susceptible to attack by electrophilic OH.
38 *
formation of OH which originate from the oxidation of H2O or From the dihydroxy product, trihydroxy product can be formed
39
OH with the help of photogenerated holes, or from the by further oxidation by releasing acetamide from solution. Then
40
primary reactions of the photogenerated electrons with dis- cleavage of aromatic ring by further oxidation yield carboxylic
41
solved oxygen.[130] The OH attack the benzene rings of methyl-
*
acids, hydroxyl acetic acid, formic acid etc. UV/TiO2 photo-
42
red leading to formation of mono or poly-hydroxylated by- catalytic decomposition of paracetamol can easily transfer
43
products c-f which further degraded to low molecular by- nitrogen in aqueous phase to volatile ammonia. According to
44
products. pathways (3), acetamide can yield oxamic acid through further
45
Stylidi et al. proposed a degradation pathway of aqueous OH oxidation because the electrophilic CO NH2 group of
*
46
solution of Acid orange 7 (AO7) dye using TiO2 suspension in acetamide makes hydrogen atoms of methyl group capable of
47
presence of solar light.[131] The proposed reaction scheme is oxidation by OH forming oxamic acid.[135] Mineralization
*
48
given below (Figure 7). According to the reaction scheme AO7 through OH oxidation of oxamic acid produceNH4 + ions,
*
49
adsorbs on the TiO2 surface. The adsorption of AO7 occurs consequently converted to nitrate.
50
through two different form of molecule, one is the oxygen of Caoet al. reported kinetics and the degradation mechanism
51
the hydrazone form (C=O) and the other is two oxygen atoms (Figure 10) of phenobarbital, a pharmaceutical and personal
52
of the sulfonate group of the dye molecule. Oxidative cleavage care product compound TiO2 aqueous solution. The photo-
53
of the azo bond of dye molecule occurs on AO7 under the catalytic degradation mechanism occur through two
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pathway.[136] Addition of OH radical into Phenobarbital mole-
*
irradiation of the solar light as a result of naphthalene-type
55
molecules as for example 2-naphthol (a) and coumarin (b) are cule leads to the formation of mono and poly hydroxyl
56
produced which are regarded as primary intermediate products. derivative of Phenobarbital in pathway 1 producing intermedi-
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© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 5. Photodegradation mechanism of crystal violet dye in aqueous Bi2WO6 dispersions.[125]
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28 Figure 6. Proposed degradation mechanism of methyl red by immobilized TiO2 and ZnO nanoparticles.[129]
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ate A and B. The hydroxyl derivative completely mineralized to catalysis in presence of photosensitizers named methylene blue
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CO2 and water when the photocatalytic reaction time is and rose bengal.[138] They identified the intermediates and
33
lengthened appropriately. In pathway 2, cleavage of pyrimidine proposed a degradation mechanism (Figure 12). At first the
34
ring takes place producing intermediate C and D which are carbamate group is eliminated from carbofuran molecule
35
further mineralized to CO2 and water. forming carbofuran phenol. Therefore, hydroxylation and keto-
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Martínez et al. studied the photocatalytic degradation of nation help to initiate decomposition of carbofuran which leads
37
diclofenac, a non-steroidal drug under both near UV Vis and to the formation of intermediates A, B, D, E. In the next step
38
UV irradiation by commercial TiO2 P25 photocatalyst, synthe- heterocyclic ring opening and hydroxylation takes place from
39
sized TiO2 (anatase and rutile) and functionalized multi-walled which substituted alcohol as for example 2 ethyl 1-hexanol, 2-
40
carbon nanotube, anatase suspensions as catalysts.[137] They also butoxyl ethanol, 1-propanol. All the substituted alcohols are
41
identified the intermediates and proposed a photocatalytic finally mineralized to CO2 and water.
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degradation pathway (Figure 11). According to pathway 1, Guo et al. reported photocatalytic degradation and it’s
43
photo cyclization to the corresponding mono halogenated mechanism (Figure 13) organocholorine pesticides, hexachlor-
44
carbazole occurs which involves loss of hydrogen and chlorine ocyclohexane using irradiation of POMs/SiO2 slurry in the near-
45
UV region.[139] According to first pathway OH radical oxidize the
*
atoms. Then, structural rearrangement leads to the formation of
46 *
the intermediate A. Then the Cl group is substituted by OH HCH molecule as a result of formation of phenyl hexachloride
47
radical producing intermediate C. In a alternative way inter- with abstraction of H +. According to second pathway aromatic
48
mediate A can undergo decarboxylation to yield intermediate B ring is consecutively undergone hydroxylation at a C Cl bond
49 *
which can further loose second chlorine atom and may suffer by OH radical. As a result, intermediate B (polyphenol) and C
50 *
OH radical addition producing intermediate D and E respec- (tetrahydroxy benzoquinone) are produced. Moreover, inter-
51
tively. According to pathway 2, Diclofenac undergoes decarbox- mediate C is converted to benzoquinone (D). Then in the third
52
ylation that leads to the formation of intermediate F that pathway aromatic ring is opened forming 1, 6 hexanedicarbox-
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undergo further dechlorination and oxidation and produce ylic acid. This dicarboxylic acid is degraded producing acetic
54
compound G, H and B. acid, formic acid which then further degraded to CO2 and HCl.
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Kuo et al. studied the degradation of Carbofuran, an Mir et al. reported the photocatalytic degradation mecha-
56
insecticide used in agricultural field, in water by solar photo- nism (Figure 14) of Bentazone, a post emergence herbicide in
57

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Figure 7. Photocatalytic degradation mechanism of acid orange 7.[131]
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H2O2 mediated aqueous suspension of TiO2 under UV light

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exposure along with recognition of intermediates.[140] At first
2
desulfonation of Bentazone yield compound A which under-
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goes addition by hydroxyl radical with side by side loss of
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isopropyl amine group leads to the formation of 2-amino-
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occurs which forms nitrosyl derivative D via intermediate C.
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Product D is further oxidized to give nitro derivative E. Finally,
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denitration of the product E yield compound F (N-isopropylben-
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zamide).
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Kaneco et al.[141] reported photocatalytic degradation mech-
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anism (Figure 15) of dibutyl phthalate, a major endocrine
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disruptor in aqueous titanium dioxide (TiO2)-suspended solution
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along with its kinetics, mineralization and reaction mechanism.
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At first the reaction undergoes by attack of OH radical formed
*
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from TiO2. There are mainly two sites of DBP for attack of OH
*
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radicals, the aliphatic chain and also the aromatic ring in the
17
DBP structure. Intermediate products (ii)-(xiii) are formed during
18
attack of OH radicals into the aliphatic chain. Moreover, they
*
19
are further oxidized through occurrence of ring-rupturing
20
reactions into aliphatic compounds containing acetic acid,
21
acetaldehyde and formic acid, which are finally mineralized to
22
CO2 and water. Another intermediate products (i) such as
23
hydroxy and dihydroxy photoproducts are formed by hydrox-
24
ylation of aromatic ring (except 5 C and 6 C) of DBP structure by
25
OH radical. Intermediates having long chain structure (xiv) and
*
26
(xv) are generated as attack of OH radicals on two carbon
*
27
atoms (5 C and 6 C) positioned in α-position with respect to
28
carboxyl group occurs. Hence, the positions are cleaved. The
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photocatalytic degradation of long chain intermediates leads to
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slow mineralization to CO2 compared to aromatic ring moiety.
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Figure 8. Proposed photocatalytic degradation mechanism of ibuprofen.[133] Table 1 depicts the study of degradation and intermediate
32
formation for different organic pollutants using TiO2 based
33
photocatalyst.
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56 Figure 9. Proposed reaction pathways during photocatalytic degradation of paracetamol.[134]
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14 Figure 10. The proposed photocatalytic degradation pathways of Phenobarbital in TiO2 aqueous solution.[136]
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Figure 11. Proposed photocatalytic degradation pathway of Diclofenac.[137]
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6. Summary which involved the utilization of titania and titania based
38
semiconductors towards photo degradation process. The tox-
39
This study provides a critical Review of photoassisted degrada- icity of the intermediates produced during degradation process
40
tion of organic pollutants in water by semiconductor nano- as well as the final degraded product is also a high concern
41
material. In this regard, advanced oxidation processes (AOP) has recently. This review assimilates elaborate study on the
42
been considered as an effective route for water purification. mechanism of photocatalytic degradation of various organic
43
This process relies on the in-situ generation of powerful pollutants.
44 *
hydroxyl radicals ( OH) in sufficient quantity to oxidize recalci-
45
trant toxic organic pollutants present in wastewater. From this
46
point of view heterogeneous photocatalysis acquires major 7. Outlook
47
importance in-terms of a non-toxic, cost-effective, easy process.
48
A number of scientific investigations have been performed, Earlier, researchers mainly focused on TiO2 because it had been
49
which elucidate suitable properties (band gap energy, carrier investigated to perform total mineralization of most of the
50
transport, crystallinity etc.) for the deliberate design of efficient organic pollutants existed in aqueous systems. Despite the
51
photocatalysts. The oxidation rates and degradation efficiency increased use and development in the past decades, TiO2-based
52
of the photocatalyst are influenced by some of the basic photocatalytic technology still suffers from some technical
53
parameters like organic pollutant concentration, photocatalyst barriers that impede its commercialization. One of the major
54
concentration, pH, reaction temperature, light intensity, irradi- limitations is the narrow photocatalytic region (l < 400 nm) and
55
ation time, inorganic ions, and oxidants. The interesting proper- ability to absorb a small fraction (< 5 %) of incident solar
56
ties of titania attracts greater attention of scientific community irradiation and indoor light, which results from its relatively
57

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Figure 13. Pathway of Photocatalytic Degradation of Aqueous hexachloro hexane.[139]
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Figure 12. Proposed degradation pathway of carbofuran.[138]
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Figure 15. Proposed photocatalytic degradation mechanism of DBP.[141]
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1 Table 1. List of studies on degradation and intermediate formation for different organic pollutants using TiO2 based photocatalyst.
2 Type of pollu- Catalyst used Catalytic condition Intermediates Ref
3 tant
Pharmaceutical compound
4
5 Ibuprofen Degussa P25-TiO2 Sonolysis with ultra- Mono and dihydroxylated products, 4- ethyl benzaldehyde, 4- (1- [142]
and Fe(NO3)3· sound frequency carboxyethyl) benzoic acid, 4-isobutyacetophenone and 4-ethylphenol
6 9H2O of 213 kHz& sonophoto-
7 catalysis
8 Phenobarbital Degussa P25-TiO2 UV light with power Monohydroxy derivative, cleavage of pyrimidine ring [136]
consumption of 125
9 watt
10 Sulfametha- Degussa P25-TiO2 UV lamp with intensity Hydroxylated derivative, sulfanilic acid, amino phenyl, pyrimidinyl, anilium [143]
11 zine (1 mW/cm2). ion, Sulfanilamide
Paracetamol P-25 TiO2 nanopar- UV light with intensity Hydroquinone, 1.4 benzoquinone, [144]
12 ticle & TiO2/cellulosic 11 watt p nitro phenol, 1,2,4-trihydroxy benzene, p amino phenol
13 fiber
14 Omeprazole TiO2 Long wave UV light pyridine and benzimidazole derivatives [145]
Metoprolol Degussa P-25 TiO2 UV light Dihydroxy derivative, trihydroxy derivative, Tetrahydroxy derivative [146]
15 Tartarate
16 Naproxen TiO2 solar irradiation with Decarboxylated product, demethylated product [147]
17 the Xe-lamp simulator
source
18 Tetracycline Nano sized TiO2 UV irradiation with Deamination, desulfurization and dealkylated product, dimethylamine [148]
19 power of 18 W
20
Pesticides, Herbicide, Insecticide and fungicide
21
22 Methomyl Degussa P-25 TiO2 UV irradiation with a De methylated product, Methomyl oxime [149]
23 power of 125 W
Diazinon Nano-TiO2 UV irradiation with a 2-isopropyl-6-methyl-pyrimidin-4-ol, diazoxon and hydroxydiazinon [150]
24 power of 125 W
25 Acetamiprid O2/TiO2 UV irradiation with a Acetaldehyde, acetic acid, formic acid [151]
26 power of 125 W
4-chloro Phosphorus modi- UV irradiation with a Hydroquinone, benzoquinone, 4-chloro catechol [152]
27 phenol fied TiO2 power of 11 W
28 Bentazone Degussa P-25 TiO2 UV irradiation with a Desulphonated product, 2-amino benzoic acid, N isopropyl benzamide [153]
29 power of 125 W
Boscalid Degussa P-25 TiO2 UV irradiation with a Monohydroxylated product, Dihydroxylated product, decarboxylated prod- [154]
30 power of 125 W uct, 2-chloro pyridine
31 Diuron Degussa P-25 TiO2 UV irradiation with a Trichloroaniline, dichloronitrobenzene,N(3,4dichlorophenyl)formamide,N,N- [155]
32 power of 125 W dimethylurea
33 Dye
34
35 Crystal violet Degussa P-25 TiO2 UV irradiation of 15 W Mono-, di-, tri-, tetra-, penta-, and hexa-N-de-methylated CV, N- [156]
hydroxymethylated product
36 Methylene TiO2, P2ABSA-modi- 1000 W xenon lamp Azure A, Azure B, Azure C, thionin [157,
37 blue fied TiO2 nanocom- 158, 159]
38 posite
Acid orange 7 TiO2 anatase suspen- UV lamp of 9 W 2 naphthol, oxime methoxy phenyl, benzaldehyde, benzophenone, [160]
39 sion toluene, 2-methyl phenol, t-butyl amine, benzyl alcohol, decen-2en-1-ol,
40 glutaric acid
41 Malachite TiO2 suspension Microwave irradiation (p-dimethylaminophenyl)(p-methylaminophenyl)phenylmethylium,(p- [161,162]
green methylaminophenyl)(p-methylaminophenyl)phenylmethylium,(p-meth-
42 ylaminophenyl)(p-aminophenyl)phenylmethylium,(4- dimethyl-aminoben-
43 zophenone, phenol, terephthalic acid, adipic acid, benzoic acid,
44
45
46
large band gap (anatase, ~ 3.2 eV). Besides sludge can be treatment techniques) employing visible and/or solar light
47
formed during photocatalytic degradation of pollutants from irradiation. The desirous goal of the nanoparticle assisted
48
which secondary pollution can be generated in the environ- photocatalysis is to achieve complete degradation and mineral-
49
ment. Again, recovery of nanosized TiO2 particles from the ization of hazardous organic pollutants present in wastewater,
50
treated water regards to both the economic concern and safety not only in laboratory scale but also in industrial scale.
51
concern. In addition, TiO2catalyzed photocatalysis exhibit poor The above mentioned technical and commercial barriers
52
selectivity i. e. lack of selectivity and action between extremely can be dissolved by tuning the nanomaterials in the following
53
perilous and less hazardous contaminants, during photocata- ways for the desirable future prospectus- i) modification of TiO2
54
lytic degradation. Hence, a requirement of highly selective catalyst to achieve the utilization of visible light ii) design and
55
catalyst which shows affinity only towards non-biodegradable development of second generation of TiO2 catalyst, with high
56
pollutants (which are inactive by biological or other common separation ability, which can be recovered and regenerated
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effectively iii)preparation of other nontoxic, cost-effective, easily [24] L. Amalric, C. Guillard, P. Pichat, Res. Chem. Intermed. 1995, 21, 33–46.
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Conflict of Interest [38] S. Iyyapushpam, S. T. Nishanti, D. Pathinettam Padiyan, J. Alloys Compd.
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ChemCatChem - 2020 - Som - Advances in Nanomaterial Based Water Treatment Approaches For Photocatalytic Degradation of

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2.1.1. Fenton’s process undergo effective oxidation of organic pollutants in

Liu et al. studied the experiment under three various light .

These intermediates are further degraded to produce smaller

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemCatChem 2020, 12, 3409 – 3433

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemCatChem 2020, 12, 3409 – 3433

H2O2 mediated aqueous suspension of TiO2 under UV light

© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 13. Pathway of Photocatalytic Degradation of Aqueous hexachloro hexane.[139]

Figure 12. Proposed degradation pathway of carbofuran.[138]

ChemCatChem 2020, 12, 3409 – 3433

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