Journal of Cleaner Production 268 (2020) 121725

Contents lists available at ScienceDirect

Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Review

Photocatalytic degradation of organic pollutants using TiO2-based

photocatalysts: A review
Dongjie Chen a, b, Yanling Cheng a, Nan Zhou a, Paul Chen a, Yunpu Wang a, c, Kun Li c,
Shuhao Huo e, Pengfei Cheng a, Peng Peng a, Renchuang Zhang a, Lu Wang a, Hui Liu d,
Yuhuan Liu c, Roger Ruan a, b, *
a
Center for Biorefining and Department of Bioproducts and Biosystems Engineering, University of Minnesota, St. Paul, MN, USA
b
Department of Food Science and Nutrition, University of Minnesota, St. Paul, MN, USA
c
College of Food Science and Engineering, Nanchang University, Jiangxi, China
d
Department of Environment Science and Engineering, Zhongkai University of Agriculture and Engineering, Guangzhou, China
e
School of Food and Biological Engineering, Jiangsu University, Zhenjiang, China

a r t i c l e i n f o a b s t r a c t

Article history: Organic compounds, generated from different industries, produce a range of the problematic pollutants
Received 14 November 2019 in wastewater. TiO2 based photocatalysts are novel materials that exhibit excellent absorption behavior
Received in revised form toward organic compounds in wastewater due to their outstanding properties including nontoxicity, high
11 April 2020
photocatalytic degradation ability, and excellent thermal and chemical stabilities. However, several
Accepted 13 April 2020
Available online 17 April 2020
challenges exist regarding TiO2 applications for organic effluents such as particle aggregation, mass
transfer limitation, poor affinity, high band energy, scattering conditions, and difficulty of recovery.
Handling Editor: Prof. Jiri Jaromir Kleme
s Therefore, more design and optimization testing need to be conducted on the treatment conditions in
order to reach higher removal efficiencies with lower costs. A variety of parameters of TiO2 based
Keywords: photocatalysts need to be studied: substrate, light intensity, dopant, particle size, structure. These pa-
Organic pollutants rameters, which affect TiO2 photocatalytic activity on organic pollutants, are discussed in the current
TiO2 based photocatalysts review. Thus, making the photocatalyst more anticipated and conducive to further research and
Photocatalytic degradation development.
Processing parameters
© 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Research methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Planning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Searching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Screening and reporting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Common organic pollutants in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Phenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3. Petroleum hydrocarbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. TiO2 photocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.1. Mechanism of TiO2 photocatalytic reaction on organic pollutants in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4.2. Limitation of TiO2 photocatalysis on organic pollutants in wastewater . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
5. Parameters affecting the photocatalytic degradation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
5.1. Intensity of light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

* Corresponding author. Center for Biorefining and Department of Bioproducts

and Biosystems Engineering, University of Minnesota, St. Paul, MN, USA.
E-mail address: [email protected] (R. Ruan).

https://doi.org/10.1016/j.jclepro.2020.121725
0959-6526/© 2020 Elsevier Ltd. All rights reserved.
2 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725

5.2. TiO2 structure and form . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5

5.3. Substrate/supported types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
5.4. pH values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7
5.5. Particle size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
5.6. Catalyst/dopant dosage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
5.7. TiO2 dopant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9
5.8. Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction Mosse et al., 2011). On the other hand, insufficient biodegradable

potential is still existing for some of organic effluent (Rathoure and
Nanostructured semiconductors show great potential for envi- Dhatwalia, 2016; Wang et al., 2012). Chemical precipitation has
ronmental remediation because of photocatalytic oxidation, which been widely used in removal of contaminants from various
is activated under the solar light or UV light (Feizpoor and Habibi- wastewaters. Based on the composition of the wastewater, chem-
Yangjeh, 2018). Numerous organic pollutants are being released ical precipitation can be used to remove ammonia (NH4þ) and
form manufacturers such as textile, paint, and leather into water phosphate (PO43), etc. However, chemical precipitation poses
bodies. The aquatic systems and human health may be seriously several disadvantages: (1) high chemical consumption such as lime,
affected by these organic effluents, which are extremely difficult to oxidants, or H2S; (2) physicochemical monitors such as pH are
be degraded or eliminated by nature (Fernandez et al., 2010). needed for the effluent; (3) high sludge generation (Crini et al.,
Several conventional methods such as biological methods, chemi- 2019); (4) the excessive chemical usually causes a secondary
cal precipitation, and membrane filtration are proposed for pollution issue (Sharma and Sanghi, 2012). Membrane filtration is
wastewater treatment. However, these methods may not always be an alternative physical method for wastewater treatment (Barakat,
very effective or feasible. Table 1 lists the strength and weakness of 2011). Separation mechanisms depend on particle size, solubility,
different treatment techniques Biological methods are commonly diffusivity, and charge. It has advantages of simple, effective, and
used for wastewater treatment, because it is economical to meet rapid removal even at high concentrations of pollutants such as
effluent standards, and proven to be accepted in the industry. A solids, microorganisms, inorganic matter, and phenols (Strong and
number of studies also reported that microalgae can be cultivated Burgess, 2008). However, most of the commercial membranes are
to apply to wastewater treatment. However, when using micro- not considered semi-permeable, the membrane with the smallest
algae, the wastewater effluent usually needs to be diluted several- pore size and reverse osmosis are not capable of restricting solute,
fold before biological treatments. Microalgae are susceptible to especially for low molecular weight non-charged organics (Bellona
concentrated toxicity, wastewater effluent may need to be diluted et al., 2004). In addition, in spite of high efficiency at lab scale,
up to five-fold with synthetic media to reduce the toxicity before commercial scale investment costs including maintenance and
adding green algae. A study indicated that undiluted wastewater operation costs are usually high for medium or small industries.
with a high NH4eN concentration of 1197 mg/L could cause adverse Moreover, low throughput or low flow rates due to clogging or
effects on the photosynthesis of S. obliquus (Ji et al., 2013). Biological fouling problems, may limit some application for membrane sep-
process is also difficult to control, operators need to handle fluc- arations at high concentrations of pollutants.
tuations in effluent composition and volumes because of variable Therefore, photocatalysis treatment shows strong potential for
wastewater composition and quantity (Morin-Crini et al., 2017; the degradation of organic pollutants (Rossetto et al., 2010).

Table 1
The strength and weakness of each available treatment techniques for organic pollutants.

Strength Weakness

Biological 1. Cost-effective and environmentally friendly 1. It has not enough capability to remove high concentration level
treatment 2. Excellent reduction of odor and color of organic waste
3. High throughput 2. Biological process is difficult to control
3. It does not diminish chemical oxygen demand values
4. Low biodegradability of some types of organic matter such as
dye
Chemical 1. Low energy consumption 1. High chemical consumption (i.e. lime, oxidants, H2S, etc.)
precipitation 2. Simple process 2. pH value needs to be monitored
3. A wide range of chemicals are available commercially 3. High sludge generation
4. Efficient removal in total organic carbon and absorbable organic halogen 4. Adjunction of non-reusable chemicals (coagulants, flocculants,
especially in pulp and paper industry aid chemicals) were required
Membrane 1. Effective and rapid 1. Relatively high cost of maintenance and operation
filtration 2. Eco-friendly, non-toxic, non-corrosive, and safe to plants and animals 2. Limited feeding rate
3. High removals of constituents 3. Permeate flux and productivity are decreased because of
membrane fouling
Traditional 1. Environmentally friendly 1. Materials are difficult to recovery and regeneration
photocatalysis 2. Low process cost, high energy saving, outstanding susceptibility 2. Degradation effectiveness reduces due to the excess of pollutant
3. Adjustment of catalyst loading is easy 3. Potential photocatalyst losses under long-term operation
 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725 3

Heterogeneous photocatalytic oxidation was claimed in 1967. 2.2. Searching

Among a variety of transition metal oxides, a rutile TiO2 electrode
had been chosen as a metal oxide which has an adequately positive The published articles between 2007 and 2020 (until March
valence band to cause oxidation. This theory has attracted 2020) were examined for the literature search. Database of Scopus
tremendous attention because it can be applied under solar light was used as search engine. Both minor and major publishers such
(Yurdakal et al., 2008). Then extensive studies have been conducted as Elsevier, Emerald, Springer and Wiley are included in this data-
to degrade and mineralize certain toxic organic compounds in base. Several keywords were chosen to identify the literature and to
wastewater. Results suggested that TiO2 was one of the most avoid the biased research. In this paper, waste management was the
effective catalysts for the removal of organic chemicals particularly central topic, disaster was the context. Thus, the keywords should
dyes and phenolic compounds from aqueous solutions (Fig. 1). be detailed from three aspects, a. photocatalytic degradation, b.
Although many reviews have summarized different photocatalysts TiO2 based photocatalyst, c. organic pollutants. In which, three
for the application of eliminating microbes and toxic chemical terms: “phenol”, “dye”, and “Petroleum hydrocarbon” were widely
compounds in wastewater, few reviews have summarized organic used by researchers interested in petrochemical wastewater
pollutant degradation under TiO2 based photocatalysts as a func- research. Furthermore, the meaning of word which is belong to
tion of various process parameters (Table 2). In the current review, “phenol”, “dye”, and “Petroleum hydrocarbon” were also taken into
the process parameters including catalyst structure, supported consideration, such as “Methylene blue”, “Rhodamine B”, “Methyl
type, pH value, particle size, dopant type, and dopant concentration orange”, “Azo dye”. 626 articles were classified as potentially
will be fully evaluated through degradation of organic pollutants relevant based on the search process.
under light irradiation.
2.3. Screening and reporting

2. Research methodology To ensure the completeness and fidelity of this review, titles and
abstracts from 626 publications were screened and evaluated
The focus of the study is to evaluate the impacts of various before choosing as relevant papers. During the first screening, the
process parameters of TiO2 based photocatalysts on the organic journal, book, and conference papers presented in English were
pollutant degradation and enable cleaner production. Therefore, selected. To further identify and select the most suitable papers, the
we conducted an appropriate approach to manage a large amount following three other criteria were evaluated. 1) Removing ana-
of information (Popay et al., 2006). This approach narrows down logues and preserve the typical literatures; 2) select articles related
the literature to the particular research question that aims to to the research subject; 3) screen the articles with high significance.
identify the factors that influence organic pollutant degradation. With respect to subject, the selected articles mainly focus on
More perception was gained for reviewers by following the meth- investigating the organic pollutant management in petrochemical
odology proposed by (Tranfield et al., 2003), four primary steps wastewater. In contrast, some researchers who addressed unsuit-
including planning, searching, screening, and reporting were uti- able wastewater or matters such as swine manure, microorgan-
lized in the following subsections to understand the topic in depth isms, metal ions, and pharmaceuticals were excluded. In terms of
(Centobelli et al., 2017). TiO2 based photocatalyst, TiO2 based catalysts used for other ap-
plications such as electrocatalytic activity and fuel were excluded.
The remaining articles were compared with each other, and then
2.1. Planning
were categorized based on process parameter used, as presented in
the structure of this review. Overall, 168 researches were summa-
At the beginning of this review, a review panel (common
rized and critically analyzed in terms of the content, abstract, and
organic pollutants in wastewater, mechanism of TiO2 photocatalytic
the important features.
reaction, limitation of TiO2 photocatalysis) was established to
discuss the research question and the needs of this review. The
3. Common organic pollutants in wastewater
following research questions were defined.

3.1. Phenol
RQ1. What is the current status of the research on organic pol-
lutants in wastewater?
Phenolic consists of aromatic compounds with one or more
RQ2. What is the limitation of TiO2 based photocatalysis on
hydroxyl groups attached to the aromatic ring. The issue of phenols
organic pollutants in wastewater?
and their derivatives have attracted more and more global concern.
RQ3. What parameters can be controlled to improve the TiO2
Domestic and industrial activities such as phenolic resin
based photocatalytic degradation?
manufacturing, oil industry, pesticide synthesis, plastics, coking
operations, wood products, pulp, textiles, detergents, and phar-
maceuticals, have discharged harmful and toxic phenolic com-
pounds to water bodies including rivers, lakes, and sea (Das et al.,
2018; Villegas et al., 2016). Some phenolic contaminants can also
be generated from aquatic environments including lignin trans-
formation, algal secretion, hydrolysable tannins, and flavonoids
(Zainudin et al., 2010). Human as well as other living creatures
worldwide are suffering from this toxic risk. Phenols, exposed in
effluent to the environment, directly pose hazards to humans as
lungs can absorb them rapidly in a short period. All forms of phe-
nols and its derivatives, due to their corrosive nature, can cause
irritation to the respiratory tract, eyes, and skin. Prolonged expo-
Fig. 1. Diagram of TiO2 photocatalysis treatment on effluent organic compounds in sure of diluted concentrations of phenol can cause serious burn
wastewater. (1e2%) and may lead to dermatitis (Rathna and Nakkeeran, 2018).
4 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725

Table 2
The recent reviews related to organic pollutant degradation using TiO2 based photocatalysts.

Descriptions Reference

These reviews provide a deep insight of doped catalyst which uses non-metals, transition metals and (Fang et al., 2017; Khaki et al., 2017; Nasirian et al., 2018)
titanium dioxide on organic pollutant.
These reviews offer possible substrates to load the TiO2 such as clay, nanotubes, multi-walled carbon (Khalid et al., 2017; Li, X. et al., 2018; Sirirerkratana et al.,
nanotubes. 2019; Szczepanik, 2017)
These reviews aim to summarize all modified nano TiO2 structures and properties. €kmen et al., 2017; Thakur and
(Li, Z. et al., 2018; So
Kandasubramanian, 2019)
These reviews only reveal partial parameters of TiO2 that affect photocatalysis (Bhanvase et al., 2017; Krsti c et al., 2018)

3.2. Dyes also react with organic compounds to provide reduction products
(equations (1)e(7)). The role of oxygen (equation) is important
Dye pollutants discharged in industrial wastewater often receive because it can react with the photo-generated electrons,
much attention due to color and toxicity. Their disposal has resulted
in serious contamination in many countries worldwide. Even a TiO2 þ hv/e þ
cb þ hvvb (1)
small amount of dyes (<1 ppm for some dyes) are considered as an
important class of contaminants in wastewater, because they can be hvþ
vb

þ OHsurface /OH (2)
visually identified by human eyes in water (Shakoor and Nasar,
2016). Dyes may cause severe contamination as more than 10,000
commercially available dyes are inevitably used in many fields such hvþ
vb
þ H2 Oabsrobed /OH þ Hþ (3)
as dyestuffs, textiles, paper, plastics, rubber, cosmetics, tanneries,
paints, and leathers (Peng et al., 2016). More than 700,000 tons of e 
cb þ Oabsrobed /O2 (4)
dyes are produced annually worldwide; approximately 12% of the
total world production of dyes is lost during processing operations hvþ þ Organic/Oxidation products (5)
vb
or manufacturing, where 20% of these lost dyes enter environment
and cause contamination (Demirbas, 2009). Various types of dyes
produced from industry poses a serious hazard to aquatic living OH þ Organic/Degradation products (6)
organisms. In addition, dyes also contribute to negative impacts on
human beings and animals, symptoms such as abdominal e
cb þ Organic/Reduction products (7)
discomfort, nausea, vomiting, diarrhea, and irritation (Shakoor and
Nasar, 2016).

4.2. Limitation of TiO2 photocatalysis on organic pollutants in

3.3. Petroleum hydrocarbon wastewater

Energy resources and raw materials generated from petroleum In total 160 articles associated with limitations of TiO2 photo-
hydrocarbons are critical for various industries. Data collected from catalysis on organic wastewater, the percentage of the articles for
1970 to 2013: International Tanker Owners Pollution Federation each limitation is shown in Fig. 2. (1) Photocatalytic degradation
Ltd., shows three time-oil spills (>700 tons) occurred in year 2013 mainly occurs on the surface of TiO2, transfer limitation of electron
(Borah and Yadav, 2017). Great attention was received because of and hole pairs inhibits TiO2 photocatalytic efficiency. Recombina-
their cataclysmic effect in large-scale marine oil spills and oil spill tion of electrode and hole charge carriers is likely to occur in titania,
accidents. Petroleum hydrocarbon pollutants are recalcitrant which leads to the suppression of photocatalytic activity (Kusiak-
compounds and are classified as priority pollutants (Costa et al., Nejman and Morawski, 2019). (2) Poor affinity of photocatalysts
2012). However, increasing demand for suitable alternatives to towards organic pollutants (i.e. hydrophobic organic pollutants):
petroleum products in everyday life are still not available in com- slow photocatalytic degradation rates were caused by low
mercial quantities (Varjani and Upasani, 2016). Offshore and adsorption of organic pollutants on the TiO2 surface. Photocatalyst
onshore petroleum industry accidental spills lead to petroleum immobilization can provide a selective affinity toward target con-
hydrocarbon pollution. This pollutant affects water bodies directly. taminants (Lee et al., 2018). (3) During photocatalytic degradation,
It is well known that the water bodies are considered, unfortu- the TiO2 nanoparticles may experience aggregation because of the
nately, as the ultimate and largest sink for petroleum hydrocarbon instability of the nanosized particle, which may prevent on the
pollutants (Sajna et al., 2015). active centers from receiving the light radiation and consequently
hamper photocatalytic activities of TiO2 (Mallakpour and Nikkhoo,
4. TiO2 photocatalyst 2014). Aggregation of TiO2 is a result of particles being bridged by
organic ionizable molecules (Cervantes-Avile s et al., 2017). (4)
4.1. Mechanism of TiO2 photocatalytic reaction on organic Higher scattering conditions as a result of TiO2 nanoparticles may
pollutants in wastewater lead to reduction of TiO2 photocatalytic activity (Minero and Vione,
2006). The appropriate TiO2 concentration and UV wavelengths is
Under light irradiation (photons), electrons and positive holes critical to increase the photocatalytic activity (Turolla et al., 2016).
are generated in the conduction (e cb
) and valence band (hvþ
vb
) of (5) For organic compound treatment in wastewater, another major
titanium dioxide according to equation (1) (Poulopoulos and practical challenge to overcome is to recover the nanosized TiO2
Philippopoulos, 2004). The holes can either react directly with particles from the treated water efficiently and safely. A previous
organic molecules (equation (5)) or form hydroxyl radicals (equa- study reported TiO2 nanosized powder is well dispersed in sus-
tion (3)) that subsequently oxidize organic molecules (equation (6)) pension and more effective than fixed support. However, a practical
(Ahmad et al., 2016; Akpan and Hameed, 2009). The electrons can issue pertinent to applications is recovering particles from the
 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725 5

Fig. 2. Limitations of TiO2 based photocatalysts on organic compounds in wastewater *the percentage of the articles related to each limitation is shown above.

wastewater. (6) High band energy of initial TiO2 photocatalyst, with increasing of LED current from 0.22 to 0.68 amps (Maki et al.,
initial TiO2 photocatalyst is considered as less energy-efficient than 2019). Similar, the efficiency of isopropanol degradation by TiO2
standard heterostructure photocatalyst as its decomposition pro- nanotube were raised rapidly to 56% with increasing UV light in-
cesses is driven by sunlight (Raza et al., 2020). further investigation tensity from 0 to 3.0 mW/cm2. However, excessive dosage of light
on improvement of the physical and chemical properties of the did not contribute to higher photocatalytic decomposition because
photocatalyst needs to be conducted to enable the development of of limited amounts of active sites on the surface of TiO2 (Cheng
visible/solar light to activate TiO2 based photocatalysts. To over- et al., 2018).
come these limitations, the TiO2 particle size, dopant type, and
concentration need to be modified to utilize wavelength to visible
light as well as increasing affinity to organic compounds. Second, 5.2. TiO2 structure and form
appropriate substrates with high separation capacity of TiO2
nanoparticles need to be recovered and regenerated effectively. The Apart from light intensity, several other forms and structures of
structure of substrates is also capable of absorbing various organic TiO2 photocatalysts were evaluated on wastewater treatment
pollutants. Third, the photocatalysis environments or other factors (Table 3). Among these various forms, Degussa P-25 TiO2 showed
such as light intensity, calcination temperature, pH, and important significantly higher photocatalytic activity compared with other
additives need to be evaluated for photocatalysis optimization. forms of TiO2 catalysts, i.e., UV100 (100% anatase, Hombikat) and
PC500 (100% anatase, Millennium inorganic chemicals). References
reported the effect of these three forms of TiO2 on the degradation
5. Parameters affecting the photocatalytic degradation of Acridine Orange, Ethidium Bromide, Triphenylmethane dye, and
found the highest degradation rate was achieved using Degussa P-
Based on the limitation mentioned in section 4.2, a variety of 25 TiO2 (Saquib and Muneer, 2003). This is due to the fact that
parameters were controlled to improve TiO2 based photocatalysts Degussa P-25 consists of small nano-crystallites of rutile (18%) that
on organic compounds in wastewater. These key parameters disperses within an anatase matrix (73%) (Jensen et al., 2004).
including intensity of light, TiO2 structure and form, substrate type, These two forms of TiO2 take synergistic effect in Degussa P-25 TiO2
pH value, and doping type affected the efficiency of the photo- during the photocatalytic activity. Anatase TiO2, with an indirect
catalysis process. These notable influential parameters will be bandgap, exhibits a longer lifetime of electrons and holes than
discussed as follow. direct band gap rutile. On the other hand, lower recombination rate
of charge carriers in anatase TiO2 as a result of the lighter effective
5.1. Intensity of light mass enables faster migration of electrons and holes from interior
to surface of anatase TiO2 (Bagbi et al., 2017; Zhang, J. et al., 2014).
The rate of electrons from valence band to conduction band was Rutile TiO2, with a smaller bandgap, is able to catch photons with
affected by the intensity of light, which then affected the rate of lower energy to generate electron/hole pairs, which was further
TiO2 photocatalytic reaction as mentioned in section 4.1. Higher utilized by anatase TiO2 (Faisal et al., 2007). The photocatalyst
intensity usually leads to significantly higher rates of photo- structure also plays a critical role in photocatalysis efficiency. The
catalysis. When the photon energy on each TiO2 active sites is TiO2 structure was optimized to expand the surface area. TiO2
sufficient, the rate of photogeneration becomes less dependent on structure was synthesized as patterns. Modified structure of TiO2
the intensity of light. The rate of photocatalysis relies on a first- with increased surface led to higher photo-catalysis than TiO2
order reaction at relatively low intensity of light (Nasirian and without structure modification (Fig. 3). Khunphonoi and
Mehrvar, 2016), half order was observed at a high intensity of Grisdanurak (2016) claimed photodecomposition rate of p-cresol
light. However, the rate of photocatalysis was no longer controlled with TiO2 nanorods was constent higher than P25 TiO2 catalyst. Liu
by intensity of light beyond an optimal level (Blake et al., 1991). et al. (2019) evaluated the evaluated photodegradation of Facet-
Therefore, adequate photon energy distribution contributes to high tailored TiO2 on phenolic pollutants, the Facet-tailored TiO2
rate of photocatalysis reaction. A research reported the degradation showed a higher efficiency to degrade phenols than P25 TiO2.
of FeeNeCeeTiO2 nanoparticles on dye increased from 10% to 98% Multi-walled-carbon nanotube/TiO2 was also developed to degrade
6 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725

Table 3
Photodegradation effect of TiO2 form and structure on organic pollutants.

Type of catalyst Organic pollutant Reaction Findings Reference

condition

TiO2 Degussa P-25 Rhodamine B UV light Initial concentration is 0.2 g/L, at 120 min, 55% degradation Bagbi et al. (2017)
TiO2 nanorods, TiO2 Degussa P-cresol UV light Degradation is 80% and 50% for TiO2 nanorods and TiO2 Degussa P-25, Khunphonoi and
P-25 respectively, after 240 min Grisdanurak (2016)
TiO2 nanoribbons and carbon Methylene blue UV light Initial concentration is 0.2 g/L, at 180 min, 97.5% degradation Shaban et al. (2018)
nanotubes
The multi-walled carbon 2,4 -dichlorophenol UV and solar Degradation is 93% and 87% for UV and solar light, respectively, after Mohammadi et al. (2014)
nanotube TiO2 light 120 min
TiO2 nanotube Orange II UV light Initial concentration is 70 mg/L, at 2000 min, 89.46% degradation Zulfiqar et al. (2018)
Nano flower-like rutile TiO2 Methylene blue Solar light Initial concentration is 5 mg/L; at 180 min; 98.95% degradation Alias et al. (2020)
Hierarchical mesoporous Methylene blue UV light Initial concentration is 6 mg/L; at 40 min; ~100% degradation Dong et al. (2020)
TiO2 nano-shell
TiO2 Degussa P-25 Acridine Orange and Solar light Highest efficiency of degradation was achieved using P-25 under Faisal et al. (2007)
ethidium bromide alkaline conditions (pH ¼ 10)
TiO2 Degussa P-25 Petroleum wastewater UVA-UVB COD was reduced by 83% after 120 min Shahrezaei et al. (2012)
TiO2 Degussa P-25 Acridine Orange and UV light Degussa P25 showed better performance than other TiO2. Faisal et al. (2007)
ethidium bromide
TiO2 Degussa P-25 Malachite Green UV light 99.9% of Malachite Green was degraded at 6 h. Chen et al. (2007)

Fig. 3. (a) The SEM micrographs of TiO2 nanorods; (b) The SEM micrographs of TiO2 nanoribbons; (c) The TEM micrographs of TiO2 Degussa P-25; (d) The TEM micrographs of Facet-
tailored TiO2.

2,4-dichlorophenol wastewater, Mohammadi et al. (2014) indicated surface. Therefore, facilitating quantum efficiency and photo-
that Multi-walled-carbon nanotube/TiO2 with weight percent ratio catalytic activities (Zhang et al., 2018).
of 60:40 could contribute significantly higher removal (75%) than
the other ratios. With respect to TiO2 nanoribbons/carbon nano-
tubes nanocomposite, the TiO2 nanoribbons/carbon nanotubes 5.3. Substrate/supported types
nanocomposite exhibited noticeable enhancement in the photo-
catalytic degradation of methylene blue when comparing with TiO2 Directly using of TiO2 powder bring several drawbacks such as
nanoribbons (Shaban et al., 2018). Consider facet-tailored TiO2 as an low light utilization, costly separation recovery and human health
example: the single-crystalline structure was optimized as a bulk issues. Selection of substrate is an optimized approach to solve
structure with the co-exposed crystal facets on the surface. The these concerns by many researches. The optical and photo-catalytic
characteristics of continuous, ordered atomic, and electronic effects can be significantly improved by incorporating different
structures contribute to rapid and consistent charge within the bulk carbon based nanomaterials such as graphene, graphene oxide,
phase (Liu et al., 2014; Zhang, A.-Y. et al., 2014). Moreover, the reduced graphene oxide, fullerene, carbon dots, single and multi-
photocatalytic epitaxial layer enables built-in electric field to carry walled carbon nanotubes (Irie et al., 2003; Suarez-Iglesias et al.,
electrons separately among different exposed facets on the solid 2017) into the semiconductor matrices. The application of the
graphene family based TiO2 on organic pollutants is depicted in
 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725 7

Table 4. The solid and intimate contact between TiO2 and carbon from 7.5% to 10% of rGO composite may be due to the surface of the
nanomaterials enables the exploitation of their cooperative effect, TiO2 semiconductor, which was covered by rGO (Brindha and
which improves its adsorption capacity. At the same time, aggre- Sivakumar, 2017). TiO2- rGO was developed through the homoge-
gation of TiO2 nanoparticles can be minimized (Stengl et al., 2011). nization treatment between rGO and TiO2. rGO is presented in
Graphene, in particular, has received the most attention among the three-dimensional porous meshes where TiO2 can be embedded
carbon-based nanomaterials since it was discovered in 2004 (Fig. 4). Graphene-TiO2 is highlighted as an effective method for
(Akhavan et al., 2011; Novoselov et al., 2004). This substrate was dyes photodecomposition and phenol photooxidation. With
equipped with a large theoretical, specific high thermal conduc- respect to removal of anionic or cationic dyes especially methylene.
tivity, surface area, high Young’s modulus, and good electrical Nanocomposites generated by hydrothermal method showed
conductivity (Zhu et al., 2010). Its excellent electron conductivity enhanced adsorption of methylene blue (cationic dye) because of
allows the flow of electrons from the semiconductor to its surface, the negatively charged surface of the GO matrix (Zhang et al., 2010).
inhibiting the electronehole recombination. One study reported Second, chemical bonds formed between TiO2 and graphene sheets
graphene sheets were able to act as acceptors and transporters of slightly reduce the band gap, the phenomenon was confirmed by a
photo generated electrons to prevent the recombination of electron previous study(Zhang et al., 2011). This graphene-TiO2 with high
(e)/hole (hþ) pairs (Hsu et al., 2013). In addition, the conduction- percentage of reactive facets caused significantly higher methylene
band potential between graphene/graphene is lower than that of blue degradation (82.5%) under visible-light irradiation than pure
the semiconductor, resulting in rapid electron migration. On the TiO2 (35.5% degradation) (Wang et al., 2012). The photocatalytic
other hand, foam-like macrostructures of graphene increase reac- performance of rGO/graphene-TiO2 on phenols was also investi-
tive sites for photocatalysis, thus, accelerated photocatalytic activ- gated. In general, enhanced photodegradation was attributed to
ities can be achieved (Zhu et al., 2010). Last but not the least, two narrower band gap and greater amount of active sites provided by
and three-dimensional structures generated by the hexagonal rings graphene-TiO2. Some studies reported mesoporous graphene-TiO2
of sp2 hybridized carbon atoms, helps to charge separation and shows highly dispersed small size anatase nanoparticles, as well as
electron transport properties (Atchudan et al., 2016; Park et al., displaying enhanced photocatalytic activities for the degradation of
2016). It has been proved by many studies that a graphene-TiO2 the organic pollutants such as phenol under the visible light (Fu
heterojunction provides much higher photocatalytic efficiency than et al., 2016; Iqbal et al., 2017). Significantly higher phenol degra-
pure TiO2. ChongYeon et al. (2013) reported that methylene blue dation rate (3e4 folds) was observed with rGO -TiO2 than pure TiO2
solution was degraded by 10% with TiO2 after 120 min, while the (Janus et al., 2012; Kim et al., 2019). In contrast, one study evaluated
degradation was raised to 33% when CuS-graphene oxide/TiO2 was phenol photodegradation under graphene-TiO2 nanocomposites
used. Similarly, Fernandez-Ibanez et al. (2015) revealed that 18.4 kJ/ and didn’t observe the increase photodegradation rate. The prob-
m2 of solar UVA dose was needed to inactivate 4 M CFU/mL of able reason may be due to the highest occupied molecular orbital of
bacteria with pure TiO2, while only consuming 12.2 kJ/m2 to reach phenol is lower than energy state of rGO sheet with photo-
the same bacteria reduction with graphene-TiO2. Graphene-TiO2 generated electron vacancies (Minella et al., 2017).
heterojunction can enhance the absorbency of light based on the
results of UVevis diffuse reflectance spectra of TiO2 and graphene-
TiO2 (Lai et al., 2016). Similarly, carbon dots were also considered as 5.4. pH values
a potential metal-free substrate to support TiO2 catalysts because of
its good performance in electron transfer, tunable optical absorp- pH value was found to have a pronounced influence on photo-
tion for organic molecules (Ge et al., 2016; Yu et al., 2016). Appro- catalytic degradation in organic pollutants, Table 5 shows the
priate graphene concentration is needed to achieve optimal optimal pH for organic pollutant degradation is acidic pH, it
photodegradation, the degradation of dyes increased with generally follows the rule that acidic pH contributes to higher
increasing content of reduced graphene oxide based (rGO) below degradation of organic pollutants than alkalic pH. In an acidic
5%. The composite with more than 5% rGO presented significantly condition, the surface of TiO2 is positively charged. As a result, the
less photocatalytic activity. The decline of photocatalytic activity condition is beneficial for TiO2 to absorb negative charged organic
compounds; high photocatalytic activity is expected to occur as a

Table 4
Photodegradation of TiO2 substrates on organic pollutants.

Organic pollutant Reaction condition Findings Reference

Type of catalyst

Graphene oxide 2-chlorophenol Solar light, initial concentration is 25 mg/L, at 240min, Pollutant was degraded by 80%. Barakat et al.
based TiO2 (2020)
Graphene oxide Bromothymol UVeVis light, initial concentration of both dye solutions is 0.5 g/L, Bromothymol blue and Rose bengal were Abadikhah et al.
based TiO2 blue/Rose bengal 0.05, 0.2, and 0.4 wt% rGO based TiO2, at 80 min degraded by 86% and 90% respectively. (2019)
Graphene oxide Rhodamine B Visible light, initial concentration is 10 mg/L, 25% concentration of Pollutant was degraded by 100%. Munikrishnappa
based TiO2 rGO based TiO2, at 80 min et al. (2019)
Graphene Bisphenol A Visible light, initial concentration is 4 mg/L, catalyst loading of 1 g/ Pollutant was degraded by 67.6%. Lai et al. (2016)
based TiO2 L, at 180 min
rGO based TiO2 Congo red Visible light, 2.5, 5, 7.5, & 10% concentration of rGO based TiO2, at Pollutant was degraded by 92%. Brindha and
120 min Sivakumar (2017)
Graphene oxide Methylene blue Visible light, initial concentration is 10 mg/L, catalyst loading of Pollutant was degraded by 98.8%. Rong et al. (2015)
based TiO2 0.8 g/L, at 100 min
Graphene Methylene blue Visible light, initial concentration is 10 mg/L, catalyst loading of Pollutant was degraded by 96%. Yang et al. (2016)
based TiO2 0.01 g/L, at 150 min
Graphene oxide Methyl orange UV light (20W), initial concentration is 10 mg/L, catalyst loading of Pollutant was degraded by ~90%. Jiang et al. (2011)
based TiO2 0.5 g/L, at 9 min
Graphene oxide Methyl orange Visible light, initial concentration is 10 mg/L, catalyst loading of Pollutant was degraded by 62% Khalid et al.
based TiO2 1 g/L, at 3 h (2013)
8 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725

Fig. 4. (a) Schematic diagram of the TiO2-rGO; (b) Morphology of the GO observed with TEM; (c) TiO2-rGO hybrids observed under TEM.

Table 5
Photodegradation of TiO2 based photocatalysts on organic pollutants at different pH.

Type of catalyst Organic pollutant Reaction condition Findings Reference

Degussa P-25 Petroleum Solar light; 170 min; pH ¼ 3-9 Optimum pH ¼ 6.8; 76% reduction of COD. Palaniandy et al. (2016)
TiO2 wastewater
TbxOy-TiO2 Phenol Visible light Optimum pH ¼ 4; 100% of phenol was degraded. Lu et al. (2017)
Degussa P-25 Petroleum UV light (UVA-UVB); 120 min; pH ¼ 2-10 Optimum pH ¼ 3; COD was reduced by 72%. Saien and Shahrezaei
TiO2 wastewater (2012)
Pt doped-TiO2 Methyl orange UV light (365 nm); 30 min of irradiation time; pH ¼ 2.5, Optimum pH ¼ 2.5; 98% of Methyl orange was Huang et al. (2008)
6.2, and 11 degraded.
Natural Methyl orange UV light; 100 min; pH ¼ 4-11 Optimum pH ¼ 4; 96.58% of Methyl orange was Li et al. (2008)
zeolites degraded.
Supported TiO2

result of high adsorption. In contrast, in an alkaline condition, increase. However, two major negative effects could occur when
significantly less interaction was caused by coulombic repulsion decreasing the particle size of TiO2 photocatalyst: 1) surface
between the negative TiO2 and organic compound anions, leading recombination of electrons and holes will increase; 2) lower utili-
to a decline of photo-catalytic reaction (Huang et al., 2008; Lu et al., zation of photons (Liu et al., 2008). Therefore, an optimum particle
2017). On the other hand, pH condition can also change the size may occur where an equilibrium between these two opposite
pathway of photocatalytic degradation for organic compounds. One effects was reached. The optimal particle size for methylene blue
study indicated intermediates of Bisphenol A were generated at a was 35 nm after investigating TiO2 particle size from 15 to 60 nm
pH of 10 with strong photocatalytic stability and was not able to be (Toyoda et al., 2004).~10 nm was likely the most optimized particle
further degraded into CO2 (Chiang et al., 2004). Similarly, Methyl size for TiO2 on phenol degradation when comparing a particle size
orange was converted to quinine at strong acidic conditions; the range from 4.5 to 12.8 nm (Liu et al., 2008).
resulting quinine could be secured by zeolite. In contrast, the ab-
sorption of Methyl orange at neutral or basic condition was very 5.6. Catalyst/dopant dosage
limited (3% degradation) (Li et al., 2008).
Catalyst dosage is also one of the most pronounced parameters
5.5. Particle size affecting photocatalytic efficiency and cost. Table 6 summarizes
effects of TiO2 dosage on different organic pollutants and exhibits
Catalyst particle size modification has been viewed as a cost- an appropriate dosage photocatalyst can contribute highest pho-
efficient enhancement that increases surface area and photo- tocatalytic activity, because more active surface area is available for
degradation. Both bulk and nanoscale TiO2 systems have been organic compound absorption when higher catalyst dosage is used.
investigated extensively and found to have significant differences Besides, more oxidative radicals and ions can be generated as a
in photochemical responses and degradation activities (Hu et al., result of higher concentration of electrons and holes. However,
2017; Zhou et al., 2018). Recent studies have indicated high excess catalyst concentration can cause agglomeration of the
pollutant adsorption as a result of increased surface areas between catalyst, and as a result, inhibit the penetration of UV/visible light/
TiO2 and contaminants. Having small drop size seems to be a way to solar light into the effluent. Therefore, photocatalytic activity is
increase the surface area (Nsib et al., 2013). There are two main hampered when the light irradiation presented is not sufficient. A
positive effects of decreasing particle size: 1) internal recombina- previous study investigated content of ZnOeTiO2 from 0.5 to 1.5 g/L
tion of electrons and holes will increased; 2) surface active sites will on azo dye degradation; the optimal catalyst dosage was found to
 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725 9

Table 6
The effect of TiO2 based-catalyst dosage on organic pollutants.

Type of Organic Reaction condition Findings Reference

catalyst pollutant

PdeTiO2 Methylene blue Visible light; 120 min; PdeTiO2 concentration at Optimum loading dosage is 0.5 wt% and 0.75 wt% of PdeTiO2 for Nguyen et al.
& methyl 0.25, 0.5, 0.75, and 1.0 wt%. Methylene blue & methyl orange, respectively; 99.4 and 92.6% were (2018)
orange degraded.
ZnOeTiO2 Azo dye UVeVis light; 180 min; TiO2 dosage from 0.5 to Optimum loading dosage is 1 g/L; 99% of Azo dye was degraded.
Caliskan et al.
1.5 g/L (2017)
AgeTiO2 Orange ІІ UV light; 60min; 0.5, 0.8, and 1.3% of Ag Optimum loading dosage is 0.5% of AgeTiO2; 20 ppm of orange ІІ was Gaidau et al.
degraded (2016)
Zrþ4-TiO2 4-chlorophenol UVeVis; 480 min; TiO2 dosage from 100-500 mg/ Optimum TiO2 dosage is 200 mg/100 mL; Optimum Zrþ4 concentration Venkatachalam
100 mL; Zrþ4 concentration from 0.5 to 7.0 mol % is 3.0 mol %; Almost 100% of 4-chlorophenol was degraded. et al. (2007)
Natural Methyl orange UV light; 100 min; TiO2 dosage from 0.006 to Photocatalytic degradation rate increased from 0.025 min1 to Li et al. (2008)
1
zeolites 0.04 g/10 mL 0.060 min with the catalyst dosage increasing from 0.006 to 0.04 g/
Supported 10 mL.
TiO2

be 1.0 g/L (Caliskan et al., 2017). However, higher catalyst loading the TiO2 dopant lead to a high electronic conductivity and low
(>1.0 g/L) scattered the light photons and led to lower photon electron resistance. As a result, effective transfer and separation of
absorption. electron and hole enhanced the degradation of the organic matters
Similarly, photocatalytic degradation increases with an (Basavarajappa et al., 2020). A variety of methods including sol-gel,
increasing amount of dopant. A dopant can act beneficially to trap mechanochemical doping, hydrothermal crystallization, and metal
electrons, and initiate reaction with water molecules, forming organic vapor deposition were used for doping metal onto TiO2. The
oxidative radicals to degrade organic pollutants. However, too dopant dosage and calcination temperature played a significant
much dopants prevent the TiO2 from capturing photons when the role in pollutant degradation. Dopant dosage was just discussed in
dopant is accumulated in excessive concentration. As a result, section 5.6. A previous study evaluated calcination temperature of
limiting the generation of electron-hole pairs and decreasing the Cu from 200 to 600  C; 100% of pollutant was removed at 300  C,
photocatalytic efficiency (Arabatzis et al., 2003; Gaidau et al., 2016). while the degradation achieved using the catalyst calcined at
A research reported that degradation efficiency increased with the 200  C was 17% lower than that achieved using the catalyst calcined
amount of dopant, which is increased from 0.07 to 0.21 mol %, while at 300  C. However, higher calcination temperature (400e600  C)
further increasing the amount of dopant to 0.28 and 0.35 mol % led caused significantly lower degradation efficiency (from 84.3 to
to the reduction of photodegradation (Chun-Te Lin et al., 2018). 69.2%) (Chun-Te Lin et al., 2018). These results indicated that an
Increasing catalyst dosage enhances removal efficiency of TiO2 appropriate calcination temperature had been identified as a crit-
based photocatalysts up to an optimum loading where an equilib- ical parameter for doping catalysts. The probable reason is owing to
rium between photo absorption and catalyst particles was reached crystallographic transformation induced by higher temperature,
(Tekbas et al., 2008; Yatmaz et al., 2004). anatase phase transformed into rutile phase when increasing the
temperature, as a result, the photocatalytic activity is reduced
(Luttrell et al., 2014). In case of metal dopant on organic wastewater
5.7. TiO2 dopant degradation, dopant such as Ag, Sn, or Zn caused different degrees
of the methylene blue degradation rate. Zn doped- TiO2 exhibits the
The unique properties including environmental purification, highest photocatalytic activity among them, because Zn acts as a
sterilization, self-cleaning surfaces, hydrogen generation, high stabilizer to the oxygen vacancies as well as a reductant for Ti3þ
photocatalytic activity, non-toxicity, and low cost of TiO2 make it a formation. The generation of O2 and Ti3þ is associated with the
good candidate for a variety of industrial applications, and is increase of hydrophilicity. These characters together play a critical
therefore considered one of the most promising photocatalysts role in improving photocatalytic properties towards organic
(Dozzi and Selli, 2013; Liu et al., 2011). However, the photoreaction wastewater (Tariq et al., 2019).
efficiency of TiO2 is severely limited to its wider band gap (>3 eV), Co-doped TiO2 generally exhibit higher visible light absorption
which hinders the application of solar light in photodegradation. than single doped TiO2 due to a synergistic effect between the two
Therefore, much effort has been devoted to shifting the absorption dopants, which increases charge carrier lifetime. A research
of TiO2 from UV to visible light range. As shown in Table 7, single- investigated co-doped C, N, SeTiO2 at different phases. Compared
doped and co-doped TiO2 photocatalysts cause organic pollutant with anatase C, N, SeTiO2 nanorods, rutile C, N, SeTiO2 nanorods
degradation in different degrees, co-doped TiO2 generally pre- exhibited enhanced degradation efficiency when irradiated by the
sented higher photocatalytic activity than single-doped TiO2. The light of higher wavelengths, even though anatase C, N, SeTiO2
ions of transition metals, such as Pd2þ, Cu2þ, Cd2þ, Cr3þ, V5þ, Fe3þ, nanorods exhibited a large surface area (Wang et al., 2017). This
Ni2þ are employed to modify the electronic structure of TiO2 by means that catalyst phase is a more important factor than surface
introducing a donor and/or acceptor level in the band gap, which area, which affects the co-doping catalytic activity. The enhance-
allows photons with some lower energy to excite a photocatalyst ment in co-doping catalytic activity is not only determined by the
and exhibit a higher photocatalytic activity under visible light (Pan low energy bandgap induced by the co-doping of C, N, and S in the
et al., 2010). On the other hand, dopant can contribute to higher TiO2, but it is also affected by the rutile structure of nanorods,
quantum efficiency of TiO2 photocatalytic reactions, which prevent which helps separate photo-induced e/hþ pairs. A synthesis of
the generated electron-hole pairs from recombining, this mixed- mesoporous C, N co-doped TiO2 hybrid shell was generated to
phase can act in a way to increase the charge transfer of electrons degrade organic dyes (Huang et al., 2017). According to the results,
and holes between rutile and anatase form of TiO2 (Liu et al., 2014; these hybrid shells displayed significantly higher photodegradation
Zhang, 2002). In the case of single non-metal dopant such as C efficiency when comparing with pure TiO2 under visible light. This
doped-TiO2, the well-arranged crystal structure and spontaneous of
10 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725

Table 7
The effect of different dopant TiO2 on organic pollutants.

Type of Organic pollutant Reaction Findings Reference

catalyst condition

Single-doped
ZrO2eTiO2 Rhodamin B Visible light; 3 h 90% of Rhodamin B was degraded Abdi et al. (2019)
ZnOeTiO2 Nitrophenol UV light; 25 min 95% of nitrophenol was degraded Cheng et al. (2016)
Fe3O4eTiO2 Rhodamine B, Visible light; 100%, 75%, and 81% were degraded for Rhodamine B, Methylene blue, and Congo Red, Djellabi et al. (2019)
Methylene blue, and 60 min respectively.
Congo Red
NeTiO2 Crystal violet dye UV light; ~100% of crystal violet dye was degraded Vaiano et al. (2019)
180 min
TCNQ/TiO2a Phenol UVeVis light; 90% of nitrophenol was degraded Jiang et al. (2014)
9 min
SiO2eTiO2 Phenol Visible light; 90% of phenol was degraded. Wang et al. (2016)
10h
TiO2; CeTiO2; Reactive Blue 19 and Visible light; up CeTiO2: 100% of dye was degraded after 60 min; SeTiO2: 100% of dye was degraded Helmy et al. (2018)
SeTiO2 Reactive Red 76 to 120 min after 120 min; <20% of dye was degraded after 120 min.
ZnOeTiO2 Az Facet-tailored TiO2 & UVeVis light; 97% of pollutants were degraded. Caliskan et al. (2017)
picture odye, 2,4-D 60 min
VeTiO2 Methylene blue Visible light; 15e30% of pollutants were degraded. Sun et al. (2008)
300 min
Zn2þ-TiO2 Congo Red Visible light; 78% of pollutants were degraded. Ishibai et al. (2008)
60 min
V5þ-TiO2 Congo Red Visible light; 44% of pollutants were degraded. Ishibai et al. (2008)
60 min
CueTiO2 Chlorophenols Visible light; 98.92% of chlorophenols was degraded. Chun-Te Lin et al. (2018)
6 h.
Zrþ4-TiO2 4-chlorophenol UVeVis light; 37.4% of 4-chlorophenol was degraded Venkatachalam et al.
480 min (2007)
Tiþ3-TiO2 Methyl orange Visible light; 3 h Doped catalysts exhibited much higher visible-light photocatalytic activity than the Zheng et al. (2013)
undoped sample (32.7 times).
BieTiO2 Methyl orange UVeVis light; 94% of methylene orange was degraded. Zhang et al. (2008)
2h
PteTiO2 Methyl orange Visible light; The pollutants levels were degraded by 87.8% when comparing with 73% using Huang et al. (2008)
90 min undoped TiO2.
SeTiO2 Methyl orange UV light; 40 min 96% of Methyl orange was degraded. Tian et al. (2009)
NeTiO2 Methyl orange UV light; 45 min 99% of Methyl orange was degraded. Peng et al. (2008)
PteTiO2 Methyl orange UV light; 30 min 86.2% of Methyl orange was degraded. Huang et al. (2008)
Co-doped
CeN co- RhB Visible light; 99% of methylene blue was degraded Allard et al. (2018)
doped TiO2 60 min
CeN co- Phenol Visible light; 84% of methylene blue was degraded Sivagami et al. (2016)
doped TiO2 150 min
N-graphene Methylene blue UV light; 70 min 85% of methylene blue was degraded Safardoust-Hojaghan
co-doped and Salavati-Niasari
TiO2 (2017)
PreCo co- Opaque dye (Acid 300e1100 nm >90% of opaque dye was degraded Yu et al. (2020)
doped TiO2 fuchsin) light; 120 min
RheSb co- Bisphenol A Visible light; 2h 98% of Bisphenol A was degraded Kim et al. (2018)
doped TiO2
NeF co- Acrylonitrile Solar light and The degradation ratio of 71.5% was achieved with the prepared catalyst after 6-min Pang et al. (2015)
doped TiO2 UV light; 60 min solar light irradiation, while 64.3% acrylonitrile was removed after 6- min UV light
irradiation.
NeS co- Congo red & Methylene Visible light; 2 h Congo: 90% degradation in 50 min, 92% degradation in 120 min Brindha and Sivakumar
doped TiO2 blue (2017)
NeZreNi co- Methylene blue Visible light; 65% of methylene blue was degraded Konstantinou et al.
doped TiO2 180 min (2001)
CueC co- Methylene blue Visible light; 90.1% of methylene blue was degraded. ChongYeon et al. (2013)
doped TiO2 120 min
CeN co- Methylene blue Visible light; 89% of methylene blue was degraded Sud and Kaur (2012)
doped TiO2 60 min
AgeN co- Methylene blue and Visible light; 20 ppm of pollutant was degraded Gaidau et al. (2016)
doped TiO2 orange ІІ 30 min
a
TCNQ is the abbreviation of 7, 7, 8, 8-Tetracyanoquinodimethane.

improvement can be attributed to the enhanced absorption of 5.8. Additives

visible light and ability of preventing electron and hole pairs
recombination with application of co-doped C and N onto TiO2. TiO2 based photocatalysts combined with some additives have
Similarly, for the metal co-doped photocatalysts, it generally ex- synergistic effects on organic effluent degradation. The photo-
hibits higher photocatalytic performance than single metal doped Fenton process is widely used to enhance photocatalytic activity
TiO2, higher photocatalysis of co-metal dopant is linked to capacity in many organic pollutants such as petroleum wastewater, phenol,
of substituting oxygen atoms with other elements that directly Rhodamine B, and Methyl orange (Table 8). The photo-Fenton
narrow the band gap (Phattalung et al., 2017). process is conducted by adding Feþ2 and H2O2 to TiO2 under
 D. Chen et al. / Journal of Cleaner Production 268 (2020) 121725 11

Table 8
The effect of Photo-Fenton-TiO2 on organic pollutants.

Type of catalyst Organic pollutant Reaction Findings Reference

condition

Photo-Fenton- Petroleum wastewater Solar light; 38% of organic pollutants were degraded. Aljuboury et al.
TiO2 180 min (2017)
Photo-Fenton- Phenol and 2,4,6- UV light; Phenol:100% degradation after 120 min; Trichlorophenol: 100% degradation after 30 min. Poulopoulos et al.
TiO2 Trichlorophenol 120 min/30 min (2019)
Photo-Fenton- 3-Chloropyridine UV light, 60 min 100% degradation of 3-Chloropyridine was achieved for Photo-Fenton and TiO2 Ortega-Liebana
TiO2 photocatalysis after 60 and 300 min, respectively. et al. (2012)
Photo-Fenton- Rhodamine B Solar light; 100% of Rhodamine B was degraded; Photocatalysis rate: Photo-Fenton-TiO2>TiO2 Zhu et al. (2019)
TiO2 120 min
Photo-Fenton- Methyl orange Solar light; 2 h 98% of Methyl orange was degraded. Zhang et al. (2019)
TiO2
Photo-Fenton- Remazol dye UV light; 180 min 90.57% of Remazol dye was degraded. Singh et al. (2019)
Fe2O3/TiO2

light; Feþ2 and H2O2 concentration are the major factors in the increased to 84% when Fe(III) was added (Poulopoulos et al., 2019).
photo-Fenton process. This advanced oxidation process (AOP) was Photo Fenton is a convenient way to facilitate the generation of
able to degrade some types of organic pollutants in wastewater hydroxyl radicals under ambient temperature and pressure
effluents. Numerous literatures have reported that AOP exhibited (Safarzadeh-Amiri et al., 1997).
outstanding effects on organic compound removal from effluents
even at low concentrations (Poulopoulos et al., 2019; Singh et al., 6. Conclusion
2019). In addition, the AOP is environmentally friendly, and
therefore, did not generate hazardous byproducts. A sufficient This study underlined the need for removal of organic con-
amount of hydroxyl radical was produced through the AOP process, taminants in wastewater effluent. Then the fundamental mecha-
which has a strong capability to degrade organic pollutants nisms of TiO2 based photocatalysts on organic pollutant
(Hermosilla et al., 2009). Hydroxyl ions produced from TiO2 pho- degradation were summarized; Common types of organic pollut-
tocatalytic activity is quite similar as mentioned above: at the ants were listed; the limitation of initial TiO2 photocatalysis on
condition of exposure of TiO2 photocatalysis to solar light, a positive organic pollutant degradation was discussed. Several parameters
hole in the valence band and an electron in the conduction band are which have critical impacts on the TiO2 based photocatalytic
released by receiving photon energy. Then holes react with water degradation were reviewed. These processing parameters such as
molecules to generate hydroxyl ions/radicals on the surface of TiO2 dopant/catalyst concentration, particle size, pH adjustment, and
particles. During the photo-Fenton process, more hydroxyl radicals substrate selection will bring instructional significance for further
can be formed according to reactions between Feþ2 and H2O2 under commercialization of TiO2 based photocatalysis. The main advan-
solar light irradiation. The mechanisms of classic photo Fenton was tages of the photocatalysis were concluded as follows: industrial
shown as equation (8) (Deng, 2009): effluent including organic compounds can be degraded or con-
verted to nontoxic chemicals with TiO2 based photocatalysts
Fe2þ þ H2 O2 /  OH þ Fe3þ þ OH (8) without generating any other pollutants; most of the needed en-
ergy resource comes from natural and unlimited solar energy;
In the presence of excess of H2O2, the Feþ2 ion can be regener-
indiscriminate degradation of different organic effluents can be
ated through the pathway shown in equations (9) and (10) below,
carried out with TiO2 based photocatalysts. However, the design
by consuming one H2O2 molecule:
and operational optimization of photocatalytic processes need to
be investigated more fully based on effluent characteristics.
Fe3þ þ H2 O2 /HO2 þ Fe2þ þ Hþ (9)
Declaration of competing interest
Fe3þ þ HO2 /O2 þ Fe2þ þ Hþ (10)
The authors declare that they have no known competing
If the Fenton process is carried out under the UVeVisible light, financial interests or personal relationships that could have
þ2
Fe species can be renewed directly through the reaction shown in appeared to influence the work reported in this paper.
equation (11). In this case, Feþ2 can be considered a true catalytic
species in the whole process. Acknowledgements
hv
Fe3þ þ H2 O/  OH þ Fe2þ þ Hþ (11) The research was supported in part by funds from National
Institute of Food and Agriculture, U.S. Department of Agriculture,
Ortega-Liebana et al. (2012) compared pollutant degradation
CAP project under 1006847, Guangzhou Science and Technology
between photo-Fenton and direct TiO2 photocatalysis on the
Plan (201807010056), and University of Minnesota Center for
degradation of 3-chloropyridine, the results indicated that TiO2
Biorefining.
photocatalysis led to some degree of mineralization of 3-
chloropyridine. However, the process took much longer time to
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