Journal of Molecular Liquids 352 (2022) 118685

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Pt-based TiO2 photocatalytic systems: A systematic review

Ali Esrafili a, Maryam Salimi b,⇑, Ahmad jonidi jafari a, Hamid Reza Sobhi c, Mitra Gholami a,
Roshanak Rezaei Kalantary a
a
Department of Environmental Health Engineering, School of Public Health, Iran University of Medical Sciences, Tehran, Iran
b
Department of Environmental Health Engineering, School of Public Health, Jiroft University of Medical Sciences, Jiroft, Iran
c
Department of Chemistry, Payame Noor University, Tehran, Iran

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

Article history: It is belived that clean energy and sustainable environment are big issues, which are linked are consid-
Received 14 May 2021 ered as great challanges all around the world. TiO2, which is known for its highly promising semiconduc-
Revised 1 February 2022 tor properties, has been applied in the fields of energy/environment-related applications. In addition, a
Accepted 2 February 2022
further attention has been paid to improve the photocatalytic efficiency of TiO2-based catalysts using sev-
Available online 07 February 2022
eral modification techniques. For this reason, the introduction of platinum (Pt), known as a noble metal,
into TiO2 structure has been considered as an effective strategy. This strategy presents a better separation
Keywords:
efficiency of electron-hole pairs resulting in a higher photocatalytic activity of the catalyst. This system-
TiO2
Platinum
atic review is centered on the synthesis, physio-chemical properties and applications of Pt-based TiO2
Photocatalysis catalysts with a special attention to energy and environmental applications. Finally; limitations, chal-
Energy and environmental applications lenges and future prospects of Pt-modified TiO2 photocatlytic systems are also briefly addressed.
Ó 2022 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1. H2 evolution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. CO2 conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. Organic transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.4. Removal of toxic chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.5. Remediation of organic contaminats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Search process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Fabrication techniques for Pt-TiO2 photocatalytic system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
4. Photocatalytic applications of Pt-TiO2 for aqueous pollutant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Photocatalytic applications of Pt-TiO2 for energy generation (H2 and CH4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

1. Introduction come the environmental degradation as an imminent problem.

This has gained a great attention amongst the scientific community
Over the past decades, many start-of-the-art and momentous [1–9]. Historically, the pioneering report by Fujishima and Honda
studies have been carried out to meet energy demand and over- provided a great opportunity to further explore TiO2 as an interest-
ing candidate material for future development of catalysts [10,11].
Since then, significant progress has been made in the field of
⇑ Corresponding author. photocatalysis due to a broad application of TiO2-based catalysts
E-mail address: [email protected] (M. Salimi).

https://doi.org/10.1016/j.molliq.2022.118685
0167-7322/Ó 2022 Elsevier B.V. All rights reserved.
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

in several fields including H2 evolution, CO2 reduction, organic 1.4. Removal of toxic chromium
transformations, removal of toxic chromium and degradation of
organic contaminant. The potential applications of TiO2-based cat- Hexavalent chromium Cr(VI), as a toxic metal ion, has been
alysts have been discussed in the literature as follows: regarded as a dangerous contaminant in various parts of the world.
It is the by-products of industrial processing such as leather, elec-
troplating, and pigment production [28]. In addition, the accumu-
1.1. H2 evolution lation of Cr(VI) in the aquatic environment is thought to have
serious impacts on the ecosystem and public health due to its high
As an important environmental issue, energy shortages has con- toxicity and carcinogenic properties [29,30]. To address that, it is
stitute a worldwide concern. Thus, it is very significant and urgent important to select and apply a suitable remediation technology.
to provide solutions to solve the global energy crisis [12]. Photo- As known, the photocatalytic reduction of Cr(VI) into Cr(III) is an
catalysis is one of the promissing techniques which is used to pro- ideal strategy for the reduction of the contamination of Cr(VI). It
duce H2 energy. In this regard, photocatalytic reforming and water is noted that Cr(III) is much less toxic in human nutrition and
splitting are both extensively employed for the evolution of hydro- can be easily removed through precipitation [31]. Up to now, the
gen [13,14]. Photocatalytic water splitting, which involves the con- applications with respect to the photocatalytic reduction of Cr
version of photon energies to hydrogen energy as an ideal chemical (VI) have been reported elsewhere [32–34].
fuel via photocatalysts materials, has attracted lots of attention for
environmental and global energy concerns in recent years [15]. In
this regard, several studies have been published in the literature, 1.5. Remediation of organic contaminats
exploring a wide variety of suitable materials for their potential
application in water splitting [16,17]. Among these reported stud- It is now well-established that organic contaminants enter the
ies, the deposition/loading of TiO2 surface with Pt (known as a pre- environment through a large variety of sources, notably wastewa-
cious noble metal) provides hydrogen evolution sites for ter treatment plants (WWTPs). These plants can be considered as
photocatalyzed water splitting [18]. In a study by Matsubara et al. the main origin of organic contaminants due to the fact that they
(2019), the loading of TiO2 with Pt nanoparticles obtained via a receive highly heterogeneous discharged from household, hospital,
polygonal barrel-sputtering method, led to an enhanced photocat- and industrial sources [35]. However, conventional physical/bio-
alytic performance of water splitting [19]. In an another research logical wastewater treatments are not sufficiently effective for
by Geng et al. (2018), the effect of size of Pt (cluster-deposited) the removal of many organic contaminants, resulting in their dis-
on r-TiO2 (1 1 0) surface for an enhanced hydrogen evolution activ- charge into the receiving environment [36,37]. Meanwhile, expo-
ity via low-temperature H2O conversion was evaluated and con- sure to them even at trace concentration levels can have adverse
firmed [20]. effects on human health and aquatic organisms [38–40]. For this
reason, photocatalysis have been introduced as an alternative
promising methods for the treatment of organic contaminants
through the formation of oxygen-containing radicals such as
1.2. CO2 conversion
OH, O
- 2 and etc [41].
Among different photocatalysts, TiO2 has been regarded as a
It is well established that carbon dioxide (CO2), also known as a potential candidate in the field of energy and environment because
greenhouse gas, is mainly derived from different naturally as well of its wonderful advantages such as durability, low cost, low toxi-
as anthropogenic activities [21]. It is also assumed that this gas can city, structural properties, and remarkable chemical and photo-
contribute to global warming leading to climate change, which is a chemical stability [42–44]. TiO2, by itself, has some inherent
big threat to the environment [22]. Thus, various kinds of materials shortcomings which restricts its exploitation [45]. For example,
have been developed in the CO2 photo-reduction field to lessen the TiO2 displays the respective wide band-gap energies of 3.2 and
effects of the above-mentioned problems [23]. It should be noted 3.0 eV for anatase and rutile, absorbing UV light making up just
that the capability of a photocatalyst systems for the absorption about 5% of the solar spectrum [46]. Furthermore, it is noted that
of light , generation of electron-hole pairs (e-/h+) as well as the the photocatalytic activity of TiO2 is restricted by the weak transfer
transportation and separation photogenerated charges, facilitates of photogenerated electron-hole pairs [47]. As earlier said, TiO2 has
the adsorption and activation of CO2 on the surface of the catalyst. three crystal structures: rutile, and anatase and brookite with the
This may trigger the efficient conversion of CO2 to CO and CH4 [24]. respective band gap energies of 3.0 eV, 3.20 eV, and 3.1[48,49]. It
is also acknowlegde that rutile and anatase are of tetragonal sys-
tem, of which, anatase is considered to exhibit the best photocat-
1.3. Organic transformations alytic activity for water reduction, while rutile shows superior
activity in the case of water oxidation [50].
Light induced transformation of organic materials is proven to Thus, TiO2 must be modified to meet the demand for the design
be a valuable tool to afford a variety of value-added organic com- of novel and highly efficient TiO2-based photocatalysts that can be
pounds [25]. To date, with the huge usage of photocatalysts usedunder visible or solar light for the environmental applications
applied in the industrial methods, significant achivements have [51,52]. Therefore, the application of the clean, renewable, avail-
been made to acheive numerous challenging organic transforma- able and inexpensive resources (visible or solar energy) has sub-
tions via the use of high temperature and pressure and generation stantially emerged as a priority in field of photocatalysis [53–57].
of harmful by-products. Consequently, photocatalysis through the To remedy (as a modification means), the deposition of a num-
organic transformations has been widely applied to achieve the ber of noble metals such as Ag, Pd, and Pt, etc., has been suggested
mentioned goals due to economic, inexhaustible, safe, and clean to improve the photocatalytic properties of TiO2 [58,59]. Amongst
features of the photocatalysis process [26].Till now, the application the above-mentioned metals, Pt has gained lots of interest due to
of Pt-based TiO2 materials has been considered as an effective its superb co-catalytic activity in a photocatalytic process. In addi-
strategy to endow a better photocatalytic organic synthesis tion, the application of Pt can also inhibit the recombination of
through incorporating the outstanding merits of each ingredient photo-generated electron-hole pairs, which results in the exten-
[27]. sion of carriers’ lifetimes [60].
2
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Table 1
Inclusion and exclusion criteria.

Inclusion
IC1- Peer-review articles
IC2- Fully text accessible
IC3- Focus of the studies is related H2 production, CO2 conversion, photocatalytic reforming, water splitting for energy, chromium removal and degradation of organic
contaminant from aqueous solutions
IC4- Articles written in English
Exclusion
EC1- Books, reviews, conference papers, letters to the editors, etc.
EC2- Not fully text accessible
EC3- Studies reporting the efficiency of Pt-TiO2 for the removal of contaminant from air, adsorption, and not related.
EC4- Peer-reviewed publications not written in English

As far as our knowledge is concerned, no systematic review on ‘‘hydrogen production”, ‘‘H2 generation”, ‘‘hydrogen generation”,
the applications of Pt-modified TiO2 for the energy/environment- ‘‘CO2 reduction”, ‘‘CO2 photoreduction”, ‘‘CO2 conversion”, ‘‘water
related applications has been published so far. Within this study, splitting”, ‘‘photocatalytic conversion”, ‘‘photocatalytic reforming”,
the preparation methods, characterization and photocatalytic per- ‘‘chromium removal”, ‘‘photodegradation”, ‘‘pollutant degrada-
formance of Pt- modified TiO2 catalysts are reviewed. In addition, tion”and ‘‘photocataly* degradation”. It is noted that manual
the limitations and future prospects of Pt-modified TiO2 are dis- searching was conducted for the additional eligible studies which
cussed. This systematic review is mainly centered on summarizing were not found through our database search strategy. After this
the recent advances on the preparation of Pt-modified TiO2 cata- stage, we considered some inclusion (IC) and exclusion (EC) crite-
lysts as well as their applications in the of energy/environment- ria, which are described at Table 1.It is higly acknowledged that we
related fields. It also tends to provide scientific-based thoughts did our best to find and comb all related articles concerning the
for the design and development of Pt-modified TiO2. objective of our study. However, we are likely to have missed
and not covered a few similar articles to our work due to the irrel-
evance of the subject of their work.
2. Search process After de-duplication, all eligible papers were monitored by two
reviewers via screening titles/abstracts and retrieved as full texts.
A keyword search was performed from 2010 until 2019 within Following that, their reference sections were searched for further
the electronic databases of Scopus and the Web of Science. The eligible articles. Any discrepancies during the screening process
search algorithm included all possible combinations of the key- were resolved by consulting with a third investigator. In total,
words extracted from the following five items: (1) ‘‘titanium diox- 3941 records were identified, of which, 1284 duplicates were
ide”, ‘‘titanium*”, ‘‘titan*” and ‘‘TiO2”; (2) ‘‘platinum”, ‘‘platin*” and removed and the rest (2657 records) were retained. Among them,
‘‘Pt”; (3) ‘‘H2 evolution”, ‘‘hydrogen evolution”, ‘‘H2 production”, 2427 records were excludede based on title and abstract. Further-

Fig. 1. Flow chart of search process.

3
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Fig. 2. Schematic representation of the (A) photodeposition and (B) chemical-reduction of Pt on TiO2 nanotubes (Reprinted with permission from Ref. [60]@ copyright 2019
Elsevier).

more, 138 articles were selected after full-text review. It should be on TiO2 nanotubes. Pt particles of Pt-doped sample from electrolyte
also mentioned that 12 articles were added after the manual B (Fig. 3C) seem to be too sharp, which may be attributed to the
search. The whole search process is depicted in Fig. 1. larger particle sizes caused by the aggregation of Pt particles
(Fig. 3D). The XPS spectra obtained from the sample (see Fig. 3E)
shows three peaks at 72.5 eV, 75.9 eV and 78.7 eV, which are
3. Fabrication techniques for Pt-TiO2 photocatalytic system assigned to Pt2+ (4f 7/2), Pt2+ (4f 5/2) and Pt4+ (4f 5/2), respectively.
Similarly, the peak appeared at 73.7 eV is indexed to the metallic Pt
For the integration of Pt and TiO2, a number of diverse synthesis (4f 5/2). By comparing nanotube TiO2 samples with nanotube Pt-
strategies have been applied which mainly relie on the ease of loaded TiO2 ones, it was found out that the photocatalytic activity
materials availability to obtain the optimal hybrid catalysts for the degradation of MO increased once the nanotube TiO2 sam-
[19,61–106]. Herein, the most frequently used synthesis proce- ples were loaded with Pt and applied under UV and visible light
dures for energy and environmental applications including irradiation. The photocatalytic performance was ranked in follow-
impregnation-reduction, non-thermal assisted sol–gel, photodepo- ing order: Pt-TiO2 NTs (electrolyte B, 400 °C) > Pt-TiO2 NTs (elec-
sition, atmospheric-pressure dielectric barrier discharge cold trolyte B, 600 °C) > Pt-TiO2 NTs (electrolyte A, 400 °C) > Pt-TiO2
plasma and chemical reduction are discussed. In a notable contri- NTs (electrolyte A, 600 °C) > TiO2 NTs (400 °C) > TiO2 NTs
bution, Lakshmanareddy and co-workers [60], two different meth- (600 °C). The authors also observed that the samples with a greater
ods, namely photo-deposition (Fig. 2A) and chemical reduction nanotubes length showed higher photocatalytic activities in the
(Fig. 2B) were applied to synthesize the Pt/TiO2 nanotubes. It was degradation of MO because of larger light penetration.
demonstrated that Pt/TiO2 nanotube-based catalysts prepared by In a further related study, Lv and co-workers [108] developed
the chemical-red uction method exhibited an excellent photocat- Pt-modified TiO2 nanotube arrays (Pt/TiO2 NTAs) by a photoreduc-
alytic degradation performance for methyl orange (MO) compared tion method (Fig. 4). The nanotubes arrays had an average diame-
to the photo-deposition method. Suitable properties such as multi- ter of  130 nm, which were composed of Pt nanoparticles (NPs)
ple oxidation states (e.g. Pt⁰, Pt2+ and Pt4+) were presented by the with the average size of 5–10 nm. The authors found out that the
authors as good justifications for selecting the chemical- Pt-modified TiO2 catalysts exhibited excellent photocatalytic activ-
reduction method. MO molecules were also degraded by holes ities in the degradation of MO under visible light illumination.
(h+) at the valance band of the catalyst, while electrons at the con- They also pointed out that the observed improved photocatalytic
duction band tend to interact with the oxidized species of Pt to efficiency could be ascribed to the surface plasmon resonance
turn them to Pt⁰. This is beneficial to the separation of photogener- (SPR) effect of Pt NPs, which hinders the recombination of photo-
ated electron-hole pairs, leading to the improvement of photocat- generated electron–hole pairs and synergistically accelerates the
alytic performance. photocatalytic process.
In a further related study, Su et al. [107] reported that the In another study, Wang et al.[109] doped Pt quantum dots
anodization of C2H2O4, 2H2O in 0.5 wt% NH4F (electrolyte A) at (QDs) on TiO2 nanotube arrays and applied the resulting catalyst
20 V for 2 h resulted in the rapid formation of TiO2 nanotube for the photodegradation of Rhodamine B under UV radation
(700 nm long) (Fig. 3A) while the nanptubes grown in anhydrous (Fig. 5, A-D). This composite catalyst exhibited a terrific pho-
dimethyl sulfoxide (DMSO) containing 1% HF (electrolyte B) at 60 V todegradation efficiency compared with pure TiO2 nanotube
for 72 h were 3 lm long (Fig. 3B). The authors loaded Pt onto TiO2 arrays, which is attributed to the crucial role of Pt QDs. In this
nanotubes via a cathodic reduction method and annealed at 400 °C study, it is assumed that the excited electrons belonging to the
and 600 °C. Fig. 3C reveals homogeneous distribution of Pt particles
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A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Fig. 3. (A, B, C, D) SEM images TiO2 nanotube (electrolyte A), TiO2 nanotube (electrolyte B), Pt-TiO2 NTs (electrolyte A), Pt-TiO2 NTs (electrolyte B) annealed at 400 °C ; (e) XPS
spectra of Pt-TiO2 NTs (Reprinted with permission from Ref. [107]@ copyright 2011 Elsevier).

the PL response and photocurrent spectra measurements (see

Fig. 5C, D).
In a related study by Yang et al., [110] the effect of Pt on the
light absorption characteristics of TiO2 hollow nanofibers (TiO2
HNFs) was investigated. Initially, TiO2 hollow nanofibers were pre-
pared by a uniaxial electrospinning method. Then, Pt/TiO2 hollow
nanofibers were obtained by a photo-reduction method (Fig. 6A).
Fig. 4. Schematic representation of the photoreduction of Pt on TiO2 nanotube As evident from the HRTEM images (see Fig. 6B-C), the observed
arrays (Pt/TiO2 NTAs) (Reprinted with permission from Ref. [108] @ copyright 2015
lattice fringe-width corresponds to the (1 1 0) rutile plane
Elsevier).
(0.325 nm) and (1 0 1) anatase plane (0.352 nm). Besides, the
observed fringe-width of 0.227 nm is probably ascribed to (1 1 1)
valence band (VB) of TiO2 nanotube arrays were transferred into
plane of Pt nanocrystals. The results regarding the degradation of
the corresponding conduction band (CB), and the photogenerated
azo dye Orange II indicated that the application of Pt/TiO2 hollow
holes were then effectively collected in the VB of TiO2 nanotube
nanofibers led to a higher photocatalytic performance compared
arrays. In addition, Pt QDs could act as an electron reservoir to trap
to pure TiO2 hollow nanofibers. This was explained by the fact that
electrons emitted from TiO2 nanotube arrays, thus suppressing the
the existence of Pt had a great influence on the photocatalytic
recombination of electron–holes in accordance with the results of activity, which led to a significantly extended optical absorption

5
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Fig. 5. (A) Rhodamine B degradation; (B) Schematic illustration of Pt quantum dots on TiO2 nanotube arrays based photocatalytic process under ultraviolet light irradiation
(<365 nm); (C) PL response of different samples; (D) Photocurrent responses of different samples (Reprinted with permission from Ref. [109] @ copyright 2015 Elsevier).

range. It is worth noting that in this study the Pt/TiO2 hollow nano- photocatalytic performance exhibited a substantial downward
fibers also exhibited higher photocatalytic activity compared to Pt- trend under both acidic (pH 3) and alkaline (pH 9) conditions. Thus,
modified commercial P25 TiO2. a high level of Pt loading can act as recombination centers and is
Wei et al. [111] studied the effect of different amounts of Pt harmful to TiO2 photocatalytic activity. On the other hand, a large
loading (0.2–1.6 wt%) over TiO2 microspheres for hydrogen pro- separation of photo-generated electron-hole pairs leads to a sharp
duction. TiO2 microspheres photocatalyst was prepared via increase in the performance of the degradation of CV using Pt/TiO2
hydrothermal method, afterward; a impregnation method was through two different pathways as follows: (1) stepwise formation
used to introduce the Pt nanoparticles. Interestingly, among differ- of N-demethylated by-products induced under acidic conditions
ently prepared photocatalysts the samples loaded with 1.2 wt% Pt (2) destruction of the conjugated structure induced at alkaline
shows the 125 times highest activity than unmodified TiO2 micro- conditions.
spheres. Enhanced photocatalytic hydrogen production activity In a further related study, a chemical reduction method was
was attributed to the role of Pt, which in turn reduced electron- introduced by Alamelu et al. [117] for the preparation of Pt-
hole pair recombination. loaded TiO2 catalyst. They found out that the degradation of Rho-
Guayaquil et al. [112] synthesized Pt-doped mesoporous TiO2 damine B was enhanced as Pt loading was increased from 1 to
by the soft template-assisted sol–gel method. The photocatalytic 5 wt%, while no enhancement was observed when Pt loading was
activity of the Pt-doped TiO2 was investigated for hydrogen pro- increased from 5 to 10 wt%. Therefore, Pt loading exceeding the
duction. Among various doped Pt photocatalysts, 2.50 wt% Pt- optimum dosage (5 wt%) could result in a lower degradation effi-
TiO2 exhibits the best hydrogen production activity which is ciency. This could be explained by the fact that an excess amount
ascribed to the role of Pt in narrowing the bandgap energy of of Pt could act as a recombination center for the photo-generated
TiO2. In another study, Yu et al.[16] successfully synthesized Pt charges followed by a lower photocatalytic performance.
deposited on TiO2 nanosheets with exposed (0 0 1) facets for In another study by Yang and Co-workers [113], the degrada-
hydrogen production in ethanol solution using as a scavenger tion of MO dye using popcorn-like Pt-modified mesoporous TiO2
reagent to trap holes. 2 wt% of loaded Pt nanoparticles displayed under visible light irradiation was investigated. The authors stud-
the highest photocatalytic activity that may be ascribed to the effi- ied on the performance of the composites under different Pt load-
cient charge separation provided by the cocatalyst. The summary ings, where 1.0% Pt/TiO2 was found out to be the optimum
of photocatalysis process by Pt/TiO2 is presented in Table 2. composite. Moreover, within this study, some comments on the
In the case of degradation of organic pollutants, the loading influence of the presence of Pt in the electronic structure of TiO2
amount of Pt is among the most important factors determining were made aided by density functional theory (DFT) calculations.
the photocatalytic performance [115]. At this point, it is necessary The results indicated that the dispersion of Pt in TiO2 retards the
to discuss the relation between the loading amounts of Pt incorpo- recombination of photogenerated electrons–holes.
rated within TiO2 structure for reaching a desirable performance. In a roughly related study, Qamar et al., [118] prepared a series
In this regard, Fan and Co-workers [116] prepared a series of Pt/ of TiO2 via sol–gel method, using different calcination tempera-
TiO2 catalysts by the photodeposition method and their photocat- tures within the range of 300–700 °C. The superior catalytic activ-
alytic performances for crystal violet (CV) dye were compared to ity (degradation rate of 0.0183 M min1  103 for triclopyr) was
that of TiO2 P25. In terms of Pt loading, it was demonstrated that reported using a catalyst calcined at 400 °C. The superior activity
the performance of 5.8 wt% Pt/TiO2 was better than that of is ascribed to the maximum surface area and appropriate crys-
0.7 wt% Pt/TiO2. But, as Pt content was increased to 7.1 wt%, the tallinity, which are both necessary to obtain good activity for a cat-

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A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Fig. 6. (A) A schematic illustration of the novel synthesis procedure of Pt/TiO2 hollow nanofibers.; (B, C) HRTEM results of Pt/TiO2 hollow nanofibers; (D) azo dye Orange II
degradation over different photocatlysts; (E) and kinetic plots of the photocatalytic degradation of azo dye Orange II (Reprinted with permission from Ref. [110]@ copyright
2017 Elsevier). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

alyst. Accordingly, TiO2 calcined at 400 °C was found out to be the propionic acid (2,4-DP) were ranked in the order of: 3%-Pt/
optimum composite. The authors also studied the catalytic perfor- TiO2 > 2.5%-Pt/TiO2 > 1.5%-Pt/TiO2 > 0.75%-Pt/TiO2 > 0.5%-Pt/
mance of the composites under different Pt loadings (05, 10, 15, TiO2 > TiO2. They concluded that by increasing the level of Pt load-
20 and 25 wt%). The catalytic performance in terms of degrada- ing on TiO2 the recombination of photogenerated electron-hole
tion rate dropped in the order of: 10 wt% Pt/TiO2 pairs is hindered, which affects the degradation performance.
(00526) > 15 wt% Pt/TiO2 (00436) > 20 wt% Pt/TiO2 Zhang and co-workers [120] also prepared Pt/ TiO2 nanotube
(00360) > 05 wt% Pt/TiO2 (00327) > 25 wt% Pt/TiO2 catalysts by a photodeposition strategy and applied them in
(00259) > TiO2 (00183). The results showed that the Pt loading malathion degradation under UV light irradiation. Different levels
of 1 wt% was found to be effective for the degradation process. of Pt loading (wt%) within TiO2 nanotube structure led to an
Moreover, the formation of the Schottky barrier at the interface enhancement in the degradation rate of malathion. They concluded
of Pt and TiO2 assists the transfer of photo-induced electrons from that under Pt loading of 0.15 wt%, the maximum photocatalytic
TiO2 conduction level. This leads to the reduction of the recombi- capability of Pt/TiO2 for the malathion degradation was observed.
nation rate of photo-induced electrons and holes, which can fur- Considering all mentioned points concerning the photocatalytic
ther enhance the photocatalytic performance of Pt/TiO2. activity of Pt/TiO2 system, it is well understood that the weak
Furthermore, Abdennouri et al. [119] loaded TiO2 with Pt in the points of TiO2 could be strengthened with the appropriate selec-
range of 0.5 to 3 wt% by a wet impregnation chemical method. tion of Pt loading levels in a photocatalytic system. Thus, it can
Within this study, photocatalytic degradation efficiencies of 2,4- be concluded that the amount of Pt nanoparticles (Pt-NPs) loaded
dichlorophenoxyacetic acid (2,4-D) and 2-(2,4-dichlorophenoxy) in a catalyst can influence its catalytic properties.

7
 A. Esrafili, M. Salimi, A. jonidi jafari et al.
Table 2
Summary of photocatalysis by Pt/TiO2.

Photocatalysts TiO2 Pt/ TiO2 Application Reaction conditions Results and comments of activity Ref.
Methods /Precursors Methods /Precursors
Pt/ TiO2 Hydrothermal: Ti(OBu)4, anhydrous alcohol, Impregnation-Reduction: TiO2, H2 54 mL water ,6 mL anhydrous methanol, Hydrogen production rate of 1.2 wt% Pt/ [111]
microspheres hydrofluoric acid hexachloroplatinic acid production 350 W high-pressure mercury lamp, UV TiO2 microspheres is about 125 times as
much as the unmodified TiO2
microspheres.
Pt / TiO2 Sol-gel: ethanol, hydrochloric acid, Pluronic H2 Ethane (2% v/v), near-UV light, Quantum yields (%) = 2.5 wt% Pt-TiO2- [112]
mesoporous F127, citric acid, titanium (IV) isopropoxide production Meso (22.6) > 5.0 wt% Pt-TiO2-Meso
(13.7) > 1.0 wt% Pt-TiO2-Meso
(9.6) > TiO2-Meso (9.3)
Pt/TiO2 Sol-gel (TiO2 spheres precursors): ammonia, Chemical Reduction: TiO2 Popcorn-Like RhB 40 mL RhB solution (20 mg L-1), 400 W Photocatalytic degradation = 1.0% Pt/ [113]
mesoporous ultra-pure water, ethanol, acetonitrile, Nanostructures, glycol, degradation metal halide lamp was used as a light TiO2
spheres tetraisopropyl titanate Hexachloroplatinic acid source, Vis
Hydrothermal : (Mesoporous TiO2 Popcorn- (96.7) > TiO2 P25 (25.2)
Like Nanostructures): TiO2 precursor,
ethanol, water, ammonia
Pt/TiO2 Ionic liquid modified sol–gel: water, [C4MIM] Atmospheric-pressure dielectric barrier Methylene 100 mL MB (10 mg L1) solution, 300 W Xe Apparent rate constants (k min1) = Pt [114]
mesoporous BF4, ethanol acetic acid, tetrabutyl titanate discharge cold plasma; blue was used as a light source, k > 400 nm (0.5 wt%)/TiO2 (0.047) > TiO2(0.023 )
Hexachloroplatinic acid, TiO2 powders. degradation
Pt/TiO2 nanotubes Hydrothermal /TiO2 particles, NaOH Photodeposition(PTP); H2 50 mL of 5% glycerol water mixture, natural H2 production (mmol. h1.g1
cat): PTC-1.0 [60]
hexachloroplatinic acid, glycerol, production solar irradiation (between 10 AM and 3 PM and PTP-1.0 (173) > TNT (3.7)
8

water, TiO2 nanotubes. on sunny days)

MO 50 mL MO (5  105 mol L1) aqueous Photocatalytic degradation of MO (%):
degradation solution, solar irradiation (average light PTC-1.0 (94) > PTP-1.0 (50.5) > TNT (49)
Chemical reduction(PTC); intensity 1.10  105 lx between 12 PM and
hexachloroplatinic acid, distilled water, 2 PM)
TiO2 nanotubes, polyvinylpyrrolidone,
Sodium borohydride.
Pt- TiO2 nanotube Potentiostatic anodization/ titanium foil Photoreduction; hexachloroplatinic MO 10 mL MO (10 mg L-1) aqueous solution, Photocatalytic degradation of MO (%): [108]
arrays (Pt/TiO2 (anode), pure graphite (cathode), acetone, acid, distilled, methanol, TiO2 NTAs, degradation 250 W metal halide lamp was as visible Pt/TiO2 NTAs (84.27) > TiO2 NTAs (2.0)
NTAs) water, ethanol, NH4F, ethylene glycol and light source, (k > 420 nm)
deionized water
Pt quantum dots/ Electrochemical anodization: Ti foils Photo irradiation–reduction; RhB 20 mL Rh B (5 mg L-1) aqueous solution, Photocatalytic degradation of Rh B (%): [109]
TiO2 nanotube (working electrodes), Pt foil (counter hexachloroplatinic , deionized water, degradation 300 W xenon lamp was used as a light Pt(0.1)- TNTAs (73.47) > Pt(0.2)-TNTAs
electrode), acetone, methanol , ethanol, ethanol , TNTA films source (with the 365 nm filter), k < 365 nm (38.71 > TNTAs (31.61) > Pt(0.3)-TNTAs

Journal of Molecular Liquids 352 (2022) 118685

deionized water, glycerol, H4F (UV) (23.76)
Pt/TiO2 hollow Simple one-step uniaxial electrospinning: Photoreduction: hexachloroplatinic Azo dye 50 mL Azo dye Orange II (20 mg L-1) The pseudo-first-rate constant (k [110]
nanofibers polyvinylpyrrolidone, Tetrabutyl titanate, acid, TiO2 HNFs, absolute ethanol, Orange II aqueous solution, 500 W Xe-arc lamp was min1) = Pt/TiO2 hollow nanofibers
Nitric acid, absolute ethanol, distilled water used as a light source (with a UV-cutoff (0.0069 ) > TiO2Pt/P25(0.0019) > TiO2
filter), k > 420 nm hollow(0.0006)
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

4. Photocatalytic applications of Pt-TiO2 for aqueous pollutant be greatly enhanced while it was decorated with the oriented Pt
removal deposits served as charge separators. Furthermore, in this study,
the enhanced separation of charge carriers and stability of Pt-NPs
Up to now, the modification of TiO2 using Pt particles has been deposited on the surface of TiO2 was investigated. In a more or less
thoroughly investigated and documented by several research related report by Lin et al., [142], the preparation of Pt-deposited
groups [121–135]. This section is mainly focused on the recent pro- TiO2 films with exposed (0 0 1) facet by a low temperature electro-
gresses in relation with Pt-based TiO2 (modified composites) used static self-assembly method was established which could drasti-
as catalyst in environmental remediation. Rosario and co-workers cally enhance the photocatalytic activity of TiO2 films in the
[136] obtained Pt-loaded TiO2 nanoparticles by a facile polymer degradation of ethenzamide under UV light irradiation. It can be
based method. The platinized TiO2 samples showed remarkable deduced that the fabrication of facets is necessary to facilitate
photocatalytic performance in the degradation of MO compared the efficient charge transportation leading to better photocatalytic
to bare TiO2. However, as Pt loading exceeded the optimum dosage, performance.
a lower degradation efficiency was observed possibly due to photo- As a result, Pt-based TiO2 photocatalyst can be a good candidate
absorption and scattering events. In a study by Barakat et. al, the for the degradation of organic contaminants. Also, it is well know
photocatalytic degradation of phenol and 2-chlorophenol by TiO2 that hexavalent chromium Cr(VI) is a potentially carcinogenic
and Pt-TiO2 catalyst was studied [137]. It was demonstrated that and mutagenic agent which is released to the environment from
the Pt-TiO2 sample exhibited an enhanced photocatalytic perfor- the anthropogenic activities and industrial processes. Therefore,
mance which is mainly attributed to the fact that Pt NPs can serve studies on the Cr(VI) removal have been considered and practiced
as an efficient electron trap favoring both the interfacial charge due to being dangerous to human health. In a study by Fan et al.,
transfer between the metal and semiconductor and the separation [143] after the successful synthesis of Pt-based TiO2 composites
of photo-generated e/h+ pairs. Within this study, the respective by photochemical deposition, they tried to remove Cr (VI) from
photodegradation rates of phenol and 2-chlorophenol in aqueous water under UV light irradiation. Furthermore, they concluded that
solution (50 mg L-1) were reported to be 87.7 and 100% at the opti- through the deposition, the removal rate for Cr(VI) could be greatly
mal conditions (Pt/TiO2, 0.5 g L-1; pH=3) and under UV light enhanced. In another study by Kim et al., [129], a photodeposition
irradiation. method was implemented for the synthesis of Pt-doped TiO2. In
In another study by Ofiarska et al. [138] the capability of Pt- this study, the oxidation of As (III) greatly facillitated the degrada-
doped TiO2 under simulated sunlight was investigated. This study tion of 4-chlorophenol (4-CP) in the presence of the Pt/TiO2 com-
centered on the photocatalytic degradation of ifosfamide and posites. As a result, Pt/TiO2 composites were found to be efficient
cyclophosphamide as anticancer agents. Moreover, it was proposed for the decontamination of the water polluted with both 4-CP
that during the oxidation of these two agents, phosphate ion and As (III). Although the application of photoactive Pt/TiO2 for
(PO34 ) is released leading to enhancing the effectiveness of the the photocatalytic removal of contaminants still is in early stages,
photocatalytic system. As mentioned, it is obvious that loading of it is expected that significant progress will be obtained in the
Pt on the surface of TiO2 (ca., Pt-doped TiO2) can enhance the future.
degradation of pollutants. It seems that the application of Pt-
doped TiO2 photocatalyst is a very interesting alternative to the 5. Photocatalytic applications of Pt-TiO2 for energy generation
traditional water treatment processes. (H2 and CH4)
It is well known that tuning the shape of Pt-NPs largely affect
the performance of a photocatalytic activity [139]. For instance, Currently, most hydrogen production is fossil resources, hence
Kovácset et al. [128] prepared the Pt-NPs of different geometry (in- emission from this process is considered as a major challenge. Con-
cluding polyhedral and spherical), which were attached to the sequently, to address these issues the application of photoenergy
commercial TiO2 (Aldrich anatase – AA, Aldrich rutile – AR. and in the form of photocatalytic processes is a promising approach
Evonik Aeroxide P25–P25) samples, and then applied the joint cat- [144–156]. Up to now, many efforts have been made to the modi-
alysts for the photocatalytic degradation of organic pollutants such fication of TiO2 with Pt with the aim of promoting its photocat-
as phenol, MO, and oxalic acid under light radiation. The shapes of alytic H2-production performance [157–194]. Photocatalytic
the catalysts decorated with Pt-NPs clearly were identified and reforming is known as one of the most promising methods to gen-
confirmed by the scanning electron microscopy (SEM) images. erate H2 fuel, which complies with the concept of converting waste
Based on the optical band gap energy values obtained from the into clean energy [195,196]. The use of glycerol as a sacrificial
DRS spectra, they found out that the light absorption range of agent for H2 production by the photoreforming process is very
P25-based composites was shape-dependent. The authors also sug- interesting. It is worth noting that, Panagiotopoulou et al.[195]
gested the degradation efficiency of phenol and MO varied with use of glycerol as sacrificial agent for H2 production via the pho-
respect to the shape of Pt-NPs in the catalyst. toreforming process. The result indicated that O2 and H2O appear
From a structural viewpoint, it is very interesting to control the playing as decisive role as an oxidant in the glycerol photo-
exposed facets of TiO2 materials by a facile and efficient route oxidation and photoreforming processes. On the other hand, add-
which eventually leads to an improvement in their physicochemi- ing the mixed-phase TiO2 to the photocatalytic reaction system
cal properties. In this regard, Wang along with his team [140] pre- improving its performance and significantly enhances the hydro-
pared and developed the Pt- loaded TiO2 of exposed (0 0 1) and gen production. For example Xu et al [197] show that the Pt loaded
(1 0 1) facets by a chemical deposition method. The developed on mixed-phase P25 (TiO2), which contains the anatase and rutile
exposed (0 0 1) facet exhibited a better photocatalytic performance heterojunction, is more active towards photocatalytic H2 evolution
compared to that of (1 0 1) in the degradation of Nitrobenzene via biomass reforming. The improved photocatalytic activity was
under visible light. In a similarly related study, the Wang research ascribed to the formation of phase junction between anatase and
group [141] reported on the enhanced photocatalytic activity of rutile. Coupling photocatalytic production of H2 with the organic
spheical TiO2 with totally exposed (0 0 1) facets using the synthesis attracts attention in the field of energy and chemical
oriented-Pt deposits prepared by a photo-chemical reduction engineering for obtaining the low-cost, clean, and sustainable gen-
method. Within this study, it was demonstrated that the photocat- eration of green energy and value-added products. For example, Yu
alytic degradation of RhB and phenol using the spherical TiO2 could et al. [198] coupled the two reactions of H2 evolution with CH4

9
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

Fig. 7. (A) photocatalytic CO and CH4 evolution rates over prepared samples (ultra thin TiO2 denoted TiO2-U and commercial TiO2 denoted as TiO2-B), (B) PL spectra, (C) UV–
vis DRS analysis, and (D) Corresponding Tauc plot for bandgap determination (Reprinted with permission from Ref.[205] @ copyright 2019 Elsevier).

conversion (into C2H6 and CO2 as the main products) over Pt/TiO2 role in trapping and transfer of photo-generated electrons from
photocatalyst systems. In their study reported that loaded Pt on the TiO2 to an acceptor, thus facilitating charge separation and
the surface of TiO2 to significantly improve its photocatalytic activ- enhancing the rate of hydrogen evolution over Pt/TiO2 photocata-
ity toward H2 production and CH4 conversion. The photocatalytic lysts. They found that ethanol can be oxidized by photoexcited h+
production of hydrogen from aqueous acetic acid represents an to yield hydrogen ions on TiO2 surface. Besides, the photoexcited
interesting option as a cleaner technology in this context. Photo- electrons are transferred to Pt catalytic sites to reduce the collected
catalytic decarboxylation of acetic acid occurs rapidly and prefer- hydrogen ions to H2 , leading to a better performance in H2 gener-
entially over photoreforming on aqueous Pt/TiO2 suspensions ation. Considering that, the overall process can be summarized
under UV–vis irradiation. Recently, Hamid etal., 2017 reported using the following equations [203]:
the formation of H2, CH4 and CO2 from photocatalytic conversion
TiO2 + hm ! e + hþ ð1Þ
of acetic acid using platinized TiO2. Based on their findings the
ratio of hydrogen to hydrocarbon formation was varied depending
on the pH. The authors provided detailed information on the pos- H2 O + hþ !Hþ + OH
ð2Þ
sible reaction pathways [199]. TiO2 modified by noble metals,
especially Pt, is deemed to be a superior mean to advance the pho- CH3 CH2 OH + OH
+ hþ !CH3 CHO + H2 O + Hþ ð3Þ
tocatalytic performance for hydrogen production [200]. It has been
found that the size of noble metal nanoparticles remarkably CH3 CH2 OH(g) + TiO(s) ! CH3 CH2 OH—Ti (s) + O—H(s) ð4Þ
impacts the charge separation and catalytic performance efficien-
cies. For instance, Dessal’s research team have carried out their CH3 CH2 OH—Ti(s) + 2 hþ !CH3 CH2 O(g) + Ti(s) + 2Hþ (s) ð5Þ
work on the effect of Pt particle size toward the the photocatalytic
H2 generation over TiO2 photocatalyst [201]. They found that the Pt
2Hþ (s) + 2e !Pt0 ! H2 (g) ð6Þ
clusters with the particle size of  1 nm and an appropriate weight
percentage (e.g., 0.2%) exhibited an optimal photocatalytic activity Recently, the use of Genetic Algorithm couple with Artificial
with the H2 evolution rate of 170 mmol g1 h1. It is demonstrated Neural Network approach have been raised as systematic tech-
that the facilitated transfer and separation of the photo-induced niques for optimizing purposes in the field of photocatalyst hydro-
charger carriers arising from the synergetic effects between highly gen production such as study conducted by Estahbanati and co-
dispersed Pt clusters and TiO2 contribute to the excellent activity. workers [204]. Considerations in their optimization were the Pt
To alleviate the energy shortage crises, Chowdhury et al proposed loading (0.02–5 wt% on TiO2), catalyst loading (0.05–5 g L1), glyc-
a photocatalytic production of clean and renewable hydrogen dri- erol concentration (0.5–50% v/v) and pH (pH 2–12). They reported
ven by solar energy from formaldehyde as the sacrificial agent via that the optimum conditions for H2 to glycerol conversion were as
Pt/TiO2 catalyst systems [202]. The best photocatalytic activity was follows: 3.1% Pt, 3.9 g L-1 catalyst, 50% glycerol (v/v), and a pH of
observed under the optimum condition as follows: pH = neutral to 4.5.
alkaline, catalyst concentration = 1 g L-1, platinum loading (wt %) The unique physical structure and chemical properties of Pt/
on TiO2 = 0.25, and light intensity Isolar, =100 mW (1 sun). Navarro TiO2 photocatalytic systems provide a promising platform used
et al. explained the role of Pt in increased photocatalytic perfor- for the research in the conversions of CO2 to valuable products,
mance of TiO2 toward hydrogen production from ethanol [203]. such as CH4. Liu et al., [205] demonstrated that higher photocat-
The authors depicted that deposited platinum has the mediating alytic activities for the reduction of CO2 with H2O were achieved
10
A. Esrafili, M. Salimi, A. jonidi jafari et al. Journal of Molecular Liquids 352 (2022) 118685

when a photoroute method was used to synthesize ultra thin TiO2 patible features of the synthesized catalysts are also a matter of
nanosheets supported the well-dispersed Pt catalysts (denoted as concern which should be taken into account. It is finally suggested
P-Pt/TiO2-U) rather than impregnation method (denoted I-Pt/ that further research on this particular topic should be performed
TiO2-U). Their results revealed that the P-Pt/TiO2-U exhibited to address all problems and challenges.
excellent photocatalytic activity for the conversion of CO2 to CH4
and CO with a yield of 66.4 and 54.2 lmol g1 h1, respectively Declaration of Competing Interest
(Fig. 7A). Also, the highest activity was ascribed to the role of Pt
nanoparticles in the efficient charge separation and the enhance- The authors declare that they have no known competing finan-
ment of light absorption ability, as proved by the PL spectroscopy cial interests or personal relationships that could have appeared
(Fig. 7B) and the UV–vis DRS (Fig. 7C-D) experiments, respectively. to influence the work reported in this paper.
Although CH4, CO and CH3OH are widely reported as photocat-
alytic CO2 conversion products, Wang et al. [206] demonstrated Acknowledgements
that ultrafine Pt loaded on the surface of TiO2 were successfully
achieved by photodeposition method, showing a synergistic This project (Number: 96-03-27-31988) has been financially
enhancement effect on the photocatalytic CO2 conversion. The supported by the Iran University of Medical Sciences (Tehran, Iran),
resulting Pt–TiO2 nanocomposite with TiO2 calcination tempera- which is hereby gratefully acknowleged.
ture of 500 °C and Pt deposition time of 1 h, exhibited the highest
production rates of CH4 (60.1 mmol g1 cat h
1
), together with a H2
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