catalysts

Review
Titanium Dioxide (TiO2) Mesocrystals: Synthesis,
Growth Mechanisms and Photocatalytic Properties
Boxue Zhang, Shengxin Cao, Meiqi Du, Xiaozhou Ye *, Yun Wang and Jianfeng Ye *
Department of Chemistry, College of Science, Huazhong Agricultural University, Wuhan 430070, China;
bx1058779150@hotmail.com (B.Z.); shengxincao@hotmail.com (S.C.); dumeiqi@webmail.hzau.edu.cn (M.D.);
wangyun@mail.hzau.edu.cn (Y.W.)
* Correspondence: xzye@mail.hzau.edu.cn (X.Y); jianfengye@mail.hzau.edu.cn (J.Y.); Tel.: +86-27-8728 4018 (J.Y.)




Received: 10 December 2018; Accepted: 11 January 2019; Published: 16 January 2019


Abstract: Hierarchical TiO2 superstructures with desired architectures and intriguing

physico-chemical properties are considered to be one of the most promising candidates for solving
the serious issues related to global energy exhaustion as well as environmental deterioration via
the well-known photocatalytic process. In particular, TiO2 mesocrystals, which are built from TiO2
nanocrystal building blocks in the same crystallographical orientation, have attracted intensive
research interest in the area of photocatalysis owing to their distinctive structural properties such as
high crystallinity, high specific surface area, and single-crystal-like nature. The deeper understanding
of TiO2 mesocrystals-based photocatalysis is beneficial for developing new types of photocatalytic
materials with multiple functionalities. In this paper, a comprehensive review of the recent advances
toward fabricating and modifying TiO2 mesocrystals is provided, with special focus on the underlying
mesocrystallization mechanism and controlling rules. The potential applications of as-synthesized
TiO2 mesocrystals in photocatalysis are then discussed to shed light on the structure–performance
relationships, thus guiding the development of highly efficient TiO2 mesocrystal-based photocatalysts
for certain applications. Finally, the prospects of future research on TiO2 mesocrystals in photocatalysis
are briefly highlighted.

Keywords: TiO2 ; photocatalysis; mesocrystals; synthesis; modification

1. Introduction
Semiconductor-based photocatalysis is well known to be one of the most effective approaches to
alleviate the serious conundrums of global energy exhaustion, as well as environmental deterioration,
by utilizing the inexhaustible solar energy [1–7]. Among various kinds of semiconductors, Titanium
dioxide (TiO2 ) is the most attractive one as a photocatalyst owing to its high photoreactivity, outstanding
chemical stability, easy availability, and cheap price [8–15]. Despite tremendous efforts having been
made toward the fabrication of TiO2 materials, as well as the investigation of their photocatalytic
properties, real applications of TiO2 in photocatalysis are still largely hampered by the wide band gap
of TiO2 (e.g., 3.2 eV for anatase and brookite, 3.0 eV for rutile), which can merely absorb ultraviolet
radiation (accounting for < 5% of solar light), and the fast recombination of photoinduced charge
carriers, which leads to low quantum efficiency [16–21]. It is always a hot topic in the research area
of materials chemistry and photocatalysis to manipulate the morphology and architecture of TiO2 to
achieve extended light response and facilitate photogenerated electron-hole separation, thus realizing
remarkably enhanced photocatalytic activity in various applications [22–26].
Recently, it has been well demonstrated that building highly ordered superstructures from
nanocrystal building blocks is very important for fabricating new materials and devices, as this kind
of nanoparticle assembly can not only display properties and functions associated with individual

Catalysts 2019, 9, 91; doi:10.3390/catal9010091 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, x FOR PEER REVIEW 2 of 26

Recently, it has been well demonstrated that building highly ordered superstructures from
nanocrystal building blocks is very important for fabricating new materials and devices, as this kind
Catalysts 2019, 9, 91 2 of 27
of nanoparticle assembly can not only display properties and functions associated with individual
nanoparticles, but can also exhibit new collective properties and advanced tunable functions [27–32].
In particular, mesocrystals,
nanoparticles, a new
but can also exhibit newtype of ordered
collective superstructure
properties and advanced builttunable
from functions
crystallographically
[27–32]. In
oriented
particular,nanocrystal
mesocrystals,subunits,
a new type have drawn superstructure
of ordered significant research interest
built from since the concept
crystallographically of
oriented
“mesocrystal” was first introduced in 2005 [33,34]. These unique ordered
nanocrystal subunits, have drawn significant research interest since the concept of “mesocrystal” superstructures were
initially
was first identified
introducedfrom the [33,34].
in 2005 studies These
of theunique
structural characteristics
ordered and growth
superstructures mechanisms
were initially of
identified
biominerals,
from the studies and ofwere proposed characteristics
the structural to be formed through
and growth a non-classical,
mechanismsparticle-mediated
of biominerals, and growth
were
process,
proposednamely,
to be formedmesoscale
throughtransformation, rather than the growth
a non-classical, particle-mediated conventional
process,classical, atom/ion-
namely, mesoscale
mediated crystallization
transformation, rather than route (Figure 1). Subsequently,
the conventional the mesocrystal
classical, atom/ion-mediated concept evolved
crystallization from the
route (Figure 1).
classical mesocrystals, which were generated via the aforementioned mesoscale
Subsequently, the mesocrystal concept evolved from the classical mesocrystals, which were generated transformation
process, to all the hierarchical
via the aforementioned materials
mesoscale built from crystallographically
transformation oriented nanocrystal
process, to all the hierarchical subunits
materials built from
regardless of the mechanism
crystallographically of formation.
oriented nanocrystal Despite
subunits the flourishing
regardless emergence
of the mechanism of reports Despite
of formation. on the
fabrication
the flourishingof mesocrystals,
emergence of the historyonofthe
reports mesocrystal
fabricationsynthesis is closelythe
of mesocrystals, related to the
history continuous
of mesocrystal
exploitation of mesocrystals
synthesis is closely related towith new compositions
the continuous and the
exploitation persistent development
of mesocrystals of synthetic
with new compositions
procedures having development
and the persistent advantages in of terms of low
synthetic cost, convenience
procedures in handling,
having advantages and of
in terms easiness in
low cost,
compositional and structural control [35–41].
convenience in handling, and easiness in compositional and structural control [35–41].

Figure 1.
Figure Schematic illustration
1. Schematic illustration of
of the
the single-crystal
single-crystal formation
formation from
from classical
classical crystallization,
crystallization, oriented
oriented
attachment and
attachment and non-classical
non-classical crystallization. Reprinted with
crystallization. Reprinted with permission
permission from
from [33].
[33]. Copyright
Copyright John
John
Wiley &
Wiley & Sons
Sons Inc.,
Inc., 2005.
2005.

To date,
To date, mesocrystals
mesocrystalswith withaabroad
broadrange
rangeofof
compositions
compositions involving
involving metal oxides
metal (e.g.,
oxides TiOTiO
(e.g., 2 [42–68],
2 [42–

68], ZnO [69–85], Fe2O3 [86–95], CuO [96–101], SnOx [102,103], Co3O4 [104–108], Ag2O [109]), metal
ZnO [69–85], Fe 2 O 3 [86–95], CuO [96–101], SnOx [102,103], Co 3 O 4 [104–108], Ag 2 O [109]), metal
chalcogenides (e.g.,
chalcogenides (e.g.,ZnSZnS[110],
[110],PbS
PbS[111–113],Ag
[111–113],Ag S [114], PbSe [115]), metals (e.g., Au [116–118],
2S2[114], PbSe [115]), metals (e.g., Au [116–118], Ag
Ag [119],
[119], Cu [120],
Cu [120], Pt [121,122],
Pt [121,122], Pd [123])
Pd [123]) haveproduced,
have been been produced, as introduced
as introduced in somein some previous
previous reviews
reviews [124–126]. Among these mesocrystals,
[124–126]. Among these mesocrystals, TiO2 mesocrystals TiO 2 mesocrystals are widely accepted
are widely accepted to be to beparticularly
particularly
promising in
promising inphotocatalytic
photocatalyticapplications
applications[127–152].
[127–152].It isItnoted
is noted
thatthat the high
the high internal
internal porosity
porosity and
and high
high surface areas of TiO 2 mesocrystals can be beneficial for the adsorption of
surface areas of TiO2 mesocrystals can be beneficial for the adsorption of reagents and provide morereagents and provide
more active
active sites sites for the
for the subsequent
subsequent photocatalytic
photocatalytic reactions,while
reactions, whilethe the well-oriented
well-oriented nanocrystal
nanocrystal
alignment provides effective conduction pathways and significantly enhances
alignment provides effective conduction pathways and significantly enhances charge transport and charge transport and
separation with TiO 2 particles [135,153]. Although significant attention has
separation with TiO2 particles [135,153]. Although significant attention has been directed tobeen directed to fabricating
TiO2 mesocrystals
fabricating with controlled
TiO2 mesocrystals morphologies,
with controlled the realization
morphologies, of TiO2 mesocrystals
the realization is always isa
of TiO2 mesocrystals
challenging
always task, probably
a challenging because the
task, probably titanium
because precursors
the titanium used are used
precursors highlyarereactive, and it is rather
highly reactive, and it
difficult to precisely control the growth dynamic
is rather difficult to precisely control the growth dynamicof TiO crystals. Additionally, considering
2 of TiO2 crystals. Additionally, considering the wide
band gap of the pristine TiO2 materials, it is also demanding to modify the mesostructure of TiO2
Catalysts 2019, 9, 91 3 of 27

mesocrystals to realize broadened light absorption, thus achieving highly efficient photocatalysis in
various applications.
In this review article, we first summarize numerous attempts toward the fabrication of TiO2
mesocrystals. Four representative synthetic routes, namely, oriented topotactic transformation, growth
on substrates, organic-additive-assisted growth in solution, and direct additive-free synthesis in
solution, are presented one by one, with a special focus being channeled towards the underlying
mesocrystallization mechanism and its controlling rules. The construction of doped TiO2 mesocrystals,
as well as TiO2 mesocrystal-based heterostructures, is also covered in this review. The potential
applications of the resultant TiO2 mesocrystal-based materials in photocatalysis are then introduced to
gain a deep understanding of the structure–performance relationships, thus providing useful guidelines
for rationally designing and fabricating highly efficient TiO2 mesocrystal-based photocatalysts for
certain applications. Finally, some future research directions in the research area are briefly discussed
and summarized.

2. Synthesis TiO2 Mesocrystals

2.1. Oriented Topotactic Transformation

Early reports on the fabrication of TiO2 mesocrystals were based on topotactic transformation
from pre-synthesized NH4 TiOF3 mesocrystals, as the titanium precursors used (e.g., TiCl4 , titanium
tetrabutoxide (TBOT), titanium tetraisopropanolate (TTIP)) are normally highly reactive, making
it rather challenging to manipulate the growth process of TiO2 crystals upon direct syntheses. In
2007, O’Brien’s group disclosed the first preparation of TiO2 mesocrystals. In a synthetic procedure,
NH4 TiOF3 mesocrystals were first prepared in the (NH4 )2 TiF6 and H3 BO3 aqueous solution with
the assistance of a nonionic surfactant (e.g., Brij 56, Brij 58, or Brij 700). After being washed with
H3 BO3 solution or sintered in air at 450 ◦ C, the as-formed NH4 TiOF3 mesocrystals were successfully
transformed into anatase TiO2 mesocrystals, with the original platelet-like shapes well preserved [42,43].
Such a topotactic transformation could proceed mainly because of the crystal structure similarity
between NH4 TiOF3 and anatase TiO2 crystals (less than 0.02% in an average lattice mismatch), and the
as-synthesized NH4 TiOF3 mesocrystals could thus serve as a crystallographically matched template
for the subsequent formation of TiO2 mesocrystals (Figure 2). Owing to the great effectiveness of
the methodology, NH4 TiOF3 mesocrystals with a variety of morphologies were obtained by simply
adjusting the reaction parameters, giving rise to a series of morphology-preserved anatase TiO2
mesocrystals [44,45,137,141,143]. In addition, single-crystalline NH4 TiOF3 crystals could also be
utilized as a template for the oriented topotactic formation of anatase TiO2 mesocrystals. For instance,
by annealing a thin layer of aqueous solution containing TiF4 , NH4 F, and NH4 NO3 on a Si wafer,
nanosheet-shaped anatase TiO2 mesocrystals enclosed by a high percentage of (001) facets were
produced (Figure 3) [135]. Despite the one-step characteristic of the synthetic process, single-crystalline
NH4 TiOF3 nanosheets were actually first generated in the precursor solution at low annealing
temperatures, which could then be easily transformed into anatase TiO2 upon further increase in
annealing temperature. With large quantities of N and F elements removed, the volume of the crystals
decreased. Pores would form within the particles, resulting in anatase TiO2 mesocrystals consisting of
anatase nanocrystals predominantly enclosed by (001) facets.
Catalysts 2019, 9,
Catalysts 2019, 9, 91
x FOR PEER REVIEW 44 of
of 27
26
Catalysts 2019, 9, x FOR PEER REVIEW 4 of 26

Figure 2. Schematic illustration of oriented topotactic transformation of NH4TiOF3 mesocrystal to

2. Schematic illustration of oriented
Figure 2. oriented topotactic
topotactic transformation
transformation of
of NH
NH44TiOF
TiOF33 mesocrystal toto
anatase TiO2 mesocrystal. The electron diffraction (SAED) patterns of the selected area illustrate
anatase TiO
TiO22 mesocrystal. The electron diffraction (SAED) patterns
The electron diffraction (SAED) patterns of the selected area illustrate
illustrate
single-crystal-like diffraction behavior for both samples. Reprinted with permission from [43].
single-crystal-like
single-crystal-like diffraction
diffraction behavior
behavior for
for both
both samples. Reprinted with
samples. Reprinted with permission
permission from
from [43].
[43].
Copyright American Chemical Society, 2008.
Copyright
Copyright American
American Chemical
Chemical Society,
Society,2008.
2008.

3. (a) Schematic presentation of oriented topotactic formation of anatase

Figure 3. anatase TiO
TiO22 mesocrystals
mesocrystals
Figure 3. (a) Schematic presentation of oriented topotactic formation of anatase TiO2 mesocrystals
TEM; and
with dominant (001) facets; (b) SEM; (c) TEM; and (d)
(d) HRTEM
HRTEM images
images of
of anatase
anatase mesocrystals.
mesocrystals. The
with dominant (001) facets; (b) SEM; (c) TEM; and (d) HRTEM images of anatase mesocrystals. The
pattern. Reprinted with permission from [135].
inset displays the related SAED pattern. [135]. Copyright American
inset displays the related SAED pattern. Reprinted with permission from [135]. Copyright American
Chemical Society, 2012.
Society, 2012.
Chemical Society, 2012.
Most
Most recently,
recently,Qi’sQi’sgroup
group proposed
proposeda newa new topotactic transformation
topotactic method
transformation for fabricating
method anatase
for fabricating
TiO 2
Most recently,
mesocrystals Qi’s
[154]. Ingroup
their proposed
synthetic a new
procedure, topotactic transformation
(010)-faceted orthorhombic method for fabricating
titanium-containing
anatase TiO2 mesocrystals [154]. In their synthetic procedure, (010)-faceted orthorhombic titanium-
anatase TiO
precursor 2 mesocrystals [154]. Infirstly
their synthetic procedure, (010)-faceted orthorhombic titanium-
containingnanosheet
precursor arrays
nanosheet werearrays synthesized
were on conducting
firstly synthesized FTO glass
on conducting substrate
FTO through
glass substrate
containing precursor
solvothermally treating nanosheet
0.1 M K 2
arrays
TiO(C were
2 O 4 ) 2
firstly
in synthesized
mixed solvents on
of conducting
deionized FTO
water glass
and substrate
diethylene
through solvothermally treating 0.1 M K2TiO(C2O4)2 in mixed solvents of deionized water and
throughAfter
glycol. solvothermally
a further treating 0.1 treatment,
M K2TiO(C 2Oas-formed
4)2 in mixed solventsnanosheet
of deionized water and
diethylene glycol. Afterhydrothermal
a further hydrothermal the
treatment, precursor
the as-formed arrays
precursor nanosheet could be
arrays
diethylene
readily glycol. After a further hydrothermal treatment, the as-formed precursor nanosheet arrays
could beconverted to (001)-faceted
readily converted anatase TiO
to (001)-faceted 2 nanosheet
anatase arrays. arrays.
TiO2 nanosheet It was revealed that thethat
It was revealed lattice
the
could be
match readilythe
between converted to (001)-faceted
orthorhombic precursor anatase
crystal TiOthe
and 2 nanosheet
tetragonal arrays. It was
anatase revealed
crystal that the
accounted for
lattice match between the orthorhombic precursor crystal and the tetragonal anatase crystal
lattice
the match transformation
topotactic between the orthorhombic
from (010)-facetedprecursor crystal
precursor and theto tetragonal
nanosheets (001)-faceted anatase
anatase crystal
TiO
accounted for the topotactic transformation from (010)-faceted precursor nanosheets to (001)-faceted2
accounted for the topotactic
nanosheets transformation from (010)-faceted precursor nanosheets to (001)-faceted
anatase TiO(Figure 4).
2 nanosheets (Figure 4).
anatase TiO2 nanosheets (Figure 4).
Catalysts 2019, 9, 91 5 of 27
Catalysts 2019, 9, x FOR PEER REVIEW 5 of 26

Figure 4. Schematic presentation of topotactic transformation from (010)-faceted precursor nanosheet

arrays
arrays toto(001)-faceted anatase
(001)-faceted TiOTiO
anatase 2 nanosheet arrays
2 nanosheet on the
arrays onbasis
the of crystal
basis of lattice
crystalmatchment between
lattice matchment
orthorhombic precursor crystal and tetragonal anatase crystal. Reprinted with permission
between orthorhombic precursor crystal and tetragonal anatase crystal. Reprinted with permission from [154].
Copyright
from [154].Springer,
Copyright2017.
Springer, 2017.

2.2. Growth on Substrates

2.2. Growth on Substrates
As presented above, topotactic transformation has been well demonstrated to be a very
As presented above, topotactic transformation has been well demonstrated to be a very useful
useful method to construct TiO2 mesocrystals. However, precursors suitable for such a topotactic
method to construct TiO2 mesocrystals. However, precursors suitable for such a topotactic
transformation are mainly limited to NH4 TiOF3 , and it is rather difficult to realize the morphological
transformation are mainly limited to NH4TiOF3, and it is rather difficult to realize the morphological
manipulation of the resultant TiO2 mesocrystals at will. Therefore, it is highly desirable to explore
manipulation of the resultant TiO2 mesocrystals at will. Therefore, it is highly desirable to explore
facile solution-phase routes toward the direct fabrication of TiO2 mesocrystals, since these kinds of
facile solution-phase routes toward the direct fabrication of TiO2 mesocrystals, since these kinds of
syntheses are normally advantageous in light of their low cost, easy modulation of morphology, and
syntheses are normally advantageous in light of their low cost, easy modulation of morphology, and
great potential for environmentally benign production of inorganic materials. In 2008, Zeng’s group
great potential for environmentally benign production of inorganic materials. In 2008, Zeng’s group
first utilized multiwalled carbon nanotubes (CNTs) as substrate to grow anatase TiO2 mesocrystals
first utilized multiwalled carbon nanotubes (CNTs) as substrate to grow anatase TiO2 mesocrystals
with controllable surface coverage [155]. It was revealed that the as-formed [001]-oriented petal-like
with controllable surface coverage [155]. It was revealed that the as-formed [001]-oriented petal-like
anatase mesocrystals were uniformly distributed on CNTs, with TiO2 nanocrystal building blocks
anatase mesocrystals were uniformly distributed on CNTs, with TiO2 nanocrystal building blocks
having diameters in the range of 2–4 nm and mesopores having a very uniform size distribution
having diameters in the range of 2–4 nm and mesopores having a very uniform size distribution
centered at 2.5 nm. Additionally, by employing graphene nanosheets as a template to control the
centered at 2.5 nm. Additionally, by employing graphene nanosheets as a template to control the
growth dynamic of TiO2 , uniform mesoporous anatase TiO2 nanospheres were successfully generated
growth dynamic of TiO2, uniform mesoporous anatase TiO2 nanospheres were successfully generated
and anchored on the graphene nanosheets (Figure 5) [156]. It is noteworthy that in comparison to the
and anchored on the graphene nanosheets (Figure 5) [156]. It is noteworthy that in comparison to the
conventionally generated porous particles constructed by randomly aggregated anatase nanocrystals,
conventionally generated porous particles constructed by randomly aggregated anatase nanocrystals,
the thus-formed mesoporous nanospheres were single-crystal-like. Detailed investigation on the growth
the thus-formed mesoporous nanospheres were single-crystal-like. Detailed investigation on the
process of the mesoporous anatase nanospheres revealed that such a graphene-nanosheet-assisted
growth process of the mesoporous anatase nanospheres revealed that such a graphene-nanosheet-
mesocrystallization route actually involved the nucleation of anatase TiO2 on graphene nanosheets
assisted mesocrystallization route actually involved the nucleation of anatase TiO2 on graphene
and subsequent oriented aggregation of tiny nanocrystals onto pre-anchored nuclei to reduce the total
nanosheets and subsequent oriented aggregation of tiny nanocrystals onto pre-anchored nuclei to
surface energy of anatase crystals. As a result, mesoporous mesocrystals of anatase TiO2 would finally
reduce the total surface energy of anatase crystals. As a result, mesoporous mesocrystals of anatase
form. Moreover, Qi’s group reported the fabrication of two-dimensional (2D) nanoarray structures
TiO2 would finally form. Moreover, Qi’s group reported the fabrication of two-dimensional (2D)
constructed from mesocrystalline rutile TiO2 nanorods on Ti substrate via a simple solution-phase
nanoarray structures constructed from mesocrystalline rutile TiO2 nanorods on Ti substrate via a
synthesis [66]. These nanorod arrays were obtained by hydrothermally treating the aqueous solution
simple solution-phase synthesis [66]. These nanorod arrays were obtained by hydrothermally
of TBOT and HCl. It was revealed that during the growth process of the mesocrystalline rutile TiO2
treating the aqueous solution of TBOT and HCl. It was revealed that during the growth process of
nanorod arrays, stem nanorods were first grown onto Ti substrate due to the high concentration
the mesocrystalline rutile TiO2 nanorod arrays, stem nanorods were first grown onto Ti substrate due
of titanium-containing precursors, and with the consumption of the precursors, the resulting low
to the high concentration of titanium-containing precursors, and with the consumption of the
concentration of reactant was responsible for the growth of the tiny nanotips with continuous crystal
precursors, the resulting low concentration of reactant was responsible for the growth of the tiny
lattices, resulting in the final mesocrystalline rutile TiO2 nanorods with a hierarchical architecture.
nanotips with continuous crystal lattices, resulting in the final mesocrystalline rutile TiO2 nanorods
with a hierarchical architecture.
Catalysts 2019, 9, 91 6 of 27
Catalysts 2019, 9, x FOR PEER REVIEW 6 of 26

Catalysts 2019, 9, x FOR PEER REVIEW 6 of 26

Figure 5. (a) SEM, (b) TEM, and (c) HRTEM images of mesoporous anatase TiO nanospheres on
Figure 5. (a) SEM, (b) TEM, and (c) HRTEM images of mesoporous anatase TiO22 nanospheres on
graphene nanosheets. The inset is the SAED pattern related to a single nanosphere; (d) Schematic
graphene nanosheets. The inset is the SAED pattern related to a single nanosphere; (d) Schematic
illustration of the growth mechanism of mesoporous anatase nanospheres. Reprinted with permission
illustration
Figure of
5. the growth
(a) SEM, (b)mechanism
TEM, and (c) ofHRTEM
mesoporous anatase
images nanospheres.
of mesoporous Reprinted
anatase with permission
TiO2 nanospheres on
from [156]. Copyright John Wiley & Sons Inc., 2011.
from graphene
[156]. Copyright John
nanosheets. Wiley
The inset&
is Sons Inc., 2011.
the SAED pattern related to a single nanosphere; (d) Schematic
illustration of the growthGrowth
2.3. Organic-Additive-Assisted mechanism of mesoporous anatase nanospheres. Reprinted with permission
in Solution
from [156]. Copyright John
2.3. Organic-Additive-Assisted Wiley in
Growth & Sons Inc., 2011.
Solution
Apart from the aforementioned solid templates or substrates, various organic additives
couldApart
2.3. from the aforementioned
Organic-Additive-Assisted
also be utilized to guide the solid
Growth templates
in Solution
formation of TiO or substrates, various organic additives could
2 mesocrystals. In 2009, Yu’s group first
also be utilized
prepared Apart to guide
hollow-sphere-shaped the formation
rutile TiO of TiO 2 mesocrystals. In 2009, Yu’s group first prepared
from the aforementioned solid 2 mesocrystals assembled
templates or substrates, by nanorod
various organicsubunits
additives via a facile
could
hollow-sphere-shaped
hydrothermal synthesis rutile
by using TiO
also be utilized to guide the formation TiCl 2 mesocrystals assembled by nanorod subunits via a facile
as the titanium source and N, N’-dicyclohexylcarbodiimide
of TiO2 mesocrystals. In 2009, Yu’s group first prepared (DCC)
4
hydrothermal synthesis
hollow-sphere-shaped
and L-serine by using TiCl
rutile TiO(Figure
as biological additives 4 as the
2 mesocrystals titanium
6) [46]. assembled source
It was proposed and N,
by nanorod N’-dicyclohexylcarbodiimide
that such subunits via a facile
hollow-sphere-shaped
(DCC) and L-serine
hydrothermal
mesocrystals as biological
weresynthesis
actually by using
formed additives
TiCl4 as (Figure
through the 6) [46].
titanium
a distinctive It was
source andproposed andthat such hollow-sphere-
N, N’-dicyclohexylcarbodiimide
crystallization transformation process,
shaped mesocrystals
(DCC) and L-serine were
as actually
biological formed
additives through
(Figure 6) a distinctive
[46]. It was crystallization
proposed
which involved the appearance of polycrystalline aggregates at the initial stage of reaction, mesoscale that such and transformation
hollow-sphere-
shaped
process, which mesocrystals
involved were actually formed
the appearance through a distinctive
of polycrystalline crystallization
aggregates atof and transformation
themesocrystals
initial stage to of nanorod
reaction,
transformation to sector-shaped mesocrystals, further transformation
process,
mesoscale which involved
transformation the appearance
to sector-shaped of polycrystalline
mesocrystals, aggregates
further at the initial
transformation stage of reaction,
of mesocrystals to
bundles upon end-to-end and side-by-side oriented attachment accompanied by assembly of sectors
mesoscale transformation to sector-shaped mesocrystals, further transformation of mesocrystals to
nanorod
to solid bundles
spheres, upon
anduponend-to-end
final generation and side-by-side oriented attachment accompanied by assembly
nanorod bundles end-to-end andof hollow spheres
side-by-side orientedvia Ostwald
attachment ripening. by
accompanied Later on, with
assembly
of
thesectors
assistanceto solid spheres,small
and final generation of hollow spheres via Ostwald ripening. Later on,
of sectors to solid spheres, and final generation of hollow spheres via Ostwald ripening. Later rod-like
of organic molecules of glacial acetic acid (HAc) and benzoic acid, on,
with
anatasetheTiOassistance of organic
mesocrystals weresmall molecules
successfully of glacialvia
fabricated acetic acid (HAc)
a simple and benzoic acid,
solvothermal rod-like
with the2 assistance of organic small molecules of glacial acetic acid (HAc) and benzoicroute acid, [127].
rod-likeThese
anatase TiO
mesocrystals
anatase TiO2 mesocrystals were successfully fabricated via a simple solvothermal route [127]. These
were proposedwere
2 mesocrystals to besuccessfully
formed through fabricated theviawell-known oriented route
a simple solvothermal attachment, and the
[127]. These
mesocrystals
mesocrystals
mesocrystallization were proposed
were proposed
process to to
was bebeformed
found to be through
formed through out
carried theunder
the well-known
well-known oriented
oriented
the synergism ofattachment,
attachment,
hydrophobic and and
the the
bonds,
mesocrystallization
p-p interactions and process
mesocrystallization processwaswas found
foundtotobe
“mixed-esters-templates”. becarried
carried out under
out
Furthermore, under thesynergism
the
Gao’s synergism
group of hydrophobic
of hydrophobic
synthesized bonds,
bonds,
spindle-shaped
p-p interactions
p-p interactions and “mixed-esters-templates”.
and “mixed-esters-templates”. Furthermore,
Furthermore,
mesoporous anatase TiO2 mesocrystals by utilizing peroxotitanium as the titanium source and Gao’s
Gao’s group
group synthesized
synthesized spindle-
spindle-
shaped shaped mesoporous
mesoporous anatase
anatase TiO 2 mesocrystals by by utilizing peroxotitanium as the titanium source
polyacrylamide (PAM) as theTiO 2 mesocrystals
polymer additive to utilizing
adjust the peroxotitanium
growth process as of
the titanium
TiO source
2 [129]. They
and and polyacrylamide
polyacrylamide (PAM)
(PAM) as as
the the polymer
polymer additive
additive to
to adjust
adjust the
the growth
growth process
processof TiO
of 2 [129]. They
TiO 2 [129]. They
proposed that these anatase mesocrystals were formed via TiO2 -PAM co-assembly, accompanied by an
proposed
proposed that that
these these anatase
anatase mesocrystalswere
mesocrystals were formed
formed via viaTiOTiO2-PAM co-assembly, accompanied by
2-PAM co-assembly, accompanied by
amorphous-to-crystalline
an amorphous-to-crystalline transformation.
transformation.
an amorphous-to-crystalline transformation.

Figure 6. (a) SEM, (b) TEM, and (c) HRTEM images of hollow spheres of rutile TiO2 mesocrystals. The
Figure 6. (a) SEM, (b) TEM, and (c) HRTEM images of hollow spheres of rutile TiO2 mesocrystals. The
inset in (a) is a magnified SEM image and the inset in (b) shows the related SAED pattern. (d) Schematic
inset in (a) is a magnified SEM image and the inset in (b) shows the related SAED pattern. (d)
illustration
Figure 6. (a)ofSEM,
Schematic the formation
illustration
(b) TEM, mechanism
of and
the formation
(c) HRTEM of the rutile
mechanism
images ofofTiO
hollow mesocrystals.
the2 rutile Reprinted
TiO 2 mesocrystals.
spheres of rutile with permission
TiO2Reprinted with The
mesocrystals.
from permission
[46]. Copyright
from American
[46]. Chemical
Copyright Society,
American 2009.Society, 2009.
Chemical
inset in (a) is a magnified SEM image and the inset in (b) shows the related SAED pattern. (d)
Schematic illustration of the formation mechanism of the rutile TiO 2 mesocrystals. Reprinted with
permission from [46]. Copyright American Chemical Society, 2009.
Catalysts 2019, 9, 91 7 of 27

In 2011,2019,
Catalysts Tartaj’s
9, x FORgroup developed a method based on inverse microemulsions to produce
PEER REVIEW 7 ofsub-100
26
nm sphere-like mesocrystalline nanostructures, which involved a two-stage temperature program [132].
In the firstInstage,
2011, the
Tartaj’s group
reaction atdeveloped a method (60
a low temperature ◦ C)
based ontriggered
inverse microemulsions to produce resulting
inverse microemulsions, sub-
100 nm
in thermal sphere-like mesocrystalline
destabilization nanostructures,
via forming nanomicellar which involved
structures smaller than a two-stage
100 nm. temperature
The subsequent
program
partial hydrolysis [132]. In the first
of TiOSO stage, sub-100-nm
produced the reaction sphere-shaped
at a low temperature
TiO (60 °C) triggered
frameworks through inverse
replicating
4 2
microemulsions, resulting in thermal destabilization via forming nanomicellar structures smaller◦
those nanomicellar structures. In the second stage, increasing the reaction temperature to 80 C or
than 100 nm. The subsequent partial hydrolysis of TiOSO4 produced sub-100-nm sphere-shaped TiO2
higher generated mesocrystalline TiO2 architectures with interstitial porosity partially filled with
frameworks through replicating those nanomicellar structures. In the second stage, increasing the
surfactants.
reactionAfter the removal
temperature to 80 °Cofor
the interstitial
higher generatedsurfactants, mesoporosity
mesocrystalline was generated
TiO2 architectures and uniform
with interstitial
spherical-shaped mesocrystalline architectures of anatase TiO 2 with
porosity partially filled with surfactants. After the removal of the interstitial surfactants, particle sizes ranging from 50
to 70 mesoporosity
nm were produced finally. Later on, this method was extended to fabricate
was generated and uniform spherical-shaped mesocrystalline architectures of anatase spherical-shaped
mesoporous
TiO2 with anatase
particleTiO 2 mesocrystals
sizes ranging from 50 with a much
to 70 nm were smaller size finally.
produced of 25 nm [133].
Later on, this method was
extended toZhao’s
Recently, fabricate spherical-shaped
group reported amesoporous anatase TiO2 mesocrystals
facile evaporation-driven orientedwith a much smaller
assembly method to
size of
fabricate 25 nm [133]. anatase TiO2 microspheres (~800 nm in diameter) with radially oriented
mesoporous
hexagonalRecently,
mesochannelsZhao’s group reported a facile evaporation-driven
and single-crystal-like pore walls (Figure oriented
7) [64].assembly method started
The synthesis to
fabricate mesoporous anatase TiO2 microspheres (~800 nm in diameter) with radially oriented
with the liquid-liquid phase separation, which was induced by the preferential evaporation of the
hexagonal mesochannels and single-crystal-like pore walls (Figure 7) [64]. The synthesis started with
solvent of tetrahydrofuran (THF) at a relatively low temperature (40 ◦ C), and spherical-shaped
the liquid-liquid phase separation, which was induced by the preferential evaporation of the solvent
PEO-PPO-PEO/TiO
of tetrahydrofuran 2 oligomer
(THF) atcomposite
a relativelymicelles with PPO (40
low temperature segments
°C), andasspherical-shaped
the core and titania-associated
PEO-PPO-
PEO PEO/TiO
segments as the shell formed at the liquid-liquid phase interface.
2 oligomer composite micelles with PPO segments as the core and titania-associated PEO
Upon further evaporation
of THF at 40 ◦as
segments C,the
theshell
concentration
formed at the ofliquid-liquid
the spherical micelles
phase increased,
interface. Upon furtherleading to the formation
evaporation of THF of
uniform
at 40mesoporous TiO2 microspheres
°C, the concentration of the spherical assembled by composite
micelles increased, leading micelles (step 1 and
to the formation 2). As the
of uniform
mesoporous TiO microspheres assembled ◦ by composite micelles
evaporation temperature increased to 80 C, the continuous evaporation of the residual THF and
2 (step 1 and 2). As the evaporation
temperature
hydrolyzed increased
solvents fromtoTBOT 80 °C,precursor
the continuous
droveevaporation
the oriented of the residual
growth THF and
of both hydrolyzed and
mesochannels
solvents from TBOT precursor drove the oriented growth of both mesochannels
nanocrystal building blocks from the initially formed spherical composite micelles along the free radial and nanocrystal
building blocks from the initially formed spherical composite micelles along the free radial and
and restricted tangential direction within the TiO2 microspheres (step 3). Radially oriented mesoporous
restricted tangential direction within the TiO2 microspheres (step 3). Radially oriented mesoporous
anatase TiO2 microspheres with single-crystal-like pore walls were produced after removal of the
anatase TiO2 microspheres with single-crystal-like pore walls were produced after removal of the
triblock copolymer
triblock copolymer templates
templates finally
finally(step
(step4).
4). It
It is
is noteworthy
noteworthy that thatbyby simply
simply adjusting
adjusting the reaction
the reaction
parameters,
parameters,mesoporous,
mesoporous, single-crystal-like,
single-crystal-like,olive-shaped, anataseTiO
olive-shaped, anatase TiO 2 mesocrystals
2 mesocrystals
constructed
constructed by by
ultrathin nanosheet subunits could also be synthesized
ultrathin nanosheet subunits could also be synthesized [65]. [65].

Figure 7. 7. Schematic
Figure presentation
Schematic presentation of theofformation
the formation
process of process of anatase
mesoporous mesoporous anatase TiO2
TiO2 microspheres
microspheres with radially
with radially orientedoriented hexagonal
hexagonal mesochannels
mesochannels and single-crystal-like
and single-crystal-like pore pore
walls walls through
through
evaporation-driven oriented
evaporation-driven assembly.
oriented assembly.Reprinted
Reprinted with permissionfrom
with permission from [64].
[64]. Copyright
Copyright American
American
Chemical
Chemical Society,
Society, 2015.2015.
Catalysts 2019,
Catalysts 2019, 9,
9, 91
x FOR PEER REVIEW 26
8 of 27

2.4. Direct Additive-Free Growth in Solution

2.4. Direct Additive-Free Growth in Solution
Considering that the introduction of solid substrates or organic additives into the reaction
Considering
system is unfavorable that the
for introduction
the large-scale of production
solid substrates or organic additives
of mesocrystals, into thehighly
it is, therefore, reaction system
desirable
is unfavorable for the large-scale production of mesocrystals, it is, therefore,
to explore facile additive-free synthetic approaches toward functional mesocrystals with controllable highly desirable to explore
facile additive-free
crystallinity, porosity,synthetic approaches
morphology, andtoward functional
architecture. mesocrystals
In 2011, Qi’s group with controllable
reported crystallinity,
the first additive-
porosity, morphology, and architecture. In 2011, Qi’s group reported the
free synthesis of nanoporous anatase TiO2 mesocrystals with a spindle-shaped morphology, single- first additive-free synthesis of
nanoporous anatase
crystal-like structure, and TiO mesocrystals with a spindle-shaped morphology, single-crystal-like
2 tunable sizes via solvothermal treatment of the solution of TBOT in HAc, structure,
and tunable sizes via solvothermal
followed by calcination in air to remove treatment of the solution
the residual organicsof(Figure
TBOT 8) in [47].
HAc,These
followed by calcination
mesocrystals were
in air to remove the residual organics (Figure 8) [47]. These mesocrystals
illustrated to be elongated along the [001] direction, having lengths mainly in the range of 300–450 were illustrated to be
elongated along the
nm and diameters of[001] direction,
200–350 nm. It washaving lengths
revealed mainly
that underinthe thesolvothermal
range of 300–450 nm andthe
conditions, diameters
reaction
of 200–350 nm. It was revealed that under the solvothermal conditions,
between TBOT and HAc firstly generated unstable titanium acetate complexes through ligand the reaction between TBOT
and HAc firstly generated unstable titanium acetate complexes through
exchange/substitution, accompanied by the release of C4H9OH. The subsequent esterification reaction ligand exchange/substitution,
accompanied
between thus-formed by the release
C4H9OH of Cand
4 H9 the
OH.solvent
The subsequent
HAc producedesterification reaction slowly.
H2O molecules betweenThen,
thus-formed
Ti-O-Ti
C H OH and the solvent HAc produced H O molecules slowly.
bonds were formed via both nonhydrolytic-condensation and hydrolysis-condensation processes,
4 9 2 Then, Ti-O-Ti bonds were formed
via both nonhydrolytic-condensation
resulting in transient amorphous fiber-like and hydrolysis-condensation
precursor. As the reactionprocesses, continued, resulting in transient
crystallized flower-
amorphous fiber-like precursor. As the reaction continued, crystallized
like precursor was generated at the expense of the fiber-like precursor. This crystallized flower-like flower-like precursor was
generated at the expense of the fiber-like precursor. This crystallized
precursor acted as a reservoir to continuously release soluble titanium-containing species to generate flower-like precursor acted
as
tiny a anatase
reservoir to continuously
nanocrystals. Theserelease soluble
tiny anatase titanium-containing
nanocrystals underwent species
orientedto generate
aggregation tinyalong
anatase
the
nanocrystals. These tiny anatase nanocrystals underwent oriented aggregation
[001] direction, together with some lateral attachment along some side facets of (101) facets, along the [001] direction,
together
accompanied with by some thelateral attachment
entrapment of in along some sidebutyl
situ produced facetsacetate.
of (101)As facets, accompanied
a result, by the
[001]-elongated,
entrapment
spindle-shaped, of inanatase
situ produced butyl acetate.
mesocrystals As a result,
were produced [001]-elongated,
when the reaction spindle-shaped,
time was long enough. anatase
mesocrystals were produced when the reaction time was long enough.
Further calcination in air would remove the butyl acetate residuals, consequently yielding Further calcination in air would
remove the butyl acetate residuals,
nanoporous anatase TiO2 mesocrystals. consequently yielding nanoporous anatase TiO 2 mesocrystals.

Figure
Figure 8. (a) SEM
8. (a) SEM and
and (b)
(b) TEM
TEM images
images of
of nanoporous
nanoporous anatase
anatase TiO
TiO22 mesocrystals
mesocrystals obtained
obtained via
via
solvothermal treatment of the solution of TBOT in HAc, followed by thermal treatment in air. The inset
solvothermal treatment of the solution of TBOT in HAc, followed by thermal treatment in air. The
is the related SAED pattern of a single mesocrystal. (c) Proposed formation mechanism of nanoporous
inset is the related SAED pattern of a single mesocrystal. (c) Proposed formation mechanism of
anatase TiO2 mesocrystals. Reprinted with permission from [47]. Copyright American Chemical
nanoporous anatase TiO2 mesocrystals. Reprinted with permission from [47]. Copyright American
Society, 2011.
Chemical Society, 2011.

After half a month of Qi’s pioneering work, Lu’s group disclosed the fabrication of anatase TiO2
mesocrystals with a single-crystal-like structure, high specific surface area, preferential exposure of
Catalysts 2019, 9, 91 9 of 27

After
Catalysts half
2019, 9, x aFOR
month
PEERof Qi’s pioneering work, Lu’s group disclosed the fabrication of anatase 9TiO
REVIEW of 26
2
mesocrystals with a single-crystal-like structure, high specific surface area, preferential exposure of
highly reactive
highly reactive (001)
(001)crystal
crystalfacets,
facets,and
andcontrollable
controllablemesoporous
mesoporousnetwork
network [130].AsAs
[130]. shown
shown inin Figure
Figure 9,
9, by
by hydrothermal
hydrothermal treating
treating the the solution
solution of TiOSO
of TiOSO 4 in 4 in tert-butyl
tert-butyl alcohol,
alcohol, anatase
anatase TiO 2 TiO 2 nanocrystals
nanocrystals were
were firstly
firstly generated,generated,
the (001)the (001)
facets of facets
which wereof which were adsorbed
preferably SO4 2− anions.
preferablybyadsorbed by SO 42− anions.
Subsequent
Subsequent
oriented oriented attachment
attachment of the anatase of the anatase nanocrystal
nanocrystal building blocksbuilding blocks
created createdclusters
anatase anatasewithclusters
the
with the
(001) (001)
facets wellfacets well protected
protected (step 1). (step
Upon 1).further
Upon further attachment
attachment of the of the building
building blocks,blocks,
anatase anatase
TiO2
TiO2 mesocrystals
mesocrystals preferentially
preferentially exposed exposed
by (001) byfacets
(001)and facets and ahaving
having a disordered
disordered mesoporous mesoporous
network
network
were were
finally finally produced
produced (step 2). (step 2). It is noteworthy
It is noteworthy that when that
thewhen
growth the was
growth was confined
confined in a scaffoldin a
scaffold
with with pore
ordered ordered pore channels,
channels, such as mesoporous
such as mesoporous silica containing
silica containing 2D (SBA-15,
2D (SBA-15, P6mm space P6mmgroup)space
group)
and and three-dimensional
three-dimensional (3D) (KIT-6,(3D) Ia3d
(KIT-6,
spaceIa3d spaceordered
group) group) ordered
mesopores, mesopores, the subsequent
the subsequent scaffold
scaffold removal
removal would lead would lead
to TiO 2 to TiO
crystals crystals
2 with with
replicated replicated
2D 2D
hexagonal hexagonal
(step 3) (step
or 3D 3) or
(step 3D
4) (step 4)
ordered
ordered structure,
network network structure,
respectively.respectively. More interestingly,
More interestingly, such a novel such a novel methodology
methodology could be extendedcould be to
extended to fabricating mesoporous single-crystal-like structures with other compositions
fabricating mesoporous single-crystal-like structures with other compositions (e.g., ZrO2 , CeO2 , etc.), (e.g., ZrO 2,

CeO2providing
thus , etc.), thuspromising
providingmaterials
promising formaterials for various applications.
various applications.

Figure 9.
Figure 9. (a) Synthesis
Synthesis ofof mesoporous
mesoporoussingle-crystal-like
single-crystal-likeanatase
anataseTiOTiO2 2mesocrystals.
mesocrystals.(1)(1)Formation
Formation of
anatase clusters through oriented attachment of anatase nanocrystal building blocks
of anatase clusters through oriented attachment of anatase nanocrystal building blocks with (001) with (001) facets
preferably
facets adsorbed
preferably by SO
adsorbed 2− ions.
by42−SOions. (2) Further attachment
(2) Further attachment of of
thethebuilding
buildingblocks
blocks resulting
resulting in in
4
mesocrystalswith
mesocrystals with preferential
preferential exposedexposed (001) and
(001) facets facets and disordered
disordered mesoporousmesoporous structure.
structure. Mesocrystals
Mesocrystals
with ordered with ordered structure
mesoporous mesoporous were structure
preparedwere
by prepared
a confined bygrowth
a confined growth
of the of the
anatase anatase
crystals in
crystals
(3) in (3)
SBA-15 SBA-15 (mesoporous
(mesoporous silica with 2D silica with 2D
ordered ordered
pore poreand
channels) channels) and(mesoporous
(4) KIT-6 (4) KIT-6 (mesoporous
silica with
3D ordered
silica with pore channels)pore
3D ordered followed by scaffold
channels) removal.
followed TEM images
by scaffold removal.of anatase mesocrystals
TEM images with
of anatase
disordered
mesocrystals mesopores (b), mesoporous
with disordered mesopores mesocrystals grownmesocrystals
(b), mesoporous within SBA-15 (c) and
grown KIT-6
within (d) followed
SBA-15 (c) and
by removal
KIT-6 of the scaffold.
(d) followed The of
by removal insets
the in (b–d) show
scaffold. the related
The insets SAED
in (b–d) show andtheFFT patterns.
related SAED Reprinted
and FFT
with permission from [130]. Copyright John Wiley & Sons Inc., 2011.
patterns. Reprinted with permission from [130]. Copyright John Wiley & Sons Inc., 2011.

The
The above two groups’
above two groups’ fascinating
fascinatingwork
workopened
openeda apromising
promisingavenue
avenueforfor the
the facile
facile synthesis
synthesis of
of porous
porous anatase
anatase mesocrystals.
mesocrystals. AnAn increasing
increasing numberofofreports
number reportsofofthe
the direct
direct fabrication
fabrication of
of TiO
TiO22
mesocrystals
mesocrystalsininsolutions
solutionswithout
without any additives
any have
additives beenbeen
have disclosed in recent
disclosed years. years.
in recent For example, Leite’s
For example,
group proposed a kinetically controlled crystallization process to produce anatase TiO
Leite’s group proposed a kinetically controlled crystallization process to produce2 anatase TiO2 mesocrystals
with a truncated
mesocrystals bipyramidal
with a truncatedmorphology,
bipyramidalwhich was realized
morphology, whichthrough a nonaqueous
was realized throughsol-gel reaction
a nonaqueous
between TiCl
sol-gel reaction
4 and n-octanol [131]. By adopting a similar method to adjust the hydrolysis
between TiCl4 and n-octanol [131]. By adopting a similar method to adjust the dynamic of
hydrolysis dynamic of TTIP in an oxalic acid aqueous solution, hierarchical rutile TiO2 mesocrystals
were produced [48]. Zhao’s group developed a facile synthetic approach to fabricate regular shaped
anatase TiO2 mesocrystals with controllable proportion of (001) and (101) facets [136]. These anatase
TiO2 mesocrystals were prepared by solvothermally treating the solution of TTIP in formic acid (FA),
Catalysts 2019, 9, 91 10 of 27

TTIP in an oxalic acid aqueous solution, hierarchical rutile TiO2 mesocrystals were produced [48]. Zhao’s
group developed a facile synthetic approach to fabricate regular shaped anatase TiO2 mesocrystals with
controllable proportion of (001) and (101) facets [136]. These anatase TiO2 mesocrystals were prepared
by solvothermally treating the solution of TTIP in formic acid (FA), and the exposed (101)/(001)
Catalysts 2019, 9, x FOR PEER REVIEW 10 of 26
ratio
could be adjusted via simply varying the duration of solvothermal treatment. Most recently, our
groupand proposed
the exposed a novel synthetic
(101)/(001) procedure
ratio for producing
could be adjusted spindle-shaped,
via simply single-crystal-like,
varying the duration of solvothermal anatase
TiO2 treatment.
mesocrystals, Mostwhichrecently,
wasour group proposed
realized a novel
by controlling thesynthetic procedure
hydrolysis rate offor producing
TiCl 3 in the spindle-
green solvent
shaped, single-crystal-like, anatase TiO 2 mesocrystals, which was realized by controlling the
PEG-400 (Figure 10) [150]. These mesocrystals constructed by ultrafine nanocrystals (~1.5–4.5 nm
hydrolysis rate of TiCl3 in the green solvent PEG-400 (Figure 10) [150]. These mesocrystals
in size) were revealed to be spindle-shaped and elongated along the [001] direction, having lengths
constructed by ultrafine nanocrystals (~1.5–4.5 nm in size) were revealed to be spindle-shaped and
predominantly of 50–85 nm and diameters of 20–40 nm. It was proposed that at the initial stage of the
elongated along the [001] direction, having lengths predominantly of 50–85 nm and diameters of 20–
reaction, the chelation of PEG-400 to titanium centers firstly resulted in the formation of a titanium
40 nm. It was proposed that at the initial stage of the reaction, the chelation of PEG-400 to titanium
precursor.
centersThis chelated
firstly resultedtitanium precursor
in the formation then underwent
of a titanium precursor.hydrolysis-condensation reaction
This chelated titanium precursor thenin the
presence of water to form Ti-O-Ti bonds, accompanied by the gradual oxidation of Ti3+ to Ti4+ by
underwent hydrolysis-condensation reaction in the presence of water to form Ti-O-Ti bonds,
the dissolved
accompanied oxygen,
by theyielding numerous
gradual oxidation of tiny
Ti3+ toanatase nanocrystals.
Ti4+ by the Theseyielding
dissolved oxygen, tiny anatase
numerousnanocrystals
tiny
wereanatase nanocrystals.
temporarily These
stabilized by tiny anatase nanocrystals
the solvent were temporarily
PEG-400 molecules stabilized
and underwent by the solvent
oriented attachment
alongPEG-400
the [001] molecules
direction, andtogether
underwent oriented
with some attachment along thealong
lateral attachment [001] direction,
some sidetogether
facetswith somefacets,
of (101)
lateral attachment along some side facets of (101) facets, resulting in the formation of
resulting in the formation of mesocrystalline anatase aggregates elongated along the [001] direction. It mesocrystalline
anatase aggregates elongated along the [001] direction. It is worth noting that continuous oriented
is worth noting that continuous oriented attachment of tiny anatase nanocrystals on the preformed
attachment of tiny anatase nanocrystals on the preformed elongated mesocrystalline aggregates
elongated mesocrystalline aggregates occurred when reaction time was prolonged, and well-defined
occurred when reaction time was prolonged, and well-defined spindle-shaped anatase TiO2
spindle-shaped anatase TiO2 mesocrystals
mesocrystals were produced
were produced when the reaction time was extended to 5 h.
when the reaction time was extended to 5 h.

Figure 10. (a)

Figure 10.SEM and (b,c)
(a) SEM TEM TEM
and (b,c) images of anatase
images TiO2 TiO
of anatase mesocrystals obtained
2 mesocrystals via hydrolysis
obtained reaction
via hydrolysis
reaction
of TiCl 3 in of TiCl
PEG-400. 3 in
The PEG-400.
insets The
in (a)insets
are in
the (a) are
related the related
particle particle
size size
distributionsdistributions
of the of the
mesocrystals.
mesocrystals.
(d) SAED pattern(d) SAED pattern
recorded on therecorded
anataseonmesocrystal
the anatase mesocrystal
shown in (c);shown(e)inHRTEM
(c); (e) HRTEM
image image
of anatase
mesocrystal; (f) A tentative mechanism for the formation of anatase mesocrystals.mesocrystals.
of anatase mesocrystal; (f) A tentative mechanism for the formation of anatase Reprinted with
Reprinted
permission fromwith permission
[150]. fromAmerican
Copyright [150]. Copyright American
Chemical Chemical
Society, 2017. Society, 2017.

In addition to the widely employed titanium sources of TBOT, TTIP, TiOSO4, and TiCl3, it has
In addition to the widely employed titanium sources of TBOT, TTIP, TiOSO4 , and TiCl3 , it has been
been well proved that titanate precursors could also be utilized for the fabrication of TiO2
well proved that titanate precursors could also be utilized for the fabrication of TiO2 mesocrystals. In 2012,
mesocrystals. In 2012, Wei’s group reported the synthesis of unique ultrathin-nanowire-constructed
Wei’srutile
group reported the synthesis of unique ultrathin-nanowire-constructed rutile TiO2 mesocrystals
TiO2 mesocrystals through direct transformation from hydrogen titanate nanowire precursors
through
(Figure 11) transformation
direct from titanate
[61]. These hydrogen hydrogen titanate
nanowire nanowire
precursors precursors
were prepared(Figure 11) [61]. These
by hydrothermally
hydrogen
treating the anatase TiO2 in KOH solution, followed by acid washing. Then the precipitatedanatase
titanate nanowire precursors were prepared by hydrothermally treating the TiO2 in
hydrogen
KOHtitanate
solution, followed
nanowires bydispersed
were acid washing.
in HNO3Then thesolution
aqueous precipitated hydrogen
and kept titanate
at 50 °C for 7 days,nanowires
generating were
single-crystal-like
dispersed in HNO3 aqueousrutile TiO 2 mesocrystals
solution at 50 ◦ C
and kepthaving lengths of about
for 7 days, 300 nm and
generating diameters 60–80rutile
single-crystal-like nm. TiO2
It was proposed
mesocrystals that such
having lengths rutile300
of about mesocrystals were actually
nm and diameters 60–80 formed
nm. It wasvia proposed
face-to-facethat
oriented
such rutile
attachment
mesocrystals of ultrathin
were actuallyhydrogen
formed via titanate nanowireoriented
face-to-face buildingattachment
blocks, accompanied by the
of ultrathin conversion
hydrogen titanate
from hydrogen titanate precursor into rutile TiO2. To further modify the morphology of the rutile
nanowire building blocks, accompanied by the conversion from hydrogen titanate precursor into rutile
TiO2 mesocrystals, Wei’s group introduced the surfactant of sodium dodecyl benzene sulfonate
(SDBS) into the reaction solution [62]. They found that SDBS played a vital role in the oriented self-
Catalysts 2019, 9, 91 11 of 27

TiO2 . To further modify the morphology of the rutile TiO2 mesocrystals, Wei’s group introduced the
surfactant of sodium dodecyl benzene sulfonate (SDBS) into the reaction solution [62]. They found that
SDBSCatalysts
played2019,a vital role
9, x FOR in the
PEER oriented self-assembly process, and rutile mesocrystals with controllable
REVIEW 11 of 26

morphologies were successfully fabricated by varying the adding amount of SDBS. Specifically, uniform
assembly process, and rutile mesocrystals with controllable morphologies were successfully
octahedral rutile TiO2 mesocrystals 100–300 nm in size were obtained when the titanate/SDBS ratio was
fabricated by varying the adding amount of SDBS. Specifically, uniform octahedral rutile TiO2
set atmesocrystals
0.09, while nanorod-shaped rutile TiO2 mesocrystals
100–300 nm in size were obtained
were fabricated when the titanate/SDBS ratio
when the titanate/SDBS ratio was set at 0.09, while
increased to 0.15. Interestingly, the morphology and
nanorod-shaped rutile TiO2 mesocrystals were fabricated when the crystalline phase of the TiOratio
titanate/SDBS 2 mesocrystals
increased to were
demonstrated to be adjustable
0.15. Interestingly, upon using
the morphology differentphase
and crystalline counterions to2 mesocrystals
of the TiO manipulate theweregrowth dynamic of
demonstrated
TiO2 to
[63]. If the conversion
be adjustable upon using of titanate
different nanowire
counterionsprecursors
to manipulatewasthe
carried out
growth in HClofaqueous
dynamic solution
TiO2 [63]. If
theof
instead conversion of titanate nanowire
HNO3 , dumbbell-shaped precursors
rutile was carried out composed
TiO2 superstructures in HCl aqueous solution
of loose insteadsubunits
nanowire of
were HNO 3, dumbbell-shaped
prepared, whereas anatase rutileTiO
TiO2 2 mesocrystals
superstructures composed
with of loose nanowire
a quasi-octahedral subunits were
or truncated-octahedral
prepared, whereas anatase TiO 2 mesocrystals with a quasi-octahedral or truncated-octahedral
morphology were obtained from H2 SO4 aqueous solution. Such a novel synthetic procedure could also
morphology were obtained from H2SO4 aqueous solution. Such a novel synthetic procedure could
be extendable for the preparation of TiO2 mesocrystals with other crystal phases. For example, by using
also be extendable for the preparation of TiO2 mesocrystals with other crystal phases. For example,
amorphous titanates as titanium precursor and oxalic acid as structure-directing agent, novel brookite
by using amorphous titanates as titanium precursor and oxalic acid as structure-directing agent,
TiO2 novel
mesocrystals
brookitewere successfully were
TiO2 mesocrystals fabricated, as well
successfully [157]. as well [157].
fabricated,

Figure 11. (a,b)

Figure TEM
11. (a,b) TEMand (c)(c)
and HRTEM
HRTEMimages
images of
of rutile TiO2 2mesocrystals
rutile TiO mesocrystals formed
formed by conversion
by conversion of of
titanate nanowire precursors in HNO
titanate nanowire precursors in HNO aqueous solution without any additives. The lower
3 3 aqueous solution without any additives. The lower left inset left inset in
(b) is in
an(b)
enlarged TEM image,
is an enlarged and the
TEM image, upper
and right inset
the upper is theisSAED
right inset pattern
the SAED related
pattern to the
related whole
to the wholeparticle.
(d) Schematic
particle. (d)illustration
Schematic of a tentative
illustration of mechanism for the formation
a tentative mechanism of rutile TiO
for the formation 2 mesocrystals.
of rutile TiO2
mesocrystals.
Reprinted Reprinted with
with permission frompermission from [61].
[61]. Copyright Copyright
Royal SocietyRoyal Society of Chemistry,
of Chemistry, 2012. 2012.

3. Modification of TiO
3. Modification 2 Mesocrystals
of TiO 2 Mesocrystals

3.1. Fabrication of Doped

3.1. Fabrication TiO
of Doped 2 Mesocrystals
TiO 2 Mesocrystals

As mentioned
As mentioned above,
above, the the pristine
pristine TiOTiO 2 can
2 can merely
merely absorb
absorb ultra-violetirradiation
ultra-violet irradiationowing
owing toto its
its wide
bandwide band gap; continuous
gap; continuous efforts haveefforts havechanneled
thus been thus been towards
channeled towards developing
developing visible-light- TiO2
visible-light-responsive
responsive for
photocatalysts TiOvarious
2 photocatalysts for various applications [8–13,16–21]. In addition to the well-known
applications [8–13,16–21]. In addition to the well-known dye sensitization,
dye sensitization, the modification of TiO2 with impurity doping was demonstrated to exhibit visible-
the modification of TiO2 with impurity doping was demonstrated to exhibit visible-light-responsive
light-responsive photocatalytic reactivity and showed improved stability upon light irradiation
photocatalytic reactivity and showed improved stability upon light irradiation [11,16,19]. Considering
[11,16,19]. Considering the novel structural characteristics of TiO2 mesocrystals, the fabrication of
the novel
metal-structural characteristics
or nonmetal-doped TiO2ofmesocrystals
TiO2 mesocrystals,
may givethe fabrication
rise of metal- or nonmetal-doped
to ideal photocatalysts for particle
TiO2 applications,
mesocrystalsand may give rise to ideal photocatalysts for particle applications,
thus has drawn considerable research interest [158–161]. For example, and thus has drawn
Majima’s
considerable research interest
group successfully prepared[158–161].
N-doped For example,
anatase Majima’s group
TiO2 mesocrystals successfullytreatment
by solvothermal preparedofN-doped
the
anatase TiO2 mesocrystals
pre-synthesized by solvothermal
TiO2 mesocrystals treatment of the
with triethanolamine pre-synthesized
[158]. Owing to the high TiOinternal
2 mesocrystals
porosity with
and high specific
triethanolamine [158].surface
Owing areatoofthe
TiOhigh
2 mesocrystals, the element
internal porosity andofhigh
N could diffuse
specific into the
surface pores
area of TiO2
easily andthe
mesocrystals, waselement
adsorbedofon Nthe surface.
could In addition,
diffuse into the by stirring
pores TiOand
easily 2 mesocrystals
was adsorbedin NaFonaqueous
the surface.
solution at room temperature, F-doped anatase TiO 2 mesocrystals could also be fabricated. It was
In addition, by stirring TiO2 mesocrystals in NaF aqueous solution at room temperature, F-doped
proposed that surface fluorination via ligand exchange between F− and surface OH groups on TiO2
anatase TiO2 mesocrystals could also be fabricated. It was proposed that surface fluorination via ligand
occurred during the stirring process, resulting in the incorporation of F into TiO 2 mesocrystals.
exchange between F− and surface OH groups on TiO2 occurred during the stirring process, resulting in
Combining these two doping strategies together would lead to the formation of N, F-codoped anatase
the incorporation of F without
TiO2 mesocrystals into TiOchanging
2 mesocrystals. Combining
the morphology, these two doping
crystallinestructure, andstrategies together
surface area of TiOwould
2
lead to the formation
mesocrystals (Figureof N,
12).F-codoped
Apart from anatase TiO2 mesocrystals
the nonmetal-doped without changing
TiO2 mesocrystals, the morphology,
it was demonstrated
that metal-doped TiO2 mesocrystals could also be synthesized. Wei’s group prepared pure rutile TiO2
Catalysts 2019, 9, 91 12 of 27

crystallinestructure, and surface area of TiO2 mesocrystals (Figure 12). Apart from the nonmetal-doped
Catalysts 2019, 9, x FOR PEER REVIEW 12 of 26
TiO2 Catalysts
mesocrystals, it was
2019, 9, x FOR demonstrated
PEER REVIEW that metal-doped TiO2 mesocrystals could also be synthesized.
12 of 26
Wei’smesocrystals
group prepared first,pure
and rutile TiO2 mesocrystals
then hydrothermally first,
treated andin
them then hydrothermally
aqueous treated
niobium oxalate them in
solution. aqueous
After
mesocrystals
niobium oxalate
a certain first,
ofand
solution.
period then hydrothermally
After a certain
hydrothermal treated
period
treatment, them inNb-doped
aqueous
of hydrothermal
homogeneous niobium
treatment, oxalate solution. Nb-doped
homogeneous
rutile TiO 2 mesocrystals After
could
rutileafinally
certain
TiO beperiod
produced
2 mesocrystals
of hydrothermal
[161]. treatment,
could finally homogeneous
be produced [161]. Nb-doped rutile TiO2 mesocrystals could
finally be produced [161].

Figure 12. Proposed

Figure synthetic
12. Proposed route
synthetic routetoward
towardN,N,F-codoped anataseTiO
F-codoped anatase TiO 2 mesocrystals.
2 mesocrystals. Reprinted
Reprinted with with
Figure
permission 12.
from
permission Proposed
[158].
from synthetic
Copyright
[158]. route
Copyright toward2016.
Elsevier,
Elsevier, N, F-codoped anatase TiO2 mesocrystals. Reprinted with
2016.
permission from [158]. Copyright Elsevier, 2016.
Recently,
Recently, thetheintroduction
introduction of of oxygen
oxygen vacancies
vacancies or Ti3+ orionsTi3+intoions
TiO2 into TiO2 oxygen-
to produce to produce
Recently,
oxygen-deficient/Ti
deficient/Ti self-doped
3+ 3+
the introduction
self-doped of oxygen vacancies
TiO2 mesostructures
TiO2 mesostructures has been well or Ti
has been3+ ions into TiO2 to produce oxygen-
acceptedwelltoaccepted
be one of to thebemostoneefficient
of the most
deficient/Ti
ways
efficient ways to self-doped
to extend3+
the light
extend TiO 2 mesostructures
theabsorption
light has2 to
region ofregion
absorption TiO been welllight
visible
of TiO accepted
to tolight
[162–166].
visible be Different
one of the
[162–166]. most
from efficient from
traditional
Different
2
ways to extend the light absorption region of TiO2 toorvisible lightis3+
doping
traditional strategies,
doping introducing
strategies, oxygen
introducing vacancies
oxygen Ti3+ ions
vacancies or Ti [162–166].
a ions is aDifferent
unique doping
uniquemethodfrom traditional
dopingthat can that
method
doping
maintainstrategies, introducing
the characteristic oxygen
nature of TiO vacancies
2. At the or same Ti time,
3+ ions this
is a kind
unique doping also
of doping methodimprovesthat can
the
can maintain the characteristic nature of TiO2 . At the same time, this kind of doping also improves the
maintain the characteristic
electroconductivity of TiO nature of TiOfacilitating
2, thereby 2. At the same time, transportation
charge this kind of doping within alsoTiOimproves the
2 particles
electroconductivity
electroconductivity
of TiO , thereby facilitating charge transportation
2 TiO2, thereby facilitating charge transportation within within TiO 2 particles [162,164,167].
[162,164,167]. In thisofregard, great efforts have been made toward preparing oxygen-deficient/Ti TiO2 particles3+
3+ self-doped TiO
In this regard,
[162,164,167].
self-doped TiO
great efforts
In2 this
mesocrystals
have
regard, great been made toward
efforts have A
[65,136,150,168]. beenpreparing
goodmade oxygen-deficient/Ti
toward
example inpreparing
this area isoxygen-deficient/Ti
that Zhao’s group 3+ 2
mesocrystals
self-doped [65,136,150,168].
reported a facileTiO2 mesocrystals
evaporation-driven A good example
[65,136,150,168]. in this
A good route
oriented assembly area
example is that Zhao’s
in thiswith
combined areapostgroup
is that reported
Zhao’s
thermal a
group
treatment facile
evaporation-driven
reported a facile oriented
in N2 atmosphere assembly
evaporation-driven
to fabricate route combined
oriented assemblywith
ultrathin-nanosheet-assembled routepost thermal
combined
olive-shaped withtreatment
post thermal
mesoporous inanatase
Ntreatment
2 atmosphere
TiO2
in N2 atmosphere
to fabricate
mesocrystals (Figureto fabricate
13) [65].ultrathin-nanosheet-assembled
ultrathin-nanosheet-assembled These mesoporous olive-shaped
mesocrystals olive-shaped
mesoporous mesoporous
anatase
were illustrated to have TiO anatase TiO2
2 mesocrystals
high surface
mesocrystals
area
(Figure 13)(~189 2(Figure
[65].mThese/g), large 13)
pore[65].
mesoporous These
volume mesoporous
(0.56 cm3/g),were
mesocrystals mesocrystals
and abundant
illustrated were
oxygen illustrated
to have vacancies toor
high surfacehave high
unsaturated
area (~189 Ti 3+m2 /g),
surface
largearea
pore(~189 m /g), large cmpore
3 /g),volume (0.56 cm /g), and vacancies
abundant oxygen vacancies or3+unsaturated Ti 3+
2 3
sites. Additionally,
volume (0.56 by thermally treating
and abundant theoxygen
anatase TiO2 mesocrystals precipitated
or unsaturated Ti from the
sites. PEG-
Additionally,
sites.
400/TiClAdditionally,
3 mixed solution by thermally treating
in vacuum, ourthegroup
anatase TiO2 mesocrystals
successfully synthesizedprecipitated from thesingle-
Ti 3+ self-doped, PEG-
by thermally treating the anatase TiO2 mesocrystals precipitated from the PEG-400/TiCl 3 mixed solution
400/TiCl 3 mixed
crystal-like, solution in vacuum,
spindle-shaped, anatase our TiO2group successfully
mesocrystals [150]. synthesized
Moreover, Ti
by3+ self-doped, single-
reducing the pre-
in vacuum, our group successfully synthesized Ti3+ self-doped, single-crystal-like, spindle-shaped,
crystal-like,
synthesized spindle-shaped,
TiO2 mesocrystalsanatase with NaBHTiO2 4,mesocrystals
oxygen-deficient [150].sheet-like
Moreover, by reducing
anatase the pre-
TiO2 mesocrystals
anatase TiO2 mesocrystals
synthesized TiO2 mesocrystals [150]. Moreover,
with NaBHby reducing the pre-synthesized TiO2 mesocrystals
4, oxygen-deficient sheet-like anatase TiO 2 mesocrystals
with
were also synthesized [168].
NaBH 4
were, oxygen-deficient
also synthesized [168]. sheet-like anatase TiO 2 mesocrystals were also synthesized [168].

Figure 13. (a) Schematic illustration of the growth process of Ti3+ self-doped olive-shaped mesoporous
Figure 13. (a)2 mesocrystals
Schematic illustration ofthe
thegrowth
growth process 3+3+
ofofTiTi self-doped olive-shaped mesoporous
Figure 13. (a)
anatase TiOSchematic illustration
throughofevaporation-driven
process oriented self-doped
assembly olive-shaped
process; (b) SEM mesoporous
image, (c)
anatase
anatase
TEMTiO TiO mesocrystals
2 mesocrystals
image, 2 through
through
(d) EPR spectra, evaporation-driven
andevaporation-driven oriented
(e) Ti2p XPS core-level oriented assembly
spectraassembly process; (b) SEM image,
SEM(c)
process;olive-shaped
of Ti self-doped
3+
(b) image,
TEM
(c) TEM image,(d)
mesoporous
image, (d) EPR spectra,
anatase
EPR spectra, and (e)
(e) Ti2p
TiO2 mesocrystals.
and XPS
The
Ti2p XPS core-level
inset in (c) is
core-level spectra of of
the SAED
spectra Ti3+ self-doped
3+
Tipattern olive-shaped
of an
self-doped individual
olive-shaped
mesoporous
mesocrystal.
mesoporous anatase anatase
TiO2 TiO
Reprinted 2 mesocrystals.
with permission
mesocrystals. The The
from inset
[65].
inset in (c) SAED
Copyright
in (c) is the isAmerican
the pattern
SAEDChemical
pattern of an individual
Society,
of an individual 2015.
mesocrystal.
mesocrystal. Reprinted with permission from [65]. Copyright American Chemical Society, 2015.
Reprinted with permission from [65]. Copyright American Chemical Society, 2015.
 x FOR PEER REVIEW
Catalysts 2019, 9, 91 26
13 of 27

3.2. Construction of TiO2 Mesocrystal-Based Heterostructures

3.2. Construction of TiO2 Mesocrystal-Based Heterostructures
Apart from the above-mentioned doping strategies, the coupling of TiO2 mesocrystals with
appropriatefrom
Apart theelements
foreign above-mentioned
to construct doping strategies, the coupling
TiO2 mesocrystal-based of TiO2 mesocrystals
heterostructures is considered with
to
appropriate foreign elements to construct TiO mesocrystal-based
be another effective way to enhance the 2 light absorbance capability as well as inhibit theheterostructures is considered to be
another effective
photoinduced way to
charge enhance
carrier the light absorbance
recombination [17,18,21].capability
Hitherto,asvarious
well askinds
inhibit ofthe photoinduced
foreign elements
charge
have been successfully utilized to modify anatase TiO2 mesocrystals [59,60,169–183]. Forhave
carrier recombination [17,18,21]. Hitherto, various kinds of foreign elements been
example,
successfully utilized to modify anatase
Sun’s group successfully fabricated spindle-like TiO 2 mesocrystals [59,60,169–183]. For example,
TiO2/CdS composites by uniformly distributing CdS Sun’s group
successfully
nanoparticles onto nanoporous anatase mesocrystals viaby
fabricated spindle-like TiO 2 /CdS composites theuniformly distributing CdS
simple hydrothermal andnanoparticles
hot-injection
onto
methods [170]. Bian’s group produced CdS quantum dot (QD)-decorated anatase TiOmethods
nanoporous anatase mesocrystals via the simple hydrothermal and hot-injection [170].
2 mesocrystals
Bian’s group produced CdS quantum dot (QD)-decorated
preferably enclosed by (001) facets via the facile solvothermal treatment anatase TiO mesocrystals preferably
2 of TiOSO4 in tert-butyl
enclosed by (001) facets via the facile solvothermal treatment
alcohol, followed by modification with CdS QDs via a simple ion-exchange treatment of TiOSO 4 in tert-butyl alcohol, followed
[175]. Majima’s
by modification with CdS QDs via a simple ion-exchange treatment
group applied a simple photodeposition method to deposit noble metal (Au, Pt) nanoparticles onto [175]. Majima’s group applied a
simple photodeposition
the pre-synthesized methodanatase
sheet-like to deposit
TiOnoble metal (Au, Pt) nanoparticles onto the pre-synthesized
2 mesocrystals and realized the fabrication of novel metal-
sheet-like
semiconductor superstructure nanocomposites [169].the
anatase TiO 2 mesocrystals and realized fabrication
Similarly, of novel
by adopting bymetal-semiconductor
a facile impregnation
superstructure nanocomposites [169]. Similarly, by adopting
method, they were also able to deposite Au nanoparticles onto TiO2 mesocrystals and by a facile impregnation method, they
fabricate
were also able
promising to deposite
plasmonic Au nanoparticles
photocatalysts [172]. onto
Moreover,TiO2 mesocrystals
to broaden the andlight-responsive
fabricate promising regionplasmonic
of TiO2
photocatalysts [172]. Moreover, to broaden the light-responsive
mesocrystals to near-infrared (NIR) light, they also loaded Au nanorods with controllable region of TiO 2 mesocrystals to
size and
near-infrared (NIR) light, they also loaded Au nanorods with controllable
tunable surface plasmon resonance (SPR) band onto anatase TiO2 mesocrystals through the well- size and tunable surface
plasmon
known ligandresonance (SPR)
exchange band onto
method [179].anatase TiO2 mesocrystals
It is noteworthy through
that in addition to the
the well-known
deposition ofligand guest
exchange method [179]. It is noteworthy that in addition to
elements onto the pre-synthesized anatase TiO2 mesocrystals, anatase TiO2 mesocrystals the deposition of guest elements
with desiredonto
the pre-synthesized
morphologies couldanatase
also be grownTiO2 mesocrystals,
on various kinds anatase TiO2 mesocrystals
of substrates. Tang’s groupwith desired
introduced morphologies
graphene
could also be grown on various kinds of substrates. Tang’s
oxide (GO) nanosheets into the reaction solution of TBOT in HAc. They found that after group introduced graphene oxide (GO)a
nanosheets into the reaction solution of TBOT in HAc. They found
solvothermal treatment at elevated temperatures, spindle-shaped anatase TiO2 mesocrystals werethat after a solvothermal treatment
at elevated temperatures,
successfully grown on the spindle-shaped
reduced graphene anatase TiO2 mesocrystals
nanosheets [171]. Laterwere on,successfully
Lu’s groupgrown on thea
dispersed
reduced graphene nanosheets [171]. Later on, Lu’s group dispersed
certain amount of graphene into the reaction system of TiOSO4 in tert-butyl alcohol. Upon microwavea certain amount of graphene
into the reaction
treatment of the system
obtained TiOSO4 in tert-butyl
of suspension, anatase alcohol. Upon microwave
TiO2 mesocages treatment of the structure
with a single-crystal-like obtained
suspension,
were found to be evenly anchored on graphene nanosheets [59]. Most recently, our evenly
anatase TiO 2 mesocages with a single-crystal-like structure were found to be group
anchored
demonstratedon graphene
that throughnanosheets [59]. Most
in situ growth recently, defective
of nanosized our groupanatase
demonstrated that through
TiO2-x mesocrystals in situ
(DTMCs)
growth
on g-C3N of4 nanosized
nanosheetsdefective
(NSs), a anatase
novel 3D/2D TiO2-xDTMC/g-C
mesocrystals (DTMCs) on g-C3 N4with
3N4 NS heterostructure
nanosheets (NSs), a
tight interfaces
novel 3D/2D DTMC/g-C N
could be formed (Figure 14) [183].
3 4 NS heterostructure with tight interfaces could be formed (Figure 14) [183].

Figure
Figure 14. (a,b) TEM
14. (a,b) TEM and
and (c)
(c) HRTEM
HRTEM images
images of
of 33.3%
33.3% g-C
g-C33N /DTMCs. The
N44/DTMCs. The inset
inset is
is the
the SAED
SAED pattern
pattern
related to the whole particle. (d) HAADF-TEM image with elemental mapping
related to the whole particle. (d) HAADF-TEM image with elemental mapping of of 33.3% g-C N /DTMCs.
3 433.3% g-
(e)
C3N4/DTMCs. (e) Schematic presentation of the in situ growth of TiO2 mesocrystals onReprinted
Schematic presentation of the in situ growth of TiO 2 mesocrystals on a g-C3 N 4 nanosheet. a g-C3N4
with permission
nanosheet. from with
Reprinted [183].permission
Copyright from
John [183].
Wiley Copyright
& Sons Inc., 2018.
John Wiley & Sons Inc., 2018.
Catalysts 2019, 9, 91 14 of 27

4. TiO2 Mesocrystals for Photocatalytic Applications

4.1. Bare TiO2 Mesocrystals for Photocatalytic Applications

Owing to the novel structural characteristics of mesocrystals, it is speculated the as-synthesized
TiO2 mesocrystals can be a promising candidate for photocatalytic applications. Liu’s group
first reported that the precipitated rod-like anatase TiO2 mesocrystals delivered relatively higher
photoreactivity toward the removal of methyl orange (MO) than the corresponding commercial P25
counterpart [127]. They ascribed the remarkably improved photocatalytic activity of the sample to its
relatively high surface area, which could provide abundant sites for adsorption capability of MO. Yu’s
group proposed that the TiO2 mesocrystals obtained in their additive-free reaction system possessed
a well-crystallized rutile phase, low band gap energy and fast electron transfer property, and could
exhibit high and stable photocatalytic activity for the removal of NO [128]. Lu’s group evaluated the
photoreactivity of the obtained single-crystal-like anatase TiO2 mesocages and found that those unique
TiO2 mesocages with 3D ordered mesoporous channels exhibited superior photocatalytic activity
toward oxidizing toluene to benzaldehyde and cinnamyl alcohol to cinnamaldehyde relative to that of
TiO2 mesocages with 2D ordered mesoporous channels, TiO2 mesocages with disordered mesoporous
channels, polycrystalline TiO2 , and P25 [130]. Leite’s group claimed that the combination of high
surface area and high crystallinity of the recrystallized mesocrystals can be more advantageous in
photocatalytic applications than the corresponding disordered aggregate of nanocrystals [131].
Despite of the great efforts mentioned above toward the investigation of the photoreactivity
of TiO2 mesocrystals, it wasn’t until 2012 that Majima’s group first illustrated the photoelectronic
properties of TiO2 superstructures, in order to shed light on the intrinsic relationships between
structural ordering and photoreactivity [135]. In their study, plate-like anatase TiO2 mesocrystals
synthesized via a topotactic transformation were selected as the target objects. These TiO2 mesocrystals
were built from crystallographically ordered anatase TiO2 nanocrystal subunits and had a high surface
area and high percentage of exposed highly reactive (001) facets. The photoconductive atomic force
microscopy and time-resolved diffuse reflectance spectroscopy (DRS) were adopted to measure the
charge transportation within the anatase mesocrystals, and the obtained results were compared with
the reference anatase nanocrystals having similar surface area. It was consequently demonstrated
that such a novel structure of anatase mesocrystals could exhibit largely enhanced charge separation
and have remarkably long-lived charges, and thus could deliver greatly enhanced photoconductivity
and photoreactivity (Figure 15). In 2015, Bian’s group carefully evaluated the influence of intercrystal
misorientation within anatase TiO2 mesocrystals on the photoreactivity of the sample. They concluded
that the misorientation of nanocrystal building blocks within anatase mesocrystals was harmful for the
effective separation of photogenerated charge carriers and thus largely suppressed the photocatalytic
efficiencies (Figure 16) [184]. Recently, Hu’s group reported that the photocatalytic properties of
anatase TiO2 mesocrystals were actually largely dependent on the interfacial defects of intergrains
within the particles [152]. They found that anatase TiO2 mesocrystal photocatalysts exhibited much
higher photocatalytic activity toward organic degradation and hydrogen evolution in comparison to
single-crystalline crystals and poly crystalline crystals, which can be attributed to the presence of an
appropriate number of interfacial defects at the intergrains and the facilitated charge carrier transport
across the highly oriented interfaces. Moreover, it is inferred that the photoreactivity of the resultant
anatase TiO2 mesocrystal could be further optimized by regulation of defects, which could be simply
achieved through annealing in redox atmospheres.
Catalysts 2019, 9, 91 15 of 27
Catalysts
Catalysts 2019,
2019, 9, x9,FOR
x FOR PEER
PEER REVIEW
REVIEW 15 26
15 of of 26

Figure15.15. Photodegradation
Photodegradation of of
(a)(a) 4-CP
4-CP and and
(b)(b) Cr(VI)
Cr(VI) usingusing various
various kinds
kinds of of
of TiOTiO as catalysts.
as2 catalysts. (c) (c)
Figure 15. Photodegradation Cr(VI) using various kinds TiO 22 as catalysts.
Time-resolved
Time-resolved diffuse diffuse reflectance
diffuse reflectance spectra
reflectance spectra observed
spectra observed at 200 ns after
observed at 200 ns after the laser the laser flash
laser flash (355-nm) during thethe
(355-nm)
flash (355-nm) during
photolysis of Meso-TiO 2 -500 in the absence and
photolysis of Meso-TiO22-500 in the absence and presence of 10 mMpresence of 10 mM 4-(methylthio)
mM 4-(methylthio)
4-(methylthio) phenyl phenyl
phenyl methanol
methanol
(MTPM)
(MTPM) as as
thethe
the probe
probe
probe molecule
molecule
molecule toestimate
estimate
totoestimate the
the
the lifetime
lifetime
lifetime of the
of of
the the charge-separated
charge-separated
charge-separated state
state
state in
inacetonitrile.(d)(d)
acetonitrile.
in acetonitrile.
(d)Differential
Differential time
time traces
traces of
of %Abs
%Abs at
at 550
550 nm
nm obtained
obtained inin the
the presence
presence
Differential time traces of %Abs at 550 nm obtained in the presence of 10 mM MTPM for of
of 1010
mM mM MTPM
MTPM forfor different
different
TiOTiO 2 samples in acetonitrile.
22 samples in acetonitrile.
Reprinted
acetonitrile. Reprinted withwith permission
permission fromfrom [135].
[135].
[135]. Copyright
Copyright
Copyright American
American Chemical
Chemical
Chemical
Society,
Society, 2012.
Society, 2012.
2012.

Figure
Figure
Figure 16. Rates
16.16.
Rates comparison
Rates comparison
comparison of
of phenol
of phenol
phenol photodegradation
photodegradation
photodegradation and H
and
and production
H22H upon
2 production
production upon TiO
upon
TiOTiO mesocrystals
2 mesocrystals
22 mesocrystals
built from
built well-ordered
from (red
well-ordered column)
(red and
column) less-ordered
and (blue
less-orderedcolumn)
(blue orientation
column) of nanocrystal
orientation
built from well-ordered (red column) and less-ordered (blue column) orientation of nanocrystal of subunits.
nanocrystal
Reprinted
subunits.
subunits. with permission
Reprinted
Reprinted with
with from [184].from
permission
permission Copyright
from American
[184].
[184]. Copyright
Copyright Chemical
American
American Society, 2015.
Chemical
Chemical Society,
Society, 2015.
2015.
4.2.4.2.
Doped
DopedTiO 2 Mesocrystals
TiO for Photocatalytic Applications
2 Mesocrystals for Photocatalytic Applications
4.2. Doped TiO 2 Mesocrystals for Photocatalytic Applications
Although
Although a number
a number of of
reports have
reports havedemonstrated
demonstrated that TiO
that 2 mesocrystals
TiO can exhibit obviously
2 mesocrystals can exhibit obviously
Although a number of reports have demonstrated that TiO 2 mesocrystals can exhibit obviously
enhanced
enhanced photocatalytic
photocatalytic performance
performance in various applications, their real application is still hampered
enhanced photocatalytic performance in in various
various applications,
applications, their
their real
real application
application is still
is still hampered
hampered
byby thethe
limited
limitedlight absorbance
light absorbance of the pristine TiO 2 with a wide band gap. By utilizing the commonly
by the limited light absorbance of of
thethe pristine
pristine TiOTiO 2 with a wide band gap. By utilizing the commonly
2 with a wide band gap. By utilizing the commonly
used
used doping
dopingstrategy, thethe
strategy, thus-prepared
thus-prepared doped
doped TiO 2 mesocrystals
TiO can therefore become visible-light
2 mesocrystals can therefore become visible-light
used doping strategy, the thus-prepared doped TiO2 mesocrystals can therefore become visible-light
responsive,
responsive, thus
thus displaying
displaying enhanced
enhanced visible-light-driven
visible-light-driven photoreactivity
photoreactivity [136,150,158,159,168].
[136,150,158,159,168]. In In
responsive, thus displaying enhanced visible-light-driven photoreactivity [136,150,158,159,168]. In
2016,
2016, Majima’s
Majima’s group
groupinvestigated
investigated thethe
photoreactivity
photoreactivity of ofN,N,F-codoped
F-codoped anatase
anatase TiO 2 mesocrystals.
TiO 2 mesocrystals.
2016, Majima’s group investigated the photoreactivity of N, F-codoped anatase TiO2 mesocrystals.
They
They found
foundthat,
that,owing
owing to to
the synergetic effect of of
N and F doping, the as-prepared product exhibited
They found that, owing to thethe synergetic
synergetic effect
effect of N N andand F doping,
F doping, thethe as-prepared
as-prepared product
product exhibited
exhibited
high
high visible-light-driven
visible-light-driven photoreactivity
photoreactivity for degradating
for degradating RhB RhBandand4-nitrophenol
4-nitrophenol (4-NP)
(4-NP) [158]. Our
[158]. Our
high visible-light-driven photoreactivity for
3+ degradating RhB and 4-nitrophenol (4-NP) [158]. Our
group
group demonstrated
demonstrated that
that the
the obtained
obtained Ti3+ self-doped
Ti self-doped anatase
anatase TiO TiO 2 mesocrystals
2 mesocrystals
showed
showed much much
higher
group demonstrated that the obtained Ti self-doped anatase TiO2 mesocrystals showed much higher
3+
higher visible-light-driven
visible-light-driven photoreactivity
photoreactivity toward toward
removingremoving
NO NOCr
and and(VI)Crcompared
(VI) compared
with withofthat
that 3+ of
visible-light-driven photoreactivity toward removing NO and Cr (VI) compared with that of Ti3+Tiself-
self-
Ti3+ self-doped
doped anatase anatase nanocrystal
nanocrystal counterparts.
counterparts. Such Such a photoreactivity
a photoreactivity enhancement
enhancement was was
mainly mainly
due
doped anatase nanocrystal counterparts. Such a photoreactivity enhancement was mainly due to to
thethe
due to the self-doping
intrinsic intrinsic self-doping
nature, nature,
high high crystallinity,
crystallinity, as well as as
highwell as highofporosity
porosity the of the
anatase anatase
mesocrystals
intrinsic self-doping nature, high crystallinity, as well as high porosity of the anatase mesocrystals
(Figure
(Figure 17)17) [150].
[150]. Most
Most recently,
recently, Majima’s
Majima’s group
group applied
applied femtosecond
femtosecond time-resolved
time-resolved DRS DRSand and single-
single-
particle
particle photoluminescence
photoluminescence (PL)
(PL) measurements
measurements to to characterize
characterize reduced
reduced TiOTiO 2 mesocrystals to get
2 mesocrystals to get
Catalysts 2019, 9, 91 16 of 27

mesocrystals
Catalysts 2019, 9,(Figure 17) [150].
x FOR PEER REVIEW Most recently, Majima’s group applied femtosecond time-resolved16DRS of 26
and single-particle photoluminescence (PL) measurements to characterize reduced TiO2 mesocrystals
to getunderstanding
deep deep understanding of the correlation
of the correlation betweenbetween oxygen deficiency,
oxygen deficiency, photogenerated
photogenerated charge
charge transfer,
transfer, and photoreactivity
and photoreactivity of the material
of the material [168].
[168]. They They confirmed
confirmed the enhanced
the enhanced light absorption
light absorption through
through
forming forming
oxygen oxygen vacancies
vacancies did not didalways
not always result
result in higher
in higher photoreactivity,and
photoreactivity, andan
an appropriate
amount of oxygen vacancies was required to improve the photogenerated charge carrier separation,
thus giving riserise to
to optimized
optimized photoreactivity.
photoreactivity.

Figure
Figure 17. (a) UV-Vis
17. (a) UV-Vis DRS,
DRS, (b)
(b) PL
PL emission
emission spectra,
spectra, and
and (c)
(c) photocurrent
photocurrent intensity
intensity of
of (i)
(i) anatase
anatase
mesocrystals and (ii) anatase nanocrystals of TiO self-doped with Ti3+3+. (d) Visible-light-driven
mesocrystals and (ii) anatase nanocrystals of TiO 2 2 self-doped with Ti . (d) Visible-light-driven
photodegradation
photodegradation of of NO
NO upon
upon (i)
(i) anatase
anatase mesocrystals
mesocrystals and
and (ii)
(ii) anatase
anatase nanocrystals
nanocrystals self-doped
self-doped with
with
Ti 3+ Reprinted with permission from [150]. Copyright John Wiley & Sons Inc., 2017.
Ti3+.. Reprinted with permission from [150]. Copyright John Wiley & Sons Inc., 2017.

4.3. Composited TiO2 Mesocrystals for Photocatalytic Applications

4.3. Composited TiO2 Mesocrystals for Photocatalytic Applications
In addition to the aforementioned doping strategy, the coupling of TiO2 mesocrystals with
In addition to the aforementioned doping strategy, the coupling of TiO2 mesocrystals with
appropriate foreign materials to construct TiO2 -mesocrystal-based heterostructures is considered to be
appropriate foreign materials to construct TiO2-mesocrystal-based heterostructures is considered to
another useful methodology to broaden the light absorbance region of the material to visible light or
be another useful methodology to broaden the light absorbance region of the material to visible light
even near-infrared (NIR) light, as well as to facilitate the mobility of photogenerated charge carriers
or even near-infrared (NIR) light, as well as to facilitate the mobility of photogenerated charge carriers
within the particle [169–183]. For example, by utilizing CdS nanocrystals to modify spindle-shaped
within the particle [169–183]. For example, by utilizing CdS nanocrystals to modify spindle-shaped
nanaporous anatase TiO2 mesocrystals, Sun’s group combined the advantages of the individual
nanaporous anatase TiO2 mesocrystals, Sun’s group combined the advantages of the individual
material, including (1) augmented specific surface area to provide more absorption and reactive
material, including (1) augmented specific surface area to provide more absorption and reactive sites;
sites; (2) TiO2 mesocrystal substrate with high crystallinity and porosity to facilitate charge transport;
(2) TiO2 mesocrystal substrate with high crystallinity and porosity to facilitate charge transport; (3)
(3) uniform distribution of CdS nanocrystals on mesocrystal surface and pores to facilitate charge
uniform distribution of CdS nanocrystals on mesocrystal surface and pores to facilitate charge
transfer, and isolate photoinduced electrons and holes in two distinct materials; (4) tight contact
transfer, and isolate photoinduced electrons and holes in two distinct materials; (4) tight contact
between anatase mesocrystals and CdS nanocrystals to minimize the photo-corrosion and leaching off
between anatase mesocrystals and CdS nanocrystals to minimize the photo-corrosion and leaching
of CdS nanocrystals; and (5) extension of the photo-response of the material [170]. As expected, this
off of CdS nanocrystals; and (5) extension of the photo-response of the material [170]. As expected,
unique spindle-shaped TiO2 /CdS photocatalyst exhibited relatively high visible-light-driven activity
this unique spindle-shaped TiO2/CdS photocatalyst exhibited relatively high visible-light-driven
toward photodegradation of RhB. Bian’s group reported that by decorating CdS QDs onto TiO2
activity toward photodegradation of RhB. Bian’s group reported that by decorating CdS QDs onto
mesocrystals with a high percentage of exposed (001) facets, considerably high visible-light-driven
TiO2 mesocrystals with a high percentage of exposed (001) facets, considerably high visible-light-
photoreactivity could be achieved when selectively oxidizing various kinds of alcohols to their
driven photoreactivity could be achieved when selectively oxidizing various kinds of alcohols to their
corresponding aldehydes [175]. Such an enhancement of the photoreactivity could be attributed
corresponding aldehydes [175]. Such an enhancement of the photoreactivity could be attributed to
to CdS QDs with improved photosensitization, porous mesostructure with high surface area, and
CdS QDs with improved photosensitization, porous mesostructure with high surface area, and
exposed (001) facets with high surface energy and large quantities of oxygen vacancies, which could
exposed (001) facets with high surface energy and large quantities of oxygen vacancies, which could
promote light absorbance in the visible light region, reactant molecule adsorption and activation, as
promote light absorbance in the visible light region, reactant molecule adsorption and activation, as
well as photogenerated charge carrier separation. Majima’s group claimed that superior electron
well as photogenerated charge carrier separation. Majima’s group claimed that superior electron
transport and enhanced photoreactivity could be realized upon fabricating noble metal (Au, Pt)
transport and enhanced photoreactivity could be realized upon fabricating noble metal (Au, Pt)
nanoparticle-loaded nanoplate-shaped anatase TiO2 mesocrystals [169]. They proposed that most of
the photogenerated electrons could migrate from the dominant surface to the edge of the TiO 2
mesocrystal with the reduction reactions mainly occurring at its lateral surfaces containing (101)
facets, as illustrated by single-molecule fluorescence spectroscopy. The as-fabricated metal-
Catalysts 2019, 9, 91 17 of 27

nanoparticle-loaded nanoplate-shaped anatase TiO2 mesocrystals [169]. They proposed that most
of the photogenerated
Catalysts 2019, 9, x FOR PEERelectrons
REVIEW could migrate from the dominant surface to the edge of the17TiO 2
of 26
mesocrystal with the reduction reactions mainly occurring at its lateral surfaces containing (101) facets,
as illustrated bynanocomposites
semiconductor single-moleculewere fluorescence
found tospectroscopy. The as-fabricated
display significant enhancementmetal-semiconductor
of the photocatalytic
nanocomposites
reaction rate in organic degradation and hydrogen production. More interestingly, by reaction
were found to display significant enhancement of the photocatalytic utilizingrate
Au
in organic degradation
nanorods to modify anatase and hydrogen production. superstructures,
TiO2 mesocrystal More interestingly, by utilizing
highly efficientAu nanorods to
photocatalytic
modify
hydrogen anatase TiO2 mesocrystal
production superstructures,irradiation
under visible-NIR-light highly efficient
couldphotocatalytic
be obtained hydrogen
[179]. Thisproduction
efficient
under
hydrogenvisible-NIR-light
production could irradiation could betoobtained
be attributed the SPR[179].
of AuThis efficient
nanorods hydrogen
which production
injected electronscould
into
be attributed
anatase TiO2 to the SPR of Au
mesocrystals andnanorods whichcharge
the facilitated injectedtransport
electronswithin
into anatase TiO2 mesocrystals
mesocrystal and
particles. Apart
the facilitated charge transport within mesocrystal particles. Apart from the adjustment
from the adjustment of deposited guest particles, it was also demonstrated that efficient defect-state- of deposited
guest
inducedparticles, it was also
hot electron demonstrated
transfer could be that efficient
found in thedefect-state-induced hot electron transfer could
as-prepared Au nanoparticles/reduced TiO2
be found in the
mesocrystal as-prepared Au
photocatalysts, nanoparticles/reduced
which lead to the enhanced TiO2photoreactivity
mesocrystal photocatalysts, which lead
of the photocatalyst in
to the enhanced photoreactivity of the photocatalyst in removing methylene
removing methylene blue (MB) [182]. Most recently, our group evaluated the photoreactivity of the blue (MB) [182]. Most
recently, our group3N
3D/2D DTMC/g-C evaluated the photoreactivity
4 NS heterostructure of the 3D/2D
with chemically DTMC/g-C
bonded 3 N4 NS heterostructure
tight interfaces and found thatwiththe
chemically
as-fabricated bonded tight interfaces
composite and found
photocatalyst that the
displayed as-fabricated
much composite photocatalyst
higher visible-light-driven displayed
photoreactivity
much
toward higher visible-light-driven
removing the pollutantsphotoreactivity
of MO and Cr(VI) toward
thanremoving the pollutants
the corresponding of MOand
DTMCs andg-CCr(VI)
3N4 than
NSs
the corresponding
counterparts DTMCs
(Figure 18)and g-C3 N
[183]. 4 NSs counterparts
Systematic (Figure 18)results
characterization [183]. Systematic
indicated characterization
that such an
results indicated
enhancement thatphotoredox
in the such an enhancement
ability of thein the photoredox
composite ability of the
photocatalyst wascomposite
based onphotocatalyst
the direct Z-
was
schemebased on the
charge direct Z-scheme
separation, charge
as verified separation,
by the as verified
·OH-trapping by the ·OH-trapping experiment.
experiment.

(a)Proposed
Figure 18. (a) ProposedZ-scheme
Z-schemecharge-carrier
charge-carrier transfer
transfer within
within DTMC/g-C
DTMC/g-C 3N43 N 4 composite.
composite. (b)
(b) XPS
XPS valence
valence bandband spectra
spectra and
and (c) (c) schematic
schematic electronic
electronic band structures
band structures of DTMCsof DTMCs
and g-Cand g-C3(d)
3N4 NSs. N4 ·NSs.
OH-
(d) ·OH-trapping
trapping PLofspectra
PL spectra of DTMCs/g-C
DTMCs/g-C 3 Ncorresponding
3N4 and the 4 and the corresponding fluorescence
fluorescence intensity
intensity upon upon
DTMCs/g-
DTMCs/g-C 3 N4 in comparison
C3N4 in comparison to DTMCs.with
to DTMCs. Reprinted Reprinted withfrom
permission permission from [183].
[183]. Copyright Copyright
John Wiley & John
Sons
Wiley & Sons Inc., 2018.
Inc., 2018.

5. Summary and Outlook

5. Summary and Outlook
In this paper, we have summarized some recent progress in fabricating TiO2 mesocrystals, with
In this paper, we have summarized some recent progress in fabricating TiO2 mesocrystals, with
special efforts being directed toward illustrating the underlying mesocrystallization process and its
special efforts being directed toward illustrating the underlying mesocrystallization process and its
controlling rules. Four representative routes toward the fabrication of TiO2 mesocrystals have been
controlling rules. Four representative routes toward the fabrication of TiO2 mesocrystals have been
illustrated: oriented topotactic transformation, growth on substrates, organic-additive-assisted growth
illustrated: oriented topotactic transformation, growth on substrates, organic-additive-assisted
in solution, and direct additive-free synthesis in solution. In line with the flourishing emergence
growth in solution, and direct additive-free synthesis in solution. In line with the flourishing
of reports on the fabrication of TiO2 mesocrystals, the trends of TiO2 mesocrystal synthesis are
emergence of reports on the fabrication of TiO2 mesocrystals, the trends of TiO2 mesocrystal synthesis
always related to the continuous exploitation of synthetic procedures having advantages like low
are always related to the continuous exploitation of synthetic procedures having advantages like low
cost, convenience in handling, and easiness of compositional and structural control. Apart from the
cost, convenience in handling, and easiness of compositional and structural control. Apart from the
fabrication of bare TiO2 mesocrystals, the construction of doped TiO2 mesocrystals, as well as TiO2
fabrication of bare TiO2 mesocrystals, the construction of doped TiO2 mesocrystals, as well as TiO2
mesocrystal-based heterostructures, are both considered to be promising strategies to further enhance
mesocrystal-based heterostructures, are both considered to be promising strategies to further
enhance the performance of TiO2 mesocrystals in various applications, and thus have also been
covered in this review. Taking into account the novel structural characteristics of TiO2 meoscrystals,
such as high crystallinity, high porosity, and oriented nanocrystal assembly, the potential
applications of the resultant TiO2 mesocrystal-based materials in photocatalysis have been discussed
Catalysts 2019, 9, 91 18 of 27

the performance of TiO2 mesocrystals in various applications, and thus have also been covered in this
review. Taking into account the novel structural characteristics of TiO2 meoscrystals, such as high
crystallinity, high porosity, and oriented nanocrystal assembly, the potential applications of the resultant
TiO2 mesocrystal-based materials in photocatalysis have been discussed to gain a deep understanding
of the structure-performance relationships, which can provide useful guidelines for designing and
fabricating highly efficient TiO2 mesocrystal-based photocatalysts for certain applications.
Despite great success having been achieved in the fabrication of TiO2 mesocrystals, the related
mesocrystallization process of TiO2 mesocrystals is still not fully understood, and deserves further
investigation. It remains an ongoing task to figure out the specific reason for the well-ordered alignment
of TiO2 nanocrystal building blocks in certain circumstances and develop facile, reproducible, and
environmentally benign synthetic approaches toward TiO2 mesocrystals with desired morphologies
and architectures. In addition, it should be pointed out that compared with the synthesis of
TiO2 mesocrystals, the application of thus-produced TiO2 mesocrystals in photocatalysis is much
less explored, suggesting the high demand of a deep investigation into TiO2 mesocrystal-based
photocatalysts in various applications. For example, although overall enhancement of photoctalytic
activity of TiO2 mesocrystals has been demonstrated in recent years, the real mechanism for the
photoreactivity enhancement in certain applications has not yet been fully understood. It is a
necessity to thoroughly examine the relationship between the structure and photocatalytic properties
of TiO2 mesocrystals, which can guide the rational design and fabrication of TiO2 mesocrystals with
desired morphologies and architectures to fully satisfy the needs of specific applications in the future.
In addition, the exploration of TiO2 mesocrystal-based photocatalysts in some more challenging
application areas, such as selective CO2 reduction, ammonia synthesis, and methanol activation,
deserves significant research attention to fully excavate their potential in photocatalytic applications.

Author Contributions: J.Y. and X.Y. chose the topic; J.Y., X.Y., B.Z., S.C., M.D., and Y.W. wrote and revised
the article.
Funding: Financial support from National Natural Science Foundation of China (21603079, 21503085), Natural
Science Foundation of Hubei Province (2015CFB175, 2015CFB233), Da Bei Nong Group Promoted Project for Young
Scholar of HZAU (2017DBN010), and Fundamental Research Funds for the Central Universities (2662015QC042)
is gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Keane, D.A.; McGuigan, K.G.; Ibáñez, P.F.; Polo-López, M.I.; Byrne, J.A.; Dunlop, P.S.M.; O’Shea, K.;
Dionysiou, D.D.; Pillai, S.C. Solar photocatalysis for water disinfection: Materials and reactor design. Catal.
Sci. Technol. 2014, 4, 1211–1226. [CrossRef]
2. Spasiano, D.; Marotta, R.; Malato, S.; Fernandez-Ibanez, P.; Somma, I.D. Solar photocatalysis: Materials,
reactors, some commercial and pre-industrialized applications. A comprehensive approach. Appl. Catal.
B Environ. 2015, 170–171, 90–123. [CrossRef]
3. Chen, D.; Zhang, X.; Lee, A.F. Synthetic strategies to nanostructured photocatalysts for CO2 reduction to
solar fuels and chemicals. J. Mater. Chem. A 2015, 3, 14487–14516. [CrossRef]
4. Marszewski, M.; Cao, S.; Yu, J.; Jaroniec, M. Semiconductor-based photocatalytic CO2 conversion. Mater. Horiz.
2015, 2, 261–278. [CrossRef]
5. Chen, S.; Takata, T.; Domen, K. Particulate photocatalysts for overall water splitting. Nat. Rev. Mater. 2017, 2,
17050. [CrossRef]
6. Zhu, S.; Wang, D. Photocatalysis: Basic principles, diverse forms of implementations and emerging scientific
opportunities. Adv. Energy Mater. 2017, 7, 1700841. [CrossRef]
7. Christoforidis, K.C.; Fornasiero, P. Photocatalytic hydrogen production: A rift into the future energy supply.
ChemCatChem 2017, 9, 1523–1544. [CrossRef]
8. Nakata, K.; Fujishima, A. TiO2 photocatalysis: Design and applications. J. Photochem. Photobiol. C
Photochem. Rev. 2012, 13, 169–189. [CrossRef]
Catalysts 2019, 9, 91 19 of 27

9. Lan, Y.; Lu, Y.; Ren, Z. Mini review on photocatalysis of titanium dioxide nanoparticles and their solar
applications. Nano Energy 2013, 2, 1031–1045. [CrossRef]
10. Schneider, J.; Matsuoka, M.; Takeuchi, M.; Zhang, J.; Horiuchi, Y.; Anpo, M.; Bahnemann, D.W. Understanding
TiO2 photocatalysis: Mechanisms and materials. Chem. Rev. 2014, 114, 9919–9986. [CrossRef]
11. Asahi, R.; Morikawa, T.; Irie, H.; Ohwaki, T. Nitrogen-doped titanium dioxide as visible-light-sensitive
photocatalyst: Designs, developments, and prospects. Chem. Rev. 2014, 114, 9824–9852. [CrossRef] [PubMed]
12. Ma, Y.; Wang, X.; Jia, Y.; Chen, X.; Han, H.; Li, C. Titanium dioxide-based nanomaterials for photocatalytic
fuel generations. Chem. Rev. 2014, 114, 9987–10043. [CrossRef] [PubMed]
13. Kapilashrami, M.; Zhang, Y.; Liu, Y.-S.; Hagfeldt, A.; Guo, J. Probing the optical property and electronic
structure of TiO2 nanomaterials for renewable energy applications. Chem. Rev. 2014, 114, 9662–9707.
[CrossRef] [PubMed]
14. Wang, X.; Li, Z.; Shi, J.; Yu, Y. One-dimensional titanium dioxide nanomaterials: Nanowires, nanorods, and
nanobelts. Chem. Rev. 2014, 114, 9346–9384. [CrossRef]
15. Li, W.; Wu, Z.; Wang, J.; Elzatahry, A.A.; Zhao, D. A perspective on mesoporous TiO2 materials. Chem. Mater.
2014, 26, 287–298. [CrossRef]
16. Pelaez, M.; Nolan, N.T.; Pillai, S.C.; Seery, M.K.; Falaras, P.; Kontos, A.G.; Dunlop, P.S.M.; Hamilton, J.W.J.;
Byrne, J.A.; O’Shea, K.; et al. A review on the visible light active titanium dioxide photocatalysts for
environmental applications. Appl. Catal. B Environ. 2012, 125, 331–349. [CrossRef]
17. Park, H.; Park, Y.; Kim, W.; Choi, W. Surface modification of TiO2 photocatalyst for environmental applications.
J. Photochem. Photobiol. C Photochem. Rev. 2013, 15, 1–20. [CrossRef]
18. Zhang, G.; Kim, G.; Choi, W. Visible light driven photocatalysis mediated via ligand-to-metal charge transfer
(LMCT): An alternative approach to solar activation of titania. Energy Environ. Sci. 2014, 7, 954–966.
[CrossRef]
19. Etacheri, V.; Valentin, C.D.; Schneider, J.; Bahnemann, D.; Pillai, S.C. Visible-light activation of TiO2
photocatalysts: Advances in theory and experiments. J. Photochem. Photobiol. C Photochem. Rev. 2015, 25,
1–29. [CrossRef]
20. Gao, M.; Zhu, L.; Ong, W.; Wang, J.; Ho, G.W. Structural design of TiO2 -based photocatalyst for H2 production
and degradation applications. Catal. Sci. Technol. 2015, 5, 4703–4726. [CrossRef]
21. Colmenares, J.C.; Varma, R.S.; Lisowski, P. Sustainable hybrid photocatalysts: Titania immobilized on carbon
materials derived from renewable and biodegradable resources. Green Chem. 2016, 18, 5736–5750. [CrossRef]
22. Zhou, W.; Fu, H. Mesoporous TiO2 : Preparation, doping, and as a composite for photocatalysis. ChemCatChem
2013, 5, 885–894. [CrossRef]
23. Wang, M.; Ioccozia, J.; Sun, L.; Lin, C.; Li, Z. Inorganic-modified semiconductor TiO2 nanotube arrays for
photocatalysis. Energy Environ. Sci. 2014, 7, 2182–2202. [CrossRef]
24. Ola, O.; Maroto-Valer, M.M. Review of material design and reactor engineering on TiO2 photocatalysis for
CO2 reduction. J. Photochem. Photobiol. C Photochem. Rev. 2015, 24, 16–42. [CrossRef]
25. Ge, M.; Li, Q.; Cao, C.; Huang, J.; Li, S.; Zhang, S.; Chen, Z.; Zhang, K.; Al-Deyab, S.S.; Lai, Y. One-dimensional
TiO2 nanotube photocatalysts for solar water splitting. Adv. Sci. 2017, 4, 1600152. [CrossRef]
26. Zhang, X.; Wang, Y.; Liu, B.; Sang, Y.; Liu, H. Heterostructures construction on TiO2 nanobelts: A powerful
tool for building high-performance photocatalysts. Appl. Catal. B Environ. 2017, 202, 620–641. [CrossRef]
27. Mann, S. Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium
and non-equilibrium conditions. Nat. Mater. 2009, 8, 781–792. [CrossRef] [PubMed]
28. Nie, Z.; Petukhova, A.; Kumacheva, E. Properties and emerging applications of self-assembled structures
made from inorganic nanoparticles. Nat. Nanotechnol. 2010, 5, 15–25. [CrossRef]
29. Talapin, D.V.; Lee, J.-S.; Kovalenko, M.V.; Shevchenko, E.V. Prospects of colloidal nanocrystals for electronic
and optoelectronic applications. Chem. Rev. 2010, 110, 389–458. [CrossRef]
30. Liu, J.-W.; Liang, H.-W.; Yu, S.-H. Macroscopic-scale assembled nanowire thin films and their functionalities.
Chem. Rev. 2012, 112, 4770–4799. [CrossRef]
31. Klinkova, A.; Choueiri, R.M.; Kumacheva, E. Self-assembled plasmonic nanostructures. Chem. Soc. Rev.
2014, 43, 3976–3991. [CrossRef]
32. Cargnello, M.; Johnston-Peck, A.C.; Diroll, B.T.; Wong, E.; Datta, B.; Damodhar, D.; Doan-Nguyen, V.V.T.;
Herzing, A.A.; Kagan, C.R.; Murray, C.B. Substitutional doping in nanocrystal superlattices. Nature 2015,
524, 450–455. [CrossRef] [PubMed]
Catalysts 2019, 9, 91 20 of 27

33. Cölfen, H.; Antonietti, M. Mesocrystals: Inorganic superstructures made by highly parallel crystallization
and controlled alignment. Angew. Chem. Int. Ed. 2005, 44, 5576–5591. [CrossRef] [PubMed]
34. Cölfen, H.; Antonietti, M. Mesocrystals and Nonclassical Crystallization; John Wiley & Sons: Chichester,
UK, 2008.
35. Zhou, L.; O’Brien, P. Mesocrystals: A new class of solid materials. Small 2008, 4, 1566–1574. [CrossRef]
[PubMed]
36. Song, R.-Q.; Cölfen, H. Mesocrystals-ordered nanoparticle superstructures. Adv. Mater. 2010, 22, 1301–1330.
[CrossRef]
37. Fang, J.; Ding, B.; Gleiter, H. Mesocrystals: Syntheses in metals and applications. Chem. Soc. Rev. 2011, 40,
5347–5360. [CrossRef] [PubMed]
38. Zhou, L.; O’Brien, P. Mesocrystals-properties and applications. J. Phys. Chem. Lett. 2012, 3, 620–628.
[CrossRef]
39. Uchaker, E.; Cao, G. Mesocrystals as electrode materials for lithium-ion batteries. Nano Today 2014, 9, 499–524.
[CrossRef]
40. Tachikawa, T.; Majima, T. Metal oxide mesocrystals with tailored structures and properties for energy
conversion and storage applications. NPG Asia Mater. 2014, 6, e100. [CrossRef]
41. Bergström, L.; Sturm (née Rosseeva), E.V.; Salazar-Alvarez, G.; Cölfen, H. Mesocrystals in biominerals and
colloidal arrays. Acc. Chem. Res. 2015, 48, 1391–1402. [CrossRef]
42. Zhou, L.; Boyle, D.S.; O’Brien, P. Uniform NH4 TiOF3 mesocrystals prepared by an ambient temperature
self-assembly process and their topotaxial conversion to anatase. Chem. Commun. 2007, 144–146. [CrossRef]
43. Zhou, L.; Smyth-Boyle, D.; O’Brien, P. A facile synthesis of uniform NH4 TiOF3 mesocrystals and their
conversion to TiO2 mesocrystals. J. Am. Chem. Soc. 2008, 130, 1309–1320. [CrossRef] [PubMed]
44. Feng, J.; Yin, M.; Wang, Z.; Yan, S.; Wan, L.; Li, Z.; Zou, Z. Facile synthesis of anatase TiO2 mesocrystal
sheets with dominant {001} facets based on topochemical conversion. CrystEngComm 2010, 12, 3425–3429.
[CrossRef]
45. Inoguchi, M.; Afzaal, M.; Tanaka, N.; O’Brien, P. The poly(ethylene glycol) assisted preparation of NH4 TiOF3
mesocrystals and their topotactic conversion to TiO2 . J. Mater. Chem. 2012, 22, 25123–25129. [CrossRef]
46. Liu, S.-J.; Gong, J.-Y.; Hu, B.; Yu, S.-H. Mesocrystals of rutile TiO2 : Mesoscale transformation, crystallization,
and growth by a biologic molecules-assisted hydrothermal process. Cryst. Growth Des. 2009, 9, 203–209.
[CrossRef]
47. Ye, J.; Liu, W.; Cai, J.; Chen, S.; Zhao, X.; Zhou, H.; Qi, L. Nanoporous anatase TiO2 mesocrystals: Additive-free
synthesis, remarkable crystalline-phase stability, and improved lithium insertion behavior. J. Am. Chem. Soc.
2011, 133, 933–940. [CrossRef] [PubMed]
48. Wang, H.; Liu, Y.; Liu, Z.; Xu, H.; Deng, Y.; Shen, H. Hierarchical rutile TiO2 mesocrystals assembled by
nanocrystals-oriented attachment mechanism. CrystEngComm 2012, 14, 2278–2282. [CrossRef]
49. Zhen, M.; Guo, X.; Gao, G.; Zhou, Z.; Liu, L. Rutile TiO2 nanobundles on reduced graphene oxides as anode
materials for Li ion batteries. Chem. Commun. 2014, 50, 11915–11918. [CrossRef]
50. Wang, H.; Sun, L.; Wang, H.; Xin, L.; Wang, Q.; Liu, Y.; Wang, L. Rutile TiO2 mesocrystallines with aggregated
nanorod clusters: Extremely rapid self-reaction of the single source and enhanced dye-sensitized solar cell
performance. RSC Adv. 2014, 4, 58615–58623. [CrossRef]
51. Fu, X.; Wang, B.; Chen, C.; Ren, Z.; Fan, C.; Wang, Z. Controllable synthesis of spherical anatase mesocrystals
for lithium ion batteries. New J. Chem. 2014, 38, 4754–4759. [CrossRef]
52. Zhou, Y.; Wang, X.; Wang, H.; Song, Y.; Fang, L.; Ye, N.; Wang, L. Enhanced dye-sensitized solar cells
performance using anatase TiO2 mesocrystals with the Wulff construction of nearly 100% exposed {101}
facets as effective light scattering layer. Dalton Trans. 2014, 43, 4711–4719. [CrossRef] [PubMed]
53. Hong, Z.; Zhou, K.; Zhang, J.; Huang, Z.; Wei, M. Facile synthesis of rutile TiO2 mesocrystals with enhanced
sodium storage properties. J. Mater. Chem. A 2015, 3, 17412–17416. [CrossRef]
54. Amarilla, J.M.; Morales, E.; Sanz, J.; Sobrados, I.; Tartaj, P. Electrochemical response in aprotic ionic liquid
electrolytes of TiO2 anatase anodes based on mesoporous mesocrystals with uniform colloidal size. J. Power
Sources 2015, 273, 368–374. [CrossRef]
55. Hong, Z.; Zhou, K.; Huang, Z.; Wei, M. Iso-oriented anatase TiO2 mesocages as a high performance anode
material for sodium-ion storage. Sci. Rep. 2015, 5, 11960. [CrossRef]
Catalysts 2019, 9, 91 21 of 27

56. Wu, D.; Cao, K.; Wang, H.; Wang, F.; Gao, Z.; Xu, F.; Guo, Y.; Jiang, K. Tunable synthesis of single-crystalline-like
TiO2 mesocrystals and their application as effective scattering layer in dye-sensitized solar cells. J. Colloid
Interface Sci. 2015, 456, 125–131. [CrossRef]
57. Wu, Q.; Yang, X.; Zhou, W.; Gao, Q.; Lu, F.; Zhuang, J.; Xu, X.; Wu, M.; Fan, H.J. “Isofacet” anatase TiO2
microcages: Topotactic synthesis and ultrastable Li-ion storage. Adv. Mater. Interfaces 2015, 2, 1500210.
[CrossRef]
58. Hong, Z.; Hong, J.; Xie, C.; Huang, Z.; Wei, M. Hierarchical rutile TiO2 with mesocrystalline structure for
Li-ion and Na-ion storage. Electrochim. Acta 2016, 202, 203–208. [CrossRef]
59. Le, Z.; Liu, F.; Nie, P.; Li, X.; Liu, X.; Bian, Z.; Chen, G.; Wu, H.B.; Lu, Y. Pseudocapacitive sodium storage
in mesoporous single-crystal-like TiO2 -graphene nanocomposite enables high-performance sodium-ion
capacitors. ACS Nano 2017, 11, 2952–2960. [CrossRef] [PubMed]
60. Peng, Y.; Le, Z.; Wen, M.; Zhang, D.; Chen, Z.; Wu, H.B.; Li, H.; Lu, Y. Mesoporous single-crystal-like
TiO2 mesocages threaded with carbon nanotubes for high-performance electrochemical energy storage.
Nano Energy 2017, 35, 44–51. [CrossRef]
61. Hong, Z.; Wei, M.; Lan, T.; Jiang, L.; Cao, G. Additive-free synthesis of unique TiO2 mesocrystals with
enhanced lithium-ion intercalation properties. Energy Environ. Sci. 2012, 5, 5408–5413. [CrossRef]
62. Hong, Z.; Wei, M.; Lan, T.; Cao, G. Self-assembled nanoporous rutile TiO2 mesocrystals with tunable
morphologies for high rate lithium-ion batteries. Nano Energy 2012, 1, 466–471. [CrossRef]
63. Hong, Z.; Xu, Y.; Liu, Y.; Wei, M. Unique ordered TiO2 superstructures with tunable morphology and
crystalline phase for improved lithium storage properties. Chem. Eur. J. 2012, 18, 10753–10760. [CrossRef]
64. Liu, Y.; Che, R.; Chen, G.; Fan, J.; Sun, Z.; Wu, Z.; Wang, M.; Li, B.; Wei, J.; Wei, Y.; et al. Radially oriented
mesoporous TiO2 microspheres with single-crystal–like anatase walls for high-efficiency optoelectronic
devices. Sci. Adv. 2015, 1, e1500166. [CrossRef]
65. Liu, Y.; Luo, Y.; Elzatahry, A.A.; Luo, W.; Che, R.; Fan, J.; Lan, K.; Al-Enizi, A.M.; Sun, Z.; Li, B.; et al.
Mesoporous TiO2 mesocrystals: Remarkable defects-induced crystallite-interface reactivity and their in situ
conversion to single crystals. ACS Cent. Sci. 2015, 1, 400–408. [CrossRef] [PubMed]
66. Cai, J.; Ye, J.; Chen, S.; Zhao, X.; Zhang, D.; Chen, S.; Ma, Y.; Jin, S.; Qi, L. Self-cleaning, broadband and
quasi-omnidirectional antireflective structures based on mesocrystalline rutile TiO2 nanorod arrays. Energy
Environ. Sci. 2012, 5, 7575–7581. [CrossRef]
67. Dai, H.; Zhang, S.; Hong, Z.; Li, X.; Xu, G.; Lin, Y.; Chen, G. Enhanced photoelectrochemical activity of a
hierarchical-ordered TiO2 mesocrystal and its sensing application on a carbon nanohorn support scaffold.
Anal. Chem. 2014, 86, 6418–6424. [CrossRef]
68. Dai, H.; Zhang, S.; Gong, L.; Li, Y.; Xu, G.; Lin, Y.; Hong, Z. The photoelectrochemical exploration of
multifunctional TiO2 mesocrystals and its enzyme-assisted biosensing application. Biosens. Bioelectron. 2015,
72, 18–24. [CrossRef]
69. Li, Z.; Gessner, A.; Richters, J.-P.; Kalden, J.; Voss, T.; Kuebel, C.; Taubert, A. Hollow zinc oxide mesocrystals
from an ionic liquid precursor (ILP). Adv. Mater. 2008, 20, 1279–1285. [CrossRef]
70. Liu, Z.; Wen, X.D.; Wu, X.L.; Gao, Y.J.; Chen, H.T.; Zhu, J.; Chu, P.K. Intrinsic dipole-field-driven mesoscale
crystallization of core-shell ZnO mesocrystal microspheres. J. Am. Chem. Soc. 2009, 131, 9405–9412.
[CrossRef]
71. Wu, X.L.; Xiong, S.J.; Liu, Z.; Chen, J.; Shen, J.C.; Li, T.H.; Wu, P.H.; Chu, P.K. Green light stimulates terahertz
emission from mesocrystal microspheres. Nat. Nanotechnol. 2011, 6, 103–106. [CrossRef]
72. Distaso, M.; Klupp Taylor, R.N.; Taccardi, N.; Wasserscheid, P.; Peukert, W. Influence of the counterion on the
synthesis of ZnO mesocrystals under solvothermal conditions. Chem. Eur. J. 2011, 17, 2923–2930. [CrossRef]
[PubMed]
73. Distaso, M.; Segets, D.; Wernet, R.; Taylor, R.K.; Peukert, W. Tuning the size and the optical properties of
ZnO mesocrystals synthesized under solvothermal conditions. Nanoscale 2012, 4, 864–873. [CrossRef]
74. Hosono, E.; Tokunaga, T.; Ueno, S.; Oaki, Y.; Imai, H.; Zhou, H.; Fujihara, S. Crystal growth process of
single-crystal-like mesoporous ZnO through a competitive reaction in solution. Cryst. Growth Des. 2012, 12,
2923–2931. [CrossRef]
75. Liu, M.-H.; Tseng, Y.-H.; Greer, H.F.; Zhou, W.; Mou, C.-Y. Dipole field guided orientated attachment of
nanocrystals to twin-brush ZnO mesocrystals. Chem. Eur. J. 2012, 18, 16104–16113. [CrossRef] [PubMed]
Catalysts 2019, 9, 91 22 of 27

76. Sun, S.; Zhang, X.; Zhang, J.; Song, X.; Yang, Z. Unusual designated-tailoring on zone-axis preferential
growth of surfactant-free ZnO mesocrystals. Cryst. Growth Des. 2012, 12, 2411–2418. [CrossRef]
77. Waltz, F.; Wissmann, G.; Lippke, J.; Schneider, A.M.; Schwarz, H.-C.; Feldhoff, A.; Eiden, S.; Behrens, P.
Evolution of the morphologies of zinc oxide mesocrystals under the influence of natural polysaccharides.
Cryst. Growth Des. 2012, 12, 3066–3075. [CrossRef]
78. Wang, H.; Xin, L.; Wang, H.; Yu, X.; Liu, Y.; Zhou, X.; Li, B. Aggregation-induced growth of hexagonal
ZnO hierarchical mesocrystals with interior space: Nonaqueous synthesis, growth mechanism, and optical
properties. RSC Adv. 2013, 3, 6538–6544. [CrossRef]
79. Wang, S.-S.; Xu, A.-W. Template-free facile solution synthesis and optical properties of ZnO mesocrystals.
Cryst. Eng. Commun. 2013, 15, 376–381. [CrossRef]
80. Peng, Y.; Wang, Y.; Chen, Q.-G.; Zhu, Q.; Xu, A.W. Stable yellow ZnO mesocrystals with efficient visible-light
photocatalytic activity. CrystEngComm 2014, 16, 7906–7913. [CrossRef]
81. Liu, J.; Hu, Z.-Y.; Peng, Y.; Huang, H.-W.; Li, Y.; Wu, M.; Ke, X.-X.; Tendeloo, G.V.; Su, B.-L. 2D ZnO
mesoporous single-crystal nanosheets with exposed {0001} polar facets for the depollution of cationic dye
molecules by highly selective adsorption and photocatalytic decomposition. Appl. Catal. B Environ. 2016,
181, 138–145. [CrossRef]
82. Liu, M.-H.; Chen, Y.-W.; Liu, X.; Kuo, J.-L.; Chu, M.-W.; Mou, C.-Y. Defect-mediated gold substitution doping
in ZnO mesocrystals and catalysis in CO oxidation. ACS Catal. 2016, 6, 115–122. [CrossRef]
83. Wang, H.; Wang, C.; Chen, Q.; Ren, B.; Guan, R.; Cao, X.; Yang, X.; Duan, R. Interface-defect-mediated
photocatalysis of mesocrystalline ZnO assembly synthesized in-situ via a template-free hydrothermal
approach. Appl. Surf. Sci. 2017, 412, 517–528. [CrossRef]
84. Liu, M.-H.; Chen, Y.-W.; Lin, T.-S.; Mou, C.-Y. Defective mesocrystal ZnO-supported gold catalysts: Facilitating
CO oxidation via vacancy defects in ZnO. ACS Catal. 2018, 8, 6862–6869. [CrossRef]
85. Liang, S.; Gou, X.; Cui, J.; Luo, Y.; Qu, H.; Zhang, T.; Yang, Z.; Yang, Q.; Sun, S. Novel cone-like ZnO
mesocrystals with coexposed (10-11) and (000-1) facets and enhanced photocatalytic activity. Inorg. Chem.
Front. 2018, 5, 2257–2267. [CrossRef]
86. Park, G.-S.; Shindo, D.; Waseda, Y.; Sugimoto, T. Internal structure analysis of monodispersed pseudocubic
hematite particles by electron microscopy. J. Colloid Interface Sci. 1996, 177, 198–207. [CrossRef]
87. Ahniyaz, A.; Sakamoto, Y.; Bergström, L. Magnetic field-induced assembly of oriented superlattices from
maghemite nanocubes. Proc. Natl. Acad. Sci. USA 2007, 104, 17570–17574. [CrossRef]
88. Fang, X.-L.; Chen, C.; Jin, M.-S.; Kuang, Q.; Xie, Z.-X.; Xie, S.-Y.; Huang, R.-B.; Zheng, L.-S. Single-crystal-like
hematite colloidal nanocrystal clusters: Synthesis and applications in gas sensors, photocatalysis and water
treatment. J. Mater. Chem. 2009, 19, 6154–6160. [CrossRef]
89. An, Z.; Zhang, J.; Pan, S.; Yu, F. Facile template-free synthesis and characterization of elliptic a-Fe2 O3
superstructures. J. Phys. Chem. C 2009, 113, 8092–8096. [CrossRef]
90. Chen, J.S.; Zhu, T.; Li, C.M.; Lou, X.W. Building hematite nanostructures by oriented attachment. Angew.
Chem. Int. Ed. 2011, 50, 650–653. [CrossRef]
91. Ma, J.; Teo, J.; Mei, L.; Zhong, Z.; Li, Q.; Wang, T.; Duan, X.; Lian, J.; Zheng, W. Porous platelike hematite
mesocrystals: Synthesis, catalytic and gas-sensing applications. J. Mater. Chem. 2012, 22, 11694–11700.
[CrossRef]
92. Duan, X.; Mei, L.; Ma, J.; Li, Q.; Wang, T.; Zheng, W. Facet-induced formation of hematite mesocrystals with
improved lithium storage properties. Chem. Commun. 2012, 48, 12204–12206. [CrossRef]
93. Fei, X.; Li, W.; Shao, Z.; Seeger, S.; Zhao, D.; Chen, X. Protein biomineralized nanoporous inorganic
mesocrystals with tunable hierarchical nanostructures. J. Am. Chem. Soc. 2014, 136, 15781–15786. [CrossRef]
94. Cai, J.; Chen, S.; Ji, M.; Hu, J.; Ma, Y.; Qi, L. Organic additive-free synthesis of mesocrystalline hematite
nanoplates via two-dimensional oriented attachment. CrystEngComm 2014, 16, 1553–1559. [CrossRef]
95. Agthe, M.; Plivelic, T.S.; Labrador, A.; Bergström, L.; Salazar-Alvarez, G. Following in real time the two-step
assembly of nanoparticles into mesocrystals in levitating drops. Nano Lett. 2016, 16, 6838–6843. [CrossRef]
96. Liu, B.; Zeng, H.C. Mesoscale organization of CuO nanoribbons: Formation of “dandelions”. J. Am. Chem. Soc.
2004, 126, 8124–8125. [CrossRef]
97. Yao, W.-T.; Yu, S.-H.; Zhou, Y.; Jiang, J.; Wu, Q.-S.; Zhang, L.; Jiang, J. Formation of uniform CuO nanorods by
spontaneous aggregation: Selective synthesis of CuO, Cu2 O, and Cu nanoparticles by a solid-liquid phase
arc discharge process. J. Phys. Chem. B 2005, 109, 14011–14016. [CrossRef]
Catalysts 2019, 9, 91 23 of 27

98. Xu, M.; Wang, F.; Ding, B.; Song, X.; Fang, J. Electrochemical synthesis of leaf-like CuO mesocrystals and
their lithium storage properties. RSC Adv. 2012, 2, 2240–2243. [CrossRef]
99. Jia, B.; Qin, M.; Zhang, Z.; Cao, Z.; Wu, H.; Chen, P.; Zhang, L.; Lu, X.; Qu, X. The formation of CuO porous
mesocrystal ellipsoids via tuning the oriented attachment mechanism. CrystEngComm 2016, 18, 1376–1383.
[CrossRef]
100. Zhang, J.; Cui, Y.; Qin, Q.; Zhang, G.; Luo, W.; Zheng, W. Nanoporous CuO mesocrystals: Low-temperature
synthesis and improved structure-performance relationship for energy storage system. Chem. Eng. J. 2018,
331, 326–334. [CrossRef]
101. Hu, J.; Zou, C.; Su, Y.; Li, M.; Han, Y.; Kong, E.S.-W.; Yang, Z.; Zhang, Y. Ultrasensitive NO2 gas sensor based
on hierarchical Cu2 O/CuO mesocrystals nanoflower. J. Mater. Chem. A 2018, 6, 17120–17131. [CrossRef]
102. Zhao, J.; Tan, R.; Guo, Y.; Lu, Y.; Xu, W.; Song, W. SnO mesocrystals: Additive-free synthesis, oxidation, and
top-down fabrication of quantum dots. CrystEngComm 2012, 14, 4575–4577. [CrossRef]
103. Chen, S.; Wang, M.; Ye, J.; Cai, J.; Ma, Y.; Zhou, H.; Qi, L. Kinetics-controlled growth of aligned mesocrystalline
SnO2 nanorod arrays for lithium-ion batteries with superior rate performance. Nano Research 2013, 6, 243–252.
[CrossRef]
104. Liu, Y.; Zhu, G.; Ge, B.; Zhou, H.; Yuan, A.; Shen, X. Concave Co3 O4 octahedral mesocrystal: Polymer-mediated
synthesis and sensing properties. CrystEngComm 2012, 14, 6264–6270. [CrossRef]
105. Wang, F.; Lu, C.; Qin, Y.; Liang, C.; Zhao, M.; Yang, S.; Sun, Z.; Song, X. Solid state coalescence growth and
electrochemical performance of plate-like Co3 O4 mesocrystals as anode materials for lithium-ion batteries. J.
Power Sources 2013, 235, 67–73. [CrossRef]
106. Su, D.; Dou, S.; Wang, G. Mesocrystal Co3 O4 nanoplatelets as high capacity anode materials for Li-ion
batteries. Nano Res. 2014, 7, 794–803. [CrossRef]
107. Hassen, D.; El-Safty, S.A.; Tsuchiya, K.; Chatterjee, A.; Elmarakbi, A.; Shenashen, M.A.; Sakai, M. Longitudinal
hierarchy Co3 O4 mesocrystals with high-dense exposure facets and anisotropic interfaces for direct-ethanol
fuel cells. Sci. Rep. 2016, 6, 24330. [CrossRef]
108. Cao, W.; Wang, W.; Shi, H.; Wang, J.; Cao, M.; Liang, Y.; Zhu, M. Hierarchical three-dimensional flower-like
Co3 O4 architectures with a mesocrystal structure as high capacity anode materials for long-lived lithium-ion
batteries. Nano Res. 2018, 11, 1437–1446. [CrossRef]
109. Fang, J.; Leufke, P.M.; Kruk, R.; Wang, D.; Scherer, T.; Hahn, H. External electric field driven 3D ordering
architecture of silver (I) oxide meso-superstructures. Nano Today 2010, 5, 175–182. [CrossRef]
110. Belman, N.; Israelachvili, J.N.; Li, Y.; Safinya, C.R.; Ezersky, V.; Rabkin, A.; Sima, O.; Golan, Y. Hierarchical
superstructure of alkylamine-coated ZnS nanoparticle assemblies. Phys. Chem. Chem. Phys. 2011, 13,
4974–4979. [CrossRef]
111. Querejeta-Fernandez, A.; Hernandez-Garrido, J.C.; Yang, H.; Zhou, Y.; Varela, A.; Parras, M.;
Calvino-Gamez, J.J.; Gonzalez-Calbet, J.M.; Green, P.F.; Kotov, N.A. Unknown aspects of self-assembly of
PbS microscale superstructures. ACS Nano 2012, 6, 3800–3812. [CrossRef]
112. Simon, P.; Rosseeva, E.; Baburin, I.A.; Liebscher, L.; Hickey, S.G.; Cardoso-Gil, R.; Eychmüller, A.; Kniep, R.;
Carrillo-Cabrera, W. PbS-organic mesocrystals: The relationship between nanocrystal orientation and
superlattice array. Angew. Chem. Int. Ed. 2012, 51, 10776–10781. [CrossRef]
113. Simon, P.; Bahrig, L.; Baburin, I.A.; Formanek, P.; Röder, F.; Sickmann, J.; Hickey, S.G.; Eychmüller, A.;
Lichte, H.; Kniep, R.; et al. Interconnection of nanoparticles within 2D superlattices of PbS/oleic acid thin
films. Adv. Mater. 2014, 26, 3042–3049. [CrossRef]
114. De la Rica, R.; Velders, A.H. Biomimetic crystallization of Ag2 S nanoclusters in nanopore assemblies. J. Am.
Chem. Soc. 2011, 133, 2875–2877. [CrossRef] [PubMed]
115. Nagaoka, Y.; Chen, O.; Wang, Z.; Cao, Y.C. Structural control of nanocrystal superlattices using organic guest
molecules. J. Am. Chem. Soc. 2012, 134, 2868–2871. [CrossRef] [PubMed]
116. Soejima, T.; Kimizuka, N. One-pot room-temperature synthesis of single-crystalline gold nanocorolla in
water. J. Am. Chem. Soc. 2009, 131, 14407–14412. [CrossRef]
117. Fang, J.; Du, S.; Lebedkin, S.; Li, Z.; Kruk, R.; Kappes, M.; Hahn, H. Gold mesostructures with tailored surface
topography and their self-assembly arrays for surface-enhanced raman spectroscopy. Nano Lett. 2010, 10,
5006–5013. [CrossRef]
Catalysts 2019, 9, 91 24 of 27

118. You, H.; Ji, Y.; Wang, L.; Yang, S.; Yang, Z.; Fang, J.; Song, X.; Ding, B. Interface synthesis of gold mesocrystals
with highly roughened surfaces for surface-enhanced Raman spectroscopy. J. Mater. Chem. 2012, 22,
1998–2006. [CrossRef]
119. Fang, J.; Ding, B.; Song, X. Self-assembly mechanism of platelike silver mesocrystal. Appl. Phys. Lett. 2007,
91, 083108. [CrossRef]
120. Cao, Y.; Fan, J.; Bai, L.; Hu, P.; Yang, G.; Yuan, F.; Chen, Y. Formation of cubic Cu mesocrystals by a
solvothermal reaction. CrystEngComm 2010, 12, 3894–3899. [CrossRef]
121. Li, T.; You, H.; Xu, M.; Song, X.; Fang, J. Electrocatalytic properties of hollow coral-like platinum mesocrystals.
ACS Appl. Mater. Interfaces 2012, 4, 6942–6948. [CrossRef]
122. Zhong, P.; Liu, H.; Zhang, J.; Yin, Y.; Gao, C. Controlled Synthesis of octahedral platinum-based mesocrystals
by oriented aggregation. Chem. Eur. J. 2017, 23, 6803–6810. [CrossRef] [PubMed]
123. Huang, X.; Tang, S.; Yang, J.; Tan, Y.; Zheng, N. Etching growth under surface confinement: An effective
strategy to prepare mesocrystalline Pd nanocorolla. J. Am. Chem. Soc. 2011, 133, 15946–15949. [CrossRef]
[PubMed]
124. Cai, J.; Qi, L. TiO2 mesocrystals: Synthesis, formation mechanisms and applications. Sci. China Chem. 2012,
55, 2318–2326. [CrossRef]
125. Hong, Z.; Wei, M. Recent progress in preparation and lithium-ion storage properties of TiO2 mesocrystals.
J. Chin. Chem. Soc. 2015, 62, 209–216. [CrossRef]
126. Zhang, P.; Tachikawa, T.; Fujitsuka, M.; Majima, T. The development of functional mesocrystals for energy
harvesting, storage, and conversion. Chem. Eur. J. 2018, 24, 6295–6307. [CrossRef]
127. Li, L.; Liu, C.-Y. Organic small molecule-assisted synthesis of high active TiO2 rod-like mesocrystals.
CrystEngComm 2010, 12, 2073–2078. [CrossRef]
128. Zhang, D.; Li, G.; Wang, F.; Yu, J.C. Green synthesis of a self-assembled rutile mesocrystalline photocatalyst.
CrystEngComm 2010, 12, 1759–1763. [CrossRef]
129. Liu, X.; Gao, Y.; Cao, C.; Luo, H.; Wang, W. Highly crystalline spindle-shaped mesoporous anatase titania
particles: Solution-phase synthesis, characterization, and photocatalytic properties. Langmuir 2010, 26,
7671–7674. [CrossRef]
130. Bian, Z.; Zhu, J.; Wen, J.; Cao, F.; Huo, Y.; Qian, X.; Cao, Y.; Shen, M.; Li, H.; Lu, Y. Single-crystal-like titania
mesocages. Angew. Chem. Int. Ed. 2011, 123, 1137–1140. [CrossRef]
131. Da Silva, R.O.; Gonçalves, R.H.; Stroppa, D.G.; Ramirez, A.J.; Leite, E.R. Synthesis of recrystallized anatase
TiO2 mesocrystals with Wulff shape assisted by oriented attachment. Nanoscale 2011, 3, 1910–1916. [CrossRef]
132. Tartaj, P. Sub-100 nm TiO2 mesocrystalline assemblies with mesopores: Preparation, characterization, enzyme
immobilization and photocatalytic properties. Chem. Commun. 2011, 47, 256–258. [CrossRef]
133. Tartaj, P.; Amarilla, J.M. Multifunctional response of anatase nanostructures based on 25 nm mesocrystal-like
porous assemblies. Adv. Mater. 2011, 23, 4904–4907. [CrossRef]
134. Jiao, W.; Wang, L.; Liu, G.; Lu, G.Q.; Cheng, H.-M. Hollow anatase TiO2 single crystals and mesocrystals
with dominant {101} facets for improved photocatalysis activity and tuned reaction preference. ACS Catal.
2012, 2, 1854–1859. [CrossRef]
135. Bian, Z.; Tachikawa, T.; Majima, T. Superstructure of TiO2 crystalline nanoparticles yields effective conduction
pathways for photogenerated charges. J. Phys. Chem. Lett. 2012, 3, 1422–1427. [CrossRef]
136. Chen, Q.; Ma, W.; Chen, C.; Ji, H.; Zhao, J. Anatase TiO2 mesocrystals enclosed by (001) and (101) facets:
Synergistic effects between Ti3+ and facets for their photocatalytic performance. Chem. Eur. J. 2012, 18,
12584–12589. [CrossRef]
137. Liu, Y.; Zhang, Y.; Li, H.; Wang, J. Manipulating the formation of NH4 TiOF3 mesocrystals: Effects of
temperature, surfactant, and pH. Cryst. Growth Des. 2012, 12, 2625–2633. [CrossRef]
138. Aoyama, Y.; Oaki, Y.; Ise, R.; Imai, H. Mesocrystal nanosheet of rutile TiO2 and its reaction selectivity as a
photocatalyst. CrystEngComm 2012, 14, 1405–1411. [CrossRef]
139. Zhou, L.; Chen, J.; Ji, C.; Zhou, L.; O’Brien, P. A facile solid phase reaction to prepare TiO2 mesocrystals with
exposed {001} facets and high photocatalytic activity. CrystEngComm 2013, 15, 5012–5015. [CrossRef]
140. Yao, X.; Liu, X.; Liu, T.; Wang, K.; Lu, L. One-step and large-scale synthesis of anatase TiO2 mesocrystals
along [001] orientation with enhanced photocatalytic performance. CrystEngComm 2013, 15, 10246–10254.
[CrossRef]
Catalysts 2019, 9, 91 25 of 27

141. Guo, Y.; Li, H.; Chen, J.; Wu, X.; Zhou, L. TiO2 mesocrystals built of nanocrystals with exposed {001} facets:
Facile synthesis and superior photocatalytic ability. J. Mater. Chem. A 2014, 2, 19589–19593. [CrossRef]
142. Chen, J.; Li, G.; Zhang, H.; Liu, P.; Zhao, H.; An, T. Anatase TiO2 mesocrystals with exposed (001) surface for
enhanced photocatalytic decomposition capability toward gaseous styrene. Catal. Today 2014, 224, 216–224.
[CrossRef]
143. Fang, Z.; Long, L.; Hao, S.; Song, Y.; Qiang, T.; Geng, B. Mesocrystal precursor transformation strategy
for synthesizing ordered hierarchical hollow TiO2 nanobricks with enhanced photocatalytic property.
CrystEngComm 2014, 16, 2061–2069. [CrossRef]
144. Lai, L.-L.; Huang, L.-L.; Wu, J.-M. K2 TiO(C2 O4 )2 -mediated synthesis of rutile TiO2 mesocrystals and their
ability to assist photodegradation of sulfosalicylic acid in water. RSC Adv. 2014, 4, 49280–49286. [CrossRef]
145. Zhang, P.; Tachikawa, T.; Bian, Z.; Majima, T. Selective photoredox activity on specific facet-dominated TiO2
mesocrystal superstructures incubated with directed nanocrystals. Appl. Catal. B 2015, 176–177, 678–686.
[CrossRef]
146. Hu, D.; Zhang, W.; Tanaka, Y.; Kusunose, N.; Peng, Y.; Feng, Q. Mesocrystalline nanocomposites of TiO2
polymorphs: Topochemical mesocrystal conversion, characterization, and photocatalytic response. Cryst.
Growth Des. 2015, 15, 1214–1225. [CrossRef]
147. Fu, X.X.; Ren, Z.M.; Fan, C.Y.; Sun, C.X.; Shi, L.; Yu, S.Q.; Qian, G.D.; Wang, Z.Y. Designed fabrication of
anatase mesocrystals constructed from crystallographically oriented nanocrystals for improved photocatalytic
activity. RSC Adv. 2015, 5, 41218–41223. [CrossRef]
148. Lai, L.-L.; Wu, J.-M. Hollow TiO2 microspheres assembled with rutile mesocrystals: Low-temperature
one-pot synthesis and the photocatalytic performance. Ceram. Int. 2015, 41, 12317–12322. [CrossRef]
149. Fu, X.; Fan, C.; Yu, S.; Shi, L.; Wang, Z. TiO2 mesocrystals with exposed {001} facets as efficient photocatalysts.
J. Alloys Compd. 2016, 680, 80–86. [CrossRef]
150. Tan, B.; Zhang, X.; Li, Y.; Chen, H.; Ye, X.; Wang, Y.; Ye, J. Anatase TiO2 mesocrystals: Green synthesis, in situ
conversion to porous single crystals, and self-doping Ti3+ for enhanced visible light driven photocatalytic
removal of NO. Chem. Eur. J. 2017, 23, 5478–5487. [CrossRef]
151. Tang, C.; Liu, L.; Li, Y.; Bian, Z. Aerosol spray assisted assembly of TiO2 mesocrystals into hierarchical hollow
microspheres with enhanced photocatalytic performance. Appl. Catal. B 2017, 201, 41–47. [CrossRef]
152. Wang, H.; Chen, Q.; Luan, Q.; Duan, R.; Guan, R.; Cao, X.; Hu, X. Photocatalytic properties dependent on the
interfacial defects of intergrains within TiO2 mesocrystals. Chem. Eur. J. 2018, 24, 17105–17116. [CrossRef]
[PubMed]
153. Hong, Z.; Dai, H.; Huang, Z.; Wei, M. Understanding the growth and photoelectrochemical properties of
mesocrystals and single crystals: A case of anatase TiO2 . Phys. Chem. Chem. Phys. 2014, 16, 7441–7447.
[CrossRef] [PubMed]
154. Zhang, Y.; Cai, J.; Ma, Y.; Qi, L. Mesocrystalline TiO2 nanosheet arrays with exposed {001} facets: Synthesis
via topotactic transformation and applications in dye-sensitized solar cells. Nano Res. 2017, 10, 2610–2625.
[CrossRef]
155. Liu, B.; Zeng, H.C. Carbon nanotubes supported mesoporous mesocrystals of anatase TiO2 . Chem. Mater.
2008, 20, 2711–2718. [CrossRef]
156. Li, N.; Liu, G.; Zhen, C.; Li, F.; Zhang, L.; Cheng, H.-M. Battery performance and photocatalytic activity of
mesoporous anatase TiO2 nanospheres/graphene composites by template-free self-assembly. Adv. Funct.
Mater. 2011, 21, 1717–1722. [CrossRef]
157. Zhang, W.; Shen, D.; Liu, Z.; Wu, N.-L.; Wei, M. Brookite TiO2 mesocrystals with enhanced lithium-ion
intercalation properties. Chem. Commun. 2018, 54, 11491–11494. [CrossRef]
158. Elbanna, O.; Zhang, P.; Fujitsuka, M.; Majima, T. Facile preparation of nitrogen and fluorine codoped TiO2
mesocrystal with visible light photocatalytic activity. Appl. Catal. B 2016, 192, 80–87. [CrossRef]
159. Zhang, P.; Fujitsuka, M.; Majima, T. TiO2 mesocrystal with nitrogen and fluorine codoping during
topochemical transformation: Efficient visible light induced photocatalyst with the codopants. Appl.
Catal. B 2016, 185, 181–188. [CrossRef]
160. Primc, D.; Niederberger, M. Synthesis and formation mechanism of multicomponent Sb-Nb:TiO2 mesocrystals.
Chem. Mater. 2017, 29, 10113–10121. [CrossRef]
161. Lan, T.; Zhang, W.; Wu, N.-L.; Wei, M. Nb-doped rutile TiO2 mesocrystals with enhanced lithium storage
properties for lithium ion battery. Chem. Eur. J. 2017, 23, 5059–5065. [CrossRef]
Catalysts 2019, 9, 91 26 of 27

162. Naldoni, A.; Allieta, M.; Santangelo, S.; Marelli, M.; Fabbri, F.; Cappelli, S.; Bianchi, C.L.; Psaro, R.; Santo, V.D.
Effect of nature and location of defects on bandgap narrowing in black TiO2 nanoparticles. J. Am. Chem. Soc.
2012, 134, 7600–7603. [CrossRef] [PubMed]
163. Pan, X.; Yang, M.-Q.; Fu, X.; Zhang, N.; Xu, Y.-J. Defective TiO2 with oxygen vacancies: Synthesis, properties
and photocatalytic applications. Nanoscale 2013, 5, 3601–3614. [CrossRef] [PubMed]
164. Chen, X.; Liu, L.; Huang, F. Black titanium dioxide (TiO2 ) nanomaterials. Chem. Soc. Rev. 2015, 44, 1861–1885.
[CrossRef]
165. Ullattil, S.G.; Narendranath, S.B.; Pillai, S.C.; Periyat, P. Black TiO2 nanomaterials: A review of recent
advances. Chem. Eng. J. 2018, 343, 708–736. [CrossRef]
166. Zhou, W.; Fu, H. Defect-mediated electron-hole separation in semiconductor photocatalysis. Inorg. Chem.
Front. 2018, 5, 1240–1254. [CrossRef]
167. Chen, X.; Liu, L.; Yu, P.Y.; Mao, S.S. Increasing solar absorption for photocatalysis with black hydrogenated
titanium dioxide nanocrystals. Science 2011, 331, 746–750. [CrossRef] [PubMed]
168. Elbanna, O.; Fujitsuka, M.; Kim, S.; Majima, T. Charge carrier dynamics in TiO2 mesocrystals with oxygen
vacancies for photocatalytic hydrogen generation under solar light irradiation. J. Phys. Chem. C 2018, 122,
15163–15170. [CrossRef]
169. Bian, Z.; Tachikawa, T.; Kim, W.; Choi, W.; Majima, T. Superior electron transport and photocatalytic abilities
of metal-nanoparticle-loaded TiO2 superstructures. J. Phys. Chem. C 2012, 116, 25444–25453. [CrossRef]
170. Gao, P.; Liu, J.; Zhang, T.; Sun, D.D.; Ng, W. Hierarchical TiO2 /CdS “spindle-like” composite with high
photodegradation and antibacterial capability under visible light irradiation. J. Hazard. Mater. 2012, 229–230,
209–216. [CrossRef]
171. Yang, X.; Qin, J.; Li, Y.; Zhang, R.; Tang, H. Graphene-spindle shaped TiO2 mesocrystal composites: Facile
synthesis and enhanced visible light photocatalytic performance. J. Hazard. Mater. 2013, 261, 342–350.
[CrossRef]
172. Bian, Z.; Tachikawa, T.; Zhang, P.; Fujitsuka, M.; Majima, T. Au/TiO2 superstructure-based plasmonic
photocatalysts exhibiting efficient charge separation and unprecedented activity. J. Am. Chem. Soc. 2014, 136,
458–465. [CrossRef] [PubMed]
173. Tachikawa, T.; Zhang, P.; Bian, Z.; Majima, T. Efficient charge separation and photooxidation on cobalt
phosphate-loaded TiO2 mesocrystal superstructures. J. Mater. Chem. A 2014, 2, 3381–3388. [CrossRef]
174. Zhang, P.; Tachikawa, T.; Fujitsuka, M.; Majima, T. Efficient charge separation on 3D architectures of
TiO2 mesocrystals packed with a chemically exfoliated MoS2 shell in synergetic hydrogen evolution.
Chem. Commun. 2015, 51, 7187–7190. [CrossRef]
175. Li, X.; Wang, J.; Men, Y.; Bian, Z. TiO2 mesocrystal with exposed (001) facets and CdS quantum dots as an
active visible photocatalyst for selective oxidation reactions. Appl. Catal. B 2016, 187, 115–121. [CrossRef]
176. Han, T.; Wang, H.; Zheng, X. Gold nanoparticle incorporation into nanoporous anatase TiO2 mesocrystal
using a simple deposition-precipitation method for photocatalytic applications. RSC Adv. 2016, 6, 7829–7837.
[CrossRef]
177. Yan, D.; Liu, Y.; Liu, C.-Y.; Zhang, Z.-Y.; Niea, S.-D. Multi-component in situ and in-step formation of
visible-light response C-dots composite TiO2 mesocrystals. RSC Adv. 2016, 6, 14306–14313. [CrossRef]
178. Tang, H.; Chang, S.; Jiang, L.; Tang, G.; Liang, W. Novel spindle-shaped nanoporous TiO2 coupled graphitic
g-C3 N4 nanosheets with enhanced visible-light photocatalytic activity. Ceram. Int. 2016, 42, 18443–18452.
[CrossRef]
179. Elbanna, O.; Kim, S.; Fujitsuka, M.; Majima, T. TiO2 mesocrystals composited with gold nanorods for highly
efficient visible-NIR-photocatalytic hydrogen production. Nano Energy 2017, 35, 1–8. [CrossRef]
180. Elbanna, O.; Fujitsuka, M.; Majima, T. g-C3 N4 /TiO2 mesocrystals composite for H2 evolution under
visible-light irradiation and its charge carrier dynamics. ACS Appl. Mater. Interfaces 2017, 9, 34844–34854.
[CrossRef]
181. Yu, X.; Fan, X.; An, L.; Liu, G.; Li, Z.; Liu, J.; Hu, P.A. Mesocrystalline Ti3+ -TiO2 hybridized g-C3 N4 for
efficient visible-light photocatalysis. Carbon 2018, 128, 21–30. [CrossRef]
182. Xue, J.; Elbanna, O.; Kim, S.; Fujitsuka, M.; Majima, T. Defect state-induced efficient hot electron transfer in
Au nanoparticles/reduced TiO2 mesocrystal photocatalysts. Chem. Commun. 2018, 54, 6052–6055. [CrossRef]
Catalysts 2019, 9, 91 27 of 27

183. Tan, B.; Ye, X.; Li, Y.; Ma, X.; Wang, Y.; Ye, J. Defective anatase TiO2-x mesocrystal growth in situ on g-C3 N4
nanosheets: Construction of 3D/2D Z-scheme heterostructures for highly efficient visible-light photocatalysis.
Chem. Eur. J. 2018, 24, 13311–13321. [CrossRef]
184. Chen, F.; Cao, F.; Li, H.; Bian, Z. Exploring the important role of nanocrystals orientation in TiO2 superstructure
on photocatalytic performances. Langmuir 2015, 31, 3494–3499. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).