Journal of Alloys and Compounds 769 (2018) 740e757

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Review

TiO2 inverse opal photonic crystals: Synthesis, modification, and

applications - A review
Jie Yu a, Juying Lei a, **, Lingzhi Wang b, Jinlong Zhang b, *, Yongdi Liu a, c, ***
a
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and
Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, PR China
b
Key Lab for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and
Technology, Shanghai, 200237, PR China
c
Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, PR China

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

Article history: TiO2 inverse opal photonic crystal (TiO2 IO PCs) that possesses the advantages of titanium dioxide
Received 6 May 2018 including non-toxicity, high refractive index (>2.5), good biocompatibility etc. and the optical charac-
Received in revised form teristics of photonic crystals containing the band gap, photonic localization, slow light effect, super prism
30 July 2018
effect and negative refraction effect has attracted tremendous interest. Its synthetic methods are usually
Accepted 31 July 2018
chemical vapor deposition, atomic layer deposition, electrochemical deposition and sol-gel method. To
Available online 3 August 2018
meet the needs of the applications in chemical sensors, solar cells, photocatalysis, high efficient mi-
crowave wire, photonic crystal fiber etc., lots of research focused on the modifications of TiO2 IO PCs by
Keywords:
TiO2
means of noble metal deposition, non-metal elements or metal ion doping, quantum dot sensitization
Inverse opal and semiconductor composite. This paper aims to review the up-to-date synthesis, modification, and
Preparation applications of TiO2 IO PCs and forecast its future development direction.
Modification © 2018 Elsevier B.V. All rights reserved.
Application

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
2. Preparation of TiO2 IO PCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
2.1. Chemical vapor deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
2.2. Atomic layer deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 741
2.3. Electrochemical deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
2.4. Sol-gel method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 742
3. Modification of TiO2 IO PCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 743
3.1. Noble metal modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
3.2. Non-metal elements or metal ions doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 744
3.3. Quantum dot sensitization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 746
3.4. Semiconductor composite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 747
3.5. Other modifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 748
4. Applications of TiO2 IO PCs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
4.1. Chemical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
4.2. SERS detection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
4.3. Solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 752
4.4. Photocatalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754

* Corresponding author.
** Corresponding author.
*** Corresponding author. State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, School of Resources and
Environmental Engineering, East China University of Science and Technology, Shanghai, 200237, PR China.
E-mail addresses: leijuying@ecust.edu.cn (J. Lei), jlzhang@ecust.edu.cn (J. Zhang), ydliu@ecust.edu.cn (Y. Liu).

https://doi.org/10.1016/j.jallcom.2018.07.357
0925-8388/© 2018 Elsevier B.V. All rights reserved.
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 741

4.5. Battery electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755

4.6. Other fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
5. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755

1. Introduction 2. Preparation of TiO2 IO PCs

TiO2, as a kind of stable, non-toxic, harmless and low price of TiO2 IO PCs is generally prepared by colloidal crystal template
materials, has a wide range of uses in the environment, energy method. Usually silica (SO2), polystyrene (PS) or polymethyl
and many other aspects. For example, in the field of photo- methacrylate (PMMA) microspheres are orderly arranged into opal
catalysis, TiO2 as a photocatalyst has been widely used in photo- photonic crystal through gravity sedimentation or centrifugal
catalytic degradation, photosynthesis, water splitting etc. [1]; in sedimentation, self-assembly method, evaporation method, dip
the field of photoelectric conversion, TiO2 has been used as an coating or electrophoresis. Then the opal photonic crystal is used as
important component of dye-sensitized solar cells [2]; in the field the template, to which the precursor or target material is filled.
of Raman spectroscopy, TiO2 with surface enhanced Raman scat- Finally, the template is removed through calcination or etching,
tering (SERS) properties has been concerned by more and more obtaining the inverse opal photonic crystal, as shown in Fig. 1.
scientists [3]. However, TiO2 also has some disadvantages, such as During the preparation, the methods for filling the precursor or
inadequate utilization of visible light, high recombination rate of target material are various mainly including chemical vapor
photo-generated electron-hole pairs and low Raman enhance- deposition, atomic layer deposition, electrochemical deposition
ment factor. and sol-gel method, which are introduced in detail in the following
With the rapid development of nanotechnology, researchers contents.
have gradually realized the close relationship between the struc-
ture and properties of the materials. The special micro structure can 2.1. Chemical vapor deposition
not only enhance the performance but also expand the application
of the materials. The common micro structures include nano- Chemical vapor deposition (CVD) is based on the principle of
spheres, nanowires, nanotubes, nanosheets, mesoporous struc- gas-phase reaction deposition, which has been successfully applied
tures, photonic crystals and so on. Among them, photonic crystals, to the preparation of II-VI semiconductors. This method mainly
which was proposed in 1987 by Yablonovitch [4] and John [5], have passes gaseous precursor into the template to get the inversion
attracted much attention due to their unique physical properties structure. For example, it is feasible to obtain silicon inverse opal
such as photonic band gap [6], slow light effect [7], photonic structure by using disilane gas as the precursor to uniformly de-
localization [8], super prism effect [9] and negative refraction effect posit silicon nanoclusters in opal interface through heat treatment
[10]. The most typical feature of photonic crystals is photonic band at appropriate temperature [14]. By using this CVD method, Hoff-
gap, which means that the propagation of the electromagnetic mann et al. [15] deposited TiO2 into the polymer colloidal crystal
wave with some frequencies is forbidden in photonic crystals. template using isopropyl titanate as the precursor which induced
Photonic crystals also have the slow light effect, that is, the velocity by light in 60e210
C under 10 mbar oxygen atmosphere, then TiO2
of the light propagation at the edge of the photonic band is reduced, was deposited into the polymer colloidal crystal template. The
and many reflections are formed inside photonic crystals, degree of crystallinity of TiO2 can be controlled by changing the
enhancing the light absorption [11]. Up to now, photonic crystals illumination conditions. Moon et al. [16] also used the method of
with several different structures have been reported, including opal CVD to prepare TiO2 IO PCs. During the preparation, opal photonic
photonic crystal and inverse opal photonic crystal. Opal photonic crystal in the arrangement of polystyrene microspheres under
crystal having the same cubic packing structure with natural opal is normal temperature and pressure was exposed to H2O and TiCl4
formed by self-assembly of monodispersed colloid particles, while steam. TiCl4 hydrolyzed to fill gaps in the opal photonic crystal, and
inverse opal photonic crystal is prepared using opal photonic then the opal template was removed to obtain the TiO2 IO PCs.
crystal as template. The inverse opal photonic crystal has a three- Inverse opal structure obtained by this method is very uniform, and
dimensional ordered porous structure with large specific surface the filling rate is controllable, but the disadvantages are that the
area and various optical properties of photonic crystals, which is temperature for the preparation is high and the device used is
having potential applications in photonic crystal interface, func- complex.
tional materials, sensor and so on [12,13].
The TiO2 with inverse opal photonic crystal structure can not 2.2. Atomic layer deposition
only retain the advantages of the original TiO2 but also possess size
adjustable pore structure, large surface area and optical properties Atomic layer deposition (ALD) is a newly developed vapor
of photonic crystals so that it has better application in the fields deposition method for forming a deposition film by the reaction of
such as photocatalysis, solar cell, Raman spectroscopy, chemical the gas precursor pulse alternately into the reactor and the chem-
sensors, electric wires and high efficient microwave photonic ical reaction on the substrate. ALD was first used for the preparation
crystal fiber. The preparation and application research of TiO2 IO of TiO2 IO PCs by King et al. [17]. In their study, SiO2 opal was used
PCs has become a research hotspot in the field of materials at as the template, and ALD growth was performed by alternating 4s
present. pulses of TiCl4 and H2O precursors, each separated by a 10 s of N2
In this review, the research on the preparation, modification and purging, while maintaining the substrate at 100
C. Finally, HF was
application of TiO2 IO PCs in recent years are summarized, mean- used to remove the template. After calcination and crystallization,
while the future development of TiO2 IO PCs is prospected. the TiO2 IO PCs with very smooth surface was obtained. Their study
742 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
Fig. 1. Template synthesis of TiO2 inverse opal structure.
also showed that the deposition and filling in low temperature is
more conducive to smooth surface formation of inverse opal pho-
tonic crystal. In addition, in their another work, also by using ALD
method, TiO2/ZnS:Mn/TiO2 multilayer inverse opal photonic crystal
was prepared by alternately depositing different materials [18], as
shown in Fig. 2. Alessandri et al. [19] prepared CeO2 inverse opal
photonic crystal at first, then used the ALD method to deposit TiO2,
getting CeO2/TiO2 composite inverse opal photonic crystal. These
two works highlight the advantage of ALD, that can be used to
achieve the uniform composite of TiO2 and other materials in the
framework. In addition, the temperature of ALD is lower than that
of CVD. Moreover, by using the ALD method, a high filling fraction
can be achieved which is similar to the CVD method. For example,
Liu et al. [20] fabricated TiO2 IO PCs using PS with different diam-
eter of 288, 390 and 510 nm as template via ALD method and
concluded that the ALD could achieve higher filling fractions (more
than 96%) compared to the conventional nanoparticles-infiltration
method. However, the deposition rate of ALD is very low, and in
most cases, only one atomic layer can be produced in each cycle.
2.3. Electrochemical deposition
The electrochemical deposition (ED) is a filling method that the
main salt ions in the electrolyte occur electrochemical reaction
under certain conditions to deposit target products into the gap of
the opal photonic crystal which works as the electrode. The
controlled ED method has an attractive feature that the growth of
the parent material in the template is obtained from the bottom to
the top. Therefore, an important advantage of this method is the
gap of the opal template can be completely filled, and it is easy to
get the exact reverse replica from the original opal template. Yang
et al. [21] used the saturated calomel electrode as reference elec-
trode, aluminum foil as the counter electrode, FTO glass arranged
Fig. 2. TiO2/ZnS:Mn/TiO2 multilayer inverse opal photonic crystal: Layer 1: 26 nmTiO2;
Layer 2: 10 nm ZnS:Mn; Layer 3: 10 nm TiO2 [18].
PS photonic crystal as working electrode, depositing in 0.02 mol/L
Ti(SO4)2, 0.1 mol/L KNO3 and 0.5 mol/L H2O2 ethanol/water solution
for 30 min. After using toluene to remove PS photonic crystal
templates, the samples were calcined in 450
C. TiO2 IO PCs crys-
tallization with long-range ordered pore structure was obtained. Xu
et al. [22] adopted three-dimensional diamond-like polymer SU8 as
template, through ED of TiO2 sol-gel, achieving TiO2 completely
filled into polymer template, gaining completely reversed replica-
tion with photonic crystal structure. However, for many materials,
it's difficult to confirm whether the material growth in the ED
process follows the law from the bottom to the top.
2.4. Sol-gel method
In the process of the sol-gel method, the raw materials con-
taining high chemical active components as precursors are mixed
evenly and filled completely in the liquid phase, which then carry
out hydrolysis and condensation reactions to form a stable and
transparent sol. Subsequently, gel with three-dimensional network
structure forms after aging. After drying, sintering and removing
the template, the inverse opal crystal structure is obtained from the
gel. Sol-gel filling method has many advantages, such as high purity
and good uniformity of the product, low synthesis temperature
(even at room temperature), easily controlled stoichiometric ratio
and reaction conditions and especially the relatively simple prep-
aration process without special expensive instruments. Therefore,
it has been widely used in the preparation of TiO2 IO PCs [23e26].
The precursors containing titanium in the preparation process of
TiO2 IO PCs using sol-gel technology are mainly titanium alkoxide
like tetrabutyl titanate Ti(O-Bu)4, and inorganic acid such as nitric
acid and hydrochloric acid is usually used as catalyst. The first step
is mixing Ti(O-Bu)4 and organic solvents such as isopropyl alcohol
or ethanol evenly. Then water droplets containing proper amount
of acid are added to the mixed solution under continuous stirring.
As a result, transparent TiO2 colloid is formed. The reaction process
is as shown in formula (1)e(3).
Hydrolysis:nTi(OR)4þ4nH2O/nTi(OH)4þ4nROH (1)
Condensation:nTi(OH)4/nTiO2þ2nH2O (2)
Total reaction:nTi(OR)4þ2nH2O/nTiO2þ4nROH (3)
The titanium alkoxide in alcohol solution firstly reacts with
water to hydrolyze, and then the hydrolyzed titanium alkoxide
form a polymer through the condensation of hydroxyl groups and
further crosslinking and branching. The size as well as the
branching and crosslinking degree of the polymer has great impact
on the thermal stability of the gel and the final inverse opal
structure such as specific surface area, pore volume and pore size
distribution. In general, the structure of the TiO2 IO PCs is very
stable if the branching and crosslinking degree of the gel polymer
chain is very high. Otherwise, the structure is fragile, and it is easy
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
to break during calcination, and the specific surface area is smaller.
In the sole-gel reaction process, to control the relative rate of hy-
drolysis and condensation reactions, acetylacetone as chelating
agent and ethylenediamine as a stabilizer can be added to stabilize
titanium ions and reduce its chemical reactivity. In addition, by
adding some special substances to the precursor solution, TiO2 IO
PCs with particular properties can be achieved. For example, by
adding tin(IV) isopropoxide into the precursor of the sol-gel pro-
cess, Jia et al. [27] fabricated rutile TiO2 IO PCs at the calcination
temperature of 500
C which was much lower than that of the
traditional synthetic method.
The preparation of TiO2 IO PCs using the sol-gel method has also
been carried out in our group [28,29]. Titanium isopropoxide was
chosen as the Ti source precursor, hydrochloric acid as catalyst for
hydrolysis, and they were mixed with ethanol and acetyl acetone.
The mixed solution was then filled into PS opal template to form a
gel. After removing the template and crystallizing TiO2 by calcina-
tion, TiO2 IO PCs were obtained. The samples with different pho-
tonic band gaps were prepared by using PS microspheres with
different particle sizes, and the samples showed different colors
under white light irradiation, as shown in Fig. 3 [28]. In addition, we
found that the sol-gel method is suitable for the preparation of IO
PCs of TiO2 composited with other components. For example, when
tetraethoxysilane, 1- butanol titanium (IV) and chromium nitrate
was mixed in the filling solution and then hydrolyzed in the gap of
the opal template, after removing the template, IO PCs with three
components of SiO2-TiO2-CrxOy can be obtained [29].
The shortage of the sol-gel method used to prepare TiO2 IO PCs is
that the initial effective filling rate is not high. There are mainly two
Fig. 3. SEM images of TiO2 inverse opal substrates prepared by the sol-gel method using opal template assembled by PS microspheres with different sizes, and the scale bar is
500 nm. The insets are photographs of the substrates under white light irradiation [28].
743
reasons. First, the filling method used in this method is liquid phase
filling. When the substrate with opal PC template is immersed in the
sol/solution, due to capillary force, the sol particles will be deposited
on the substrate. After moving the substrate out of the sol/solution,
the evaporation of water/alcohol causes the sol to condense on the
substrate. At the same time, gel appears between particles. In the
drying stage, the solvent in the gel pore is removed and the liquid-
gas interface is formed inside the pore. And the pore structure of
the gel is finally collapsed as a result of surface tension. Besides,
contraction of the gel layer also makes the pore collapse. Therefore,
it is essential to repeat the filling process to fill the pore resulted
from the gel contraction in order to improve the filling rate. Second,
the gel contains lots of organic matters, which must be removed in
the subsequent sintering process. As a result, the effective solid
components in the filling material become less. Experiments
demonstrate that in the process of sintering for densification, the
volume of TiO2 IO PCs prepared by the sol-gel method contracts a lot,
and the general contraction rate is 15%e30% after the removal of
organic matters. Such a large shrinkage may increase the cracks of
the materials and the irregular degree of the periodic arrangement.
3. Modification of TiO2 IO PCs
TiO2 IO PCs possesses both the advantages of TiO2 and inverse
opal photonic crystals. In addition, a large number of studies have
shown that chemical or physical modification can further improve
the performance of TiO2 IO PCs and even endow it with new per-
formances. The modifications to TiO2 IO PCs which have been re-
ported are as follows.
744 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
3.1. Noble metal modification
Noble metal deposition is considered as one of the methods
which can effectively improve the catalytic activity of TiO2. Noble
metals such as Au, Ag, Pt, Rh, and Pd can be deposited on the surface
of TiO2 and work as electron trap to promote the separation of
photo-generated electrons and holes. In addition, noble metals can
expand the response region of TiO2 to visible light through the
surface plasmon absorption (SPA). Thus there have been a lot of
researchers using noble metal deposition to modify TiO2 IO PCs. For
example, TiO2 IO PCs was immersed to the AgNO3 solution heated
to 50
C to load Ag nanoparticles by Yang et al. [30]. TEM and
HRTEM images clearly showed that Ag nanoparticles with sizes of
5e10 nm were well dispersed on the surface of the material (Fig. 4).
The UV-Vis spectra showed that the deposition of Ag nanoparticles
could effectively enhance the absorption of the material in the
visible region and fluorescence spectra showed that the deposition
of Ag nanoparticles could greatly promote the separation of photo-
generated electrons and holes. Combining the deposition of Ag
nanoparticles with the inverse opal structure can make the visible
light photocatalytic activity of the materials greatly improved.
Through a hydrothermal method, Kim et al. [31] deposited Au
nanoparticles (Ag NPs) with the diameter of 30 nm to the surface of
TiO2 IO PCs. In addition, the TiO2 IO PCs used in their study was
surface textured with mesoporous structure. Due to surface plas-
mon resonance and adequate surface area, the introduction of Au
NPs and the properly designed dimension enhanced optical prop-
erties of TiO2 IO PCs, achieving a maximum photocurrent density of
0.8 mA cm2 which was 2.86 times higher than that of bare TiO2 IO
PCs.
Boppella et al. [32] coated Au NPs onto reduced graphene oxide
(rGO) decorated TiO2 IO PCs. The modification process is shown in
Fig. 5. After the preparation of TiO2 IO PCs, they were first immersed
in a poly (allylamine hydrochloride) solution with a concentration
of 0.5 g/L for 2 h and then dipped into a GO suspension for 5 h, and
subsequently treated under Ar flow at 500
C for 3 h. After that the
obtained composite of rGO and TiO2 IO PCs (TiO2@rGO) was
immersed in the prepared citrate capped Au colloidal solution
during varying periods of time. Samples were then dried at 100
C
for 1 h, and the final product (TiO2@rGO@Au) was obtained. The
photoelectrochemical (PEC) performances of TiO2@rGO@Au
exhibited the highest photocurrent density of 1.29 mA cm2 at
Fig. 4. TEM (a) and HRTEM (b) images of Ag deposited TiO2 IO PCs [30].
1.23 V vs RHE, while that of TiO2@rGO or TiO2@Au was only
0.8 mA cm2 or 0.76 mA cm2, indicating that the incorporation of
rGO and the plasmonic effect of Au NPs could jointly improve the
charge separation/transportation efficiency.
Liu et al. [33] used optical deposition method to deposit Pt
nanoparticles to the surface of TiO2 IO PCs. The size of Pt particles
dispersed well on the surface of TiO2 IO PCs was around 3 nm, and
there was no aggregation observed (Fig. 6a). XPS analysis (Fig. 6b)
demonstrated that Pt nanoparticles were deposited in zero valent,
forming a Schottky barrier between Pt and TiO2. Therefore Pt can
effectively capture electrons and inhibit the recombination of
photo-generated electrons and holes when it is used in photo-
catalysis. In addition, the TiO2 in the material showed an anatase
phase with fine crystallinity, which was also beneficial to the
photocatalytic applications like photocatalytic water splitting.
In addition to deposition of noble metals on the surface of TiO2
IO PCs, Du et al. also reported doping of Au nanoparticles into the
skeleton of TiO2 IO PCs by simultaneously filling Au and titanium
precursor into the PC template [34]. The results showed that the Au
nanoparticles were uniformly dispersed in the TiO2 matrix, and the
particle size was below 20 nm which could be adjusted by con-
trolling the filling amount of the alkaline catalyst triethanolamine
liquid. In addition, with the introduction of Au nanoparticles into
the framework, the refractive index of the material increased and
the reflection peak red-shifted, as shown in Fig. 7.
3.2. Non-metal elements or metal ions doping
Non-metal elements or metal ions doping is that introducing
non-metal elements or metal ions to the framework of TiO2 IO PCs
through physical or chemical modification in order to improve the
photochemical properties of TiO2 IO PCs.
Li et al. [35] added tetramethyl ammonium hydroxide in the
filling solution when preparing TiO2 IO PCs by a sol-gel method, and
consequently nitrogen doped TiO2 IO PCs was obtained. The sam-
ples without nitrogen doping had weak absorption in the visible
region longer than 500 nm (Fig. 8a), but the absorption intensity
was significantly enhanced after the doping of nitrogen (Fig. 8b).
Due to the synergistic effect of nitrogen doping and inverse opal
structure, this material had good visible light absorption and the
photocatalytic activity was significantly enhanced.
Yang et al. [36] also used similar sol-gel method to fill SiO2
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 745

Fig. 5. Scheme for the coating processes of TiO2 IO PCs with rGO and Au NPs [32].

photonic crystal template with the addition of [(NH4)2TiF6] in the
filling solution, successfully preparing TiO2 IO PCs co-doped with N
and F. The successful doping of N and F elements was proved by XPS
and Raman spectra, and the visible light absorption of the co-doped
samples was improved obviously. And by increasing the calcination
temperature to 350
C, the single F doped sample could also be
obtained. When comparing the photocatalytic activity of the two
kinds of materials, the co-doped sample exhibited higher catalytic
activity which was 1.7 times that of the single F doped sample.
Liu et al. [37] introduced nitrogen into rGO composited TiO2 IO
PCs. Schematic illustration for the synthesis process of the sample is
shown in Fig. 9. PS@TiO2 coreeshell structure was prepared
through slow hydrolysis of titanium tetraisopropoxide on the sur-
face of PS, and then GO sheets were assembled with PS@TiO2 via
electrostatic interaction and coagulated. Finally, PS template was
removed, GO was reduced and nitrogen was introduced to both
TiO2 and rGO by calcination at an NH3/Ar atmosphere. The final
product displayed a higher specific capacity of 115 m mA h g1 and
64 mA h g1 at a current density of 1 and 10 A g1, respectively than
that of rGO@TiO2 IO PCs without N doping (108 and 45 mA h g1 at
1 and 10 mA h g1, respectively). The improved cyclability and rate
capability can be attributed to the synergistic interaction between
the unique structure design and nitrogen doping.
Deng et al. [38] prepared TiO2 IO PCs doped with the rare earth
metal ion Tb3þ. Firstly, they obtained pure TiO2 IO PCs by the sol-gel
filling method. Secondly, the solution containing Tb3þ was dropped
to the TiO2 IO PCs. After drying in air, TiO2 IO PCs doped with
Tb3þwas obtained. Comparing with ordinary porous TiO2 films
doped with Tb3þ, TiO2 IO PCs doped with Tb3þ emitted photo-
luminescence which was suppressed at 540 nm and enhanced at
484 nm (Fig. 10) due to the presence of the photonic bandgap of
TiO2 IO PCs at 540 nm. The photon capture caused by Prague plane
lattice reflection makes fluorescence emission suppressed when
the fluorescence emission peak overlaps with the photonic
bandgap. According to the redistribution of the photon state den-
sity, the photon density at the peak wavelength of the reflection
spectrum of the photonic crystal is low and squeezed to the edge of
the stopband, so the spontaneous emission of Tb3þ ions increases at
484 nm. The appropriate combination of fluorescent materials and
photonic crystals can provide new ideas for the design and fabricate

Fig. 6. (a) TEM image of Pt-TiO2 inverse opal and the size distribution histogram of Pt nanoparticles (inset); (b) XPS spectrum of loaded Pt nanoparticles [33].
746 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
Fig. 7. Reflection spectrum of PS PC template, TiO2 IO PCs and gold-nanoparticle-
incorporated TiO2 IO PCs [34].
of light-emitting diodes, low-threshold lasers and other efficient
optical devices.
In addition, Yang et al. [39] prepared TiO2 IO PCs co-doped with
the rare earth metal ions Yb3þ and Er3þ. Wherein Er3þ is ideal rare
earth metal ion with upconversion luminescence function and Yb3þ
is a commonly used sensitizer that can increase the absorption
cross section so as to improve the conversion efficiency. The two
kinds of ions were doped into the TiO2 lattice, and the upconversion
emission properties were studied. The conclusion of this study is
similar to that of Deng et al. [38], the photonic band gap signifi-
cantly affected the conversion luminescence of Yb3þ and Er3þ co-
doped TiO2 IO PCs. When the band gap of the photonic band is
overlapped with the emission band of Er3þ ion, the upconversion
luminescence is significantly suppressed.
3.3. Quantum dot sensitization
Apart from noble metal modification and non-metal or metal
ion doping, semiconductor quantum dots (such as CdS, CdSe, CdTe
Fig. 8. Absorption spectra of TiO2 inverse opal (a) and nitrogen-doped TiO2 inverse opal (b) [35].
and InP) sensitization is considered as one of the most promising
modification methods for TiO2 IO PCs. The unique properties of the
quantum dots make the band gap of TiO2 to be easily tuned in a
wide range, and the photogenerated electrons to be effectively
transferred.
Cho et al. [40] reported CdSe deposited TiO2 IO PCs. For the
preparation, they dipped the inverse opal TiO2 electrode into
ethanol solution of 3-mercapto propionic acid for 24 h to make
carboxylic acid bound to hydroxyl groups on the surface of TiO2.
Subsequently, the TiO2 inverse opal electrode absorbed with 3-
mercaptopropionic acid was impregnated with CdSe quantum
dots solution, as shown in Fig. 11. Finally, toluene was used to
completely elute 3-mercaptopropionic acid physically adsorbed on
the TiO2 IO PCs, and then TiO2 IO PC film with uniformly deposited
CdSe quantum dots was obtained. The absorption of TiO2 IO PCs
films sensitized by the CdSe was extended to 650 nm, and showed a
higher photocurrent density.
Cheng et al. [41] prepared CdS quantum dots sensitized TiO2 IO
PCs. CdS quantum dots as “tentacles” can greatly improve the
capture ability to the visible light of materials, while the periodic
arranged pore channels of the inverse opal structure provide large
surface area for quantum dots as electron transport channels. For
the preparation of the material, they used PS microspheres as the
template and prepared TiO2 IO PCs through multi-ALD method,
after which successive ionic layer adsorption and reaction (SILAR)
route was adopted to achieve the CdS quantum dots sensitized TiO2
IO PCs. Because of the higher refractive index of CdS than TiO2, the
reflection peaks of the photonic band gap of CdS quantum dots
sensitized TiO2 IO PCs showed obvious redshift (Fig. 12), and the
reflection peaks is symmetric indicating that CdS was uniformly
dispersed on TiO2 IO PCs. The absorption to visible light of the
materials was enhanced, and the photocurrent density was
increased 200 times than that before sensitization.
In addition, Xiong et al. [42] prepared CdS/CdSe quantum dots
co-sensitized TiO2 IO PCs. The CdS quantum dots were loaded by
spin coating, and CdSe quantum dots were loaded by chemical
deposition on the surface of TiO2 IO PCs. The light absorption of the
co-sensitized material was better than that of only CdSe sensitized
material. Besides, TiO2/CdS/CdSe has stepwise structure of band
edge that the conduction band position of TiO2 is just below that of
CdS and above that of CdSe. As a result, CdS/CdSe quantum dots co-
sensitized TiO2 IO PCs can not only improve the absorption of light,
but also promote the separation of photogenerated electrons and
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 747

Fig. 9. Schematic illustration of the synthesis process for N-GO@TiO2 IO PCs [37].

Fig. 10. Photoluminescence spectra of Tb3þ embedded in TiO2 inverse opal (A) and
Tb3þ mixed in TiO2 porous film (B) [38].
(2.4 eV) and CdSe (1.77 eV) because of its greater visible light
absorbance. Therefore, CdTe quantum dots have also been studied
for the modification of TiO2 IO PCs [43]. When CdTe quantum dots
were adsorbed on TiO2 IO PCs, gains in light harvesting occur near
the absorption edges to both the blue and to the red of a stop-band
centered at 600 nm. The gain in light harvesting is attributed to
photonic effects trapping light in the inverse opal combining with
the great visible light absorbance of CdTe quantum dots.
Chen et al. [44] immobilized all-inorganic perovskite
CsPbBr1.5I1.5 quantum dots to TiO2 IO PCs for expanding the
photocurrent response of photoelectrochemical sensor. In the
modification process, through the slow volatilization of cyclo-
hexane, the CsPbBr1.5I1.5 quantum dots were self-organized into the
framework of the TiO2 IO PCs deposited on a glass substrate, which
was dropped vertically into the CsPbBr1.5I1.5 quantum dots cyclo-
hexane solution. After washing with 0.1 M PBS to remove uncon-
nected CsPbBr1.5I1.5 quantum dots, 6 mL of 0.5% Nafion was used to
form a Nafion membrane for fixing the CsPbBr1.5I1.5 quantum dot
modification on the TiO2 IO PCs surface. After quantum dot modi-
fication, the visible light spectrum of the material red shifted to
640 nm covering the whole visible region.

holes of the material. When the material was used in solar cell, the
photocurrent and energy conversion efficiency can be improved
significantly.
Recently, CdTe with a band gap of 1.45 eV has attracted more
attention than the larger band gap cadmium chalcogenides CdS
3.4. Semiconductor composite
This method refers to using other semiconductor materials to
modify the TiO2 inverse opal to form the heterojunction structure.
The photogenerated electrons or holes of TiO2 can be transferred to

Fig. 11. Fabrication of CdSe-sensitized TiO2 inverse opal films [40].

748 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
Fig. 12. Specular reflectance spectra at 20
incidence for (a) TiO2 IO PCs, (b) CdS quantum dots sensitized TiO2 IO PCs fabricated from 288 nm, 510 nm and 900 nm sized PS sphere
templates [41].
the conduction or valence band of another semiconductor, pro-
longing the lifetime of the generated electrons and holes,
improving the performance in the applications for photocatalysis
and photoelectrochemistry. The mechanism is shown in Fig. 13.
Kim et al. [45] reported Nb2O5-coated TiO2 IO PCs. Nb2O5 was
loaded to TiO2 IO PCs by spin coating the ethanol solution of NbCl5
and then calcining at 500
C. The times of loading can control the
thickness of Nb2O5. XPS, SEM and TEM proved the successful
loading of Nb2O5. Since the conduction band position of Nb2O5 is
100 meV higher than that of TiO2, Nb2O5 and TiO2 can interact to
effectively improve the photoelectrochemical properties of mate-
rials. Song et al. [46] decorated CdSe nanoparticles on the frame-
work of an N-doped TiO2 IO PCs to obtain a visible-light-driven
photocatalyst via a hydrothermal treatment at 180
C for 8 h. Due
to the N-doping and CdSe sensitization, the photocatalytic effi-
ciency of CdSe/N-TiO2 IO PCs achieved a 5.5 times enhancement for
photocatalytic degradation of RhB under visible light.
Alessandri et al. [19] composited CeO2 with TiO2 in inverse opal
structure. First, the three-dimensional ordered macroporous CeO2
was prepared from the colloidal crystal template. Second, TiO2 films
was grown in CeO2 inverse opal by ALD method, obtaining CeO2/
Fig. 13. Mechanism of charge transfer in composite semiconductor photocatalyst with
heterojunction structure.
TiO2 inverse opal composite with average pore size of about 90 nm
(Fig. 14 a). The thickness of the TiO2 layer can be adjusted by con-
trolling the times of ALD. XRD (Fig. 14 b) result showed that CeO2
and TiO2 were successfully composited. CeO2/TiO2 inverse opal
composite showed better photocatalytic activity than pure TiO2 IO
PCs. Similarly, by using the ALD method, Li et al. [47] modified TiO2
IO PCs with MoS2 to form TiO2/MoS2 core/shell IO PCs. The as
fabricated TiO2/MoS2 IO PCs exhibits obvious stopband reflecting
peaks, which can be tuned by varying the diameter of the opal
template as well as the thickness of MoS2 layer. This composite
material with IO PC structure can prove to be potential candidates
for solar energy conversion due to their high surface area and
photonic crystal properties.
Our research group [29] composited TiO2 with CrxOy in the
skeleton of SiO2 inverse opal photonic crystal, preparing TiO2/
CrxOy/SiO2 inverse opal photonic crystal. The samples appeared
the characteristic absorption peak of O/Cr (VI) charge transfer at
280 nm and 370 nm, and the absorption peak of polymeric Cr (VI) at
about 440 nm. With the increase of Cr content, an obvious ab-
sorption peak appeared in the range of 600 nme700 nm which was
due to d-d electronic transitions of Cr (III) from Cr2O3 nanoclusters,
which made the material possess obvious visible light absorption.
In addition, UV-DRS, XRD and other characterizations confirmed
that Cr and Ti formed oxo-bridged Cr-O-Ti, leading to charge
transfer from metal to metal through the oxygen bridge bond.
3.5. Other modifications
Apart from the above methods, carbon deposition is a feasible
method to modify TiO2 IO PCs. Lee et al. [48] pyrolysised phenolic
resin in high temperature to form carbon layer coated on TiO2 IO
PCs. The results of XRD (Fig. 15 a) showed that the pure TiO2 IO PCs
calcined at low temperature (500
C) was mainly anatase while that
calcined at higher temperature (850
C) was mainly rutile. When
the amount of carbon deposition was low, 50% of anatase in TiO2 IO
PCs modified by carbon deposition converted to rutile after calcined
at 850
C. When the amount of carbon deposition was high, only
10% of anatase converted to rutile. UV-Vis results (Fig. 15 b) showed
that the absorption edge of pure TiO2 IO PCs was at 390 nm, cor-
responding to the band gap of rutile (3.1 eV), while the absorption
edge of low carbon-TiO2 IO PCs shifted to 480 nm and the
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 749

Fig. 14. (a) Preparation of CeO2/TiO2 inverse opals and (b) GAXRD patterns of CeO2/TiO2 inverse opal samples [19].

absorption of visible light was enhanced due to a part of carbon
doping into TiO2 or depositing on the surface. The strong absorption
of visible light of the samples coated with high amount of carbon is
mainly because the deposited carbon layer deposition can absorb
visible light. The change of the crystal phase and the light ab-
sorption of TiO2 IO PCs brought by the carbon deposition can
greatly influence the photocatalytic activity.
Quan et al. [49] used a conductive polymer poly3-
hexylthiophene (P3HT) to modify TiO2 IO PCs. The synthetic strat-
egy of bilayer TiO2/P3HT IO PCs is shown in Fig. 16. Firstly, TiO2 IO
PCs was prepared by a liquid phase deposition (LPD) which was the
same as the sol-gel method. Secondly, TiO2 IO PCs was spin coated
with TiO2 nano-particles. Thirdly, the sample was modified with
P3HT by impregnation, getting bilayer TiO2/P3HT. Their results
showed that the heterojunction formed between TiO2 and P3HT can
promote the separation of photogenerated electrons and holes.
Besides, P3HT can be used as the absorbers of visible light and the
inverse opal photonic crystal structure can further promote the
absorption of visible light so that the bilayer TiO2/P3HT can be used
as an effective visible light photocatalyst. Park et al. also modified
TiO2 IO PCs with P3HT and the material was applied for solar cells
[50]. In their study, P3HT was infiltrated into the nanopores of TiO2
IO PCs in vacuum at 200
C after spin coating. Characterizations of
morphology and surface properties revealed that the P3HT chains
completely infiltrated the nanoporous matrix of TiO2 IO PCs. And
obviously enhanced photovoltaic performance was achieved by the
TiO2-IO/P3HT devices.
In addition to modifying TiO2 IO PCs with chemical substances
different from itself as mentioned above, Park et al. [51] reported
self-modification of TiO2 IO PCs with its nanorods to form 1D TiO2
nanorod-planted TiO2 IO PCs. Nanorods grown inside the confined
geometry of the 3D macroporous IO structure can increase the
surface area of the material and improve the ability of electron
transportation. When the material was used as a photo-electrode
for dye sensitized solar cells, a great improvement of the photo-
current density to 14.84 mA cm2 was achieved with a photon-to-
electric conversion efficiency of 6.3% under 1 sun illumination.
Eftekhari et al. [52] prepared sandwich-structured TiO2 inverse
opal (S-IO-TiO2) comprised of a top and a bottom TiO2 IO PC layer as
Fig. 17a and b shown. The stopband's red edge of TiO2 IO PCs with
pore diameters of 140 nm using PS microspheres with size of
175 nm as template overlapped with the TiO2 electronic excitation
energy at 380 nm and the stopband's blue edge of the middle PC
layer with pore diameters of 180 nm using PS microspheres with
size of 230 nm as template overlapped with the excitation energy of
TiO2 (shown in Fig. 17c). This sandwich structure served as an un-
conventional FabryeṔ́ erot microcavity resonator benefits the cir-
culation of the slow photons in the middle layer and results in the
enhancement of light scattering at layer interfaces.
Du et al. [53] introduced mesopores and graphene into TiO2 IO
PCs to make physical and chemical modifications simultaneously.
They mixed the titanium precursor, graphene and mesoporous
template P123 in liquid and the mixture was filled into the photonic
crystal template. The photonic crystal templates and mesoporous

Fig. 15. (a) XRD patterns of the pristine TiO2 inverse opal (prepared at 500
C), bare TiO2 inverse opal (prepared at 850
C), low-C-TiO2 inverse opal, and high-C TiO2 inverse opal
films. (b) UVevis diffuse-reflectance absorption spectra of the bare TiO2 inverse opal, low-C-TiO2 inverse opal, and high-C-TiO2 inverse opal samples [48].
750 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757

Fig. 16. Illustration for the preparation of bilayer TiO2/P3HT [49].

template were removed by calcination in argon atmosphere. TiO2
IO PCs with mesopores and graphene in the framework was ob-
tained after the removal of the templates. Introducing mesopores
into the framework made the material have larger specific surface
area and pore volume. The interconnected mesopores and macro-
pores are favorable for the diffusion and transfer of reactants in
catalytic reactions. Furthermore, graphene is an excellent material
as electron acceptor and good for electron to transfer. As combining
the two kinds of modifications, the material exhibited excellent
photocatalytic activity for degradation of dye pollutants.
Yu et al. [54] also introduced ordered mesoporous to TiO2 IO PCs
composited rGO. In addition, they introduced layers of P25 to form
a quadruple-layer structure (QTiMMFs) as Fig. 18a and b shown.
Fig. 18c shows the SEM image of the as-prepared QTiMMFs. Peri-
odically ordered macroporous structure can be observed obviously.
And the TEM image (Fig. 18d) reveals that the macroporous walls
possess ordered mesopores. When light is irradiated on the mate-
rial, the periodic macropores enable multiple light reflection and
scattering within the structure (Fig. 18b). Meanwhile, mesoporous
channels increase the accessible surface area of the film which can
enhance the absorption of active substances. These factors could
contribute to make an improved light harvesting and thus increase
the conversion efficiency.
4. Applications of TiO2 IO PCs
TiO2 IO PCs are widely used in many fields, such as chemical
sensors, surface enhanced Raman (SERS) detection, solar cell,
photocatalysis, battery electrodes, attracting wide attention.
4.1. Chemical sensors
Because of the high refractive index and the optical properties of
photonic crystals, TiO2 IO PCs has a good application in sensors. Li
et al. [55] prepared TiO2 IO PCs film with large area and uniform
structure using monodispersed PMMA colloidal spheres with par-
ticle size of 295 nm as a template, and used it as the substrate
material for constructing the sensor for detecting refractive index of
solvents. They investigated the changes of the peak positions of
methanol, acetone, isopropyl alcohol, propanol, n-butanol and
glycerol solvents with different refractive index. It was found that
the sensor could detect the solvents with the refractive index of
0.01 difference. Jiang et al. [56] also used TiO2 IO PCs as the sub-
strate material of the sensor which was placed in ethanol solutions
of different concentrations for detecting the change of bandgap
position. It's concluded that the sensor could detect the refractive
index less than 0.002 of different solutions, and the band gap po-
sition of TiO2 IO PCs changed more obviously than that of PS opal
photonic crystal, which meant the detection sensitivity of the
sensor made up of TiO2 IO PCs was better, as shown in Fig. 19. Apart
from that, another research work of Li et al. [57] also showed that
the detection sensitivity of TiO2 IO PCs was better than that of PS
opal photonic crystal and SiO2 inverse opal photonic crystal, which
is because TiO2 with bigger refractive index easily formed larger
refractive index difference with the detected organic solvent.
Chiang et al. [58] fabricated TiO2 IO PCs with high refractive index

Fig. 17. (a) Scheme for the fabrication of sandwich-structured TiO2 inverse opal (S-IO-TiO2). (b) Cross-sectional SEM image of S-IO- TiO2, the scale bar is 1 mm. (c) UV-vis trans-
mission of monolithic (R and B), heterostructure and sandwich-structured inverse opal films in water. The shaded region indicates the electronic absorption band of TiO2 [52].
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 751

Fig. 18. (a) Cross-sectional SEM image of QTiMMFs; (b) Scheme for the light pathways within QTiMMFs; (c) A typical top view SEM image of TiO2 IO PCs with IOM; (d) TEM image of
QTiMMFs [54].

sensitivity by multi-cycle dip-infiltration-coating of PS PC template.
The reflection spectroscopic measurements with respective
refractive index sensitivities of 296 and 286 nm/RIU of the TiO2 IO
PCs for alcohol mixtures and aqueous sucrose solutions character-
ized by Bragg reflection spectroscopy agree with the theoretical
calculations of photonic band and Bragg law, showing that the
refractive index of the infiltrated liquid sample in the TiO2 IO PCs
can be predicted from the measurement results.
In addition to the detection of liquid phase, TiO2 IO PCs was also
used to detect gas phase. Song et al. [59] used TiO2 IO PCs modified
by polyaniline (PANI) to achieve a simple and rapid detection of
NH3-HCl steam. When the material was exposed to NH3 and HCl
vapor respectively, it showed the obvious reversible color change
(Fig. 20a). The peak position of the reflection spectrum of the ma-
terial also had obvious shift (Fig. 20b). By using this inverse opal
photonic crystal materials, detection of acid steam can be realized
in the naked eye without using any optical or electronic equipment.
4.2. SERS detection
SERS technology is widely used in the detection of chemicals.
Apart from metals like Au, Ag and Cu, SERS ability of

Fig. 19. Shifts in stop band positions of PS opals (a) and TiO2 inverse opal (b) in ethanol solutions with different concentration [56].
752 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
Fig. 20. (a) Photographs of PANI infiltrated TiO2 inverse opal corresponding to
different exposure times to NH3 and HCl vapors. (b) The reflectance spectra of a PANI
infiltrated TiO2 inverse opal exposed to NH3eHCl vapors [59].
semiconductors has also been reported. As a typical semiconductor,
TiO2 has become a research hotspot in the field of SERS [60,61].
However, the SERS sensitivity of TiO2 substrate is lower than
that of the conventional metal substrate. Our group applied TiO2 IO
PCs for SERS detection of small organic molecules for the first time
and found that the detection sensitivity to methylene blue using
TiO2 IO PCs can be significantly higher than that using ordinary TiO2
substrate (Fig. 21) [28]. Through designed experiments, we proved
that the enhancement of the Raman signal resulted from the
multiple scattering of laser in TiO2 IO PCs. We also found that the
coupling between the laser wavelength and the photonic band gap
position had a great effect on the Raman enhancement. When the
laser wavelength overlapped with the photonic band gap, the
Raman enhancement was the weakest. When the laser wavelength
Fig. 21. Comparison between Raman spectra of MB with various concentrations
detected by TiO2 IO PCs, TiO2 planar, and P25. The SEM image of TiO2 IO PCs is shown
in the inset [28].
was in the slow light effect region of the photonic crystal, the
Raman enhancement was the best. The SERS substrate made up of
TiO2 IO PCs can be quickly recovered under simulated solar light
irradiation and repeatedly used.
In addition, our group uniformly dispersed Au nanoclusters with
catalytic activity to the surface of TiO2 IO PCs with SERS activity,
preparing the materials with catalysis/SERS bi-functions [62]. The
reduction of 4-nitrobenzenethiol (4-NTP) was taken as the catalytic
reaction for detection, in which 4-NTP was reduced to 4-
Aminothiophenol (4-ATP) with NaBH4 as reducing agent and Au
as catalyst. Combining Au and TiO2 IO PCs made the catalytic re-
action could take place and meanwhile be monitored by SERS. And
charge transfer (CT) is the mechanism of the SERS ability for TiO2,
which is different from that of the traditional metal SERS substrate.
Therefore, it will not cause the plasma resonance and there is no
“hot spot” effect, so that it can avoid the side reactions which occur
during the SERS detection process by using traditional metals. Us-
ing TiO2 IO PCs as a substrate, Yan et al. [63] investigated the
photocatalytic oxidation of p-aminothiophenol (PATP) to 4, 40 -
dimercaptoazobenzene (DMAB) by finely resolved SERS. Their re-
sults showed that PATP molecules dispersed on TiO2 IO PCs
possessed stronger signals than those on P25 under the irradiation
of 532 nm laser spectra. Besides, they found that the peak intensity
of N]N, C-S and C-C appearing at 1437 cm1, 1089 cm1, 1593 cm1
decreased following the first order kinetic equation, demonstrating
the feasibility of SERS for self-tracking the photocatalytic process.
Zhao et al. [64] dispersed and deposited Ag nanoparticles (NPs)
on the walls of TiO2 IO PCs via an electroless deposition process. The
Ag-decorated TiO2 IO PCs showed high SERS enhancement for R6G
with the detection limit of 1010 mol/L. Their study indicates that
the magnitude of SERS signal enhancement depends on Ag-loading
cycles and pore sizes of TiO2 IO PCs. Li et al. [65] prepared Ni-doped
TiO2 IO PCs for the first time as a bifunctional material applied to
SERS substrate and photocatalyst via a casting and calcination
process by using PS spheres array as the template and
Ni(NO3)2$6H2O as Ni source. Fig. 22A shows that the characteristic
peaks of 4-mercaptobenzoic acid (4-MBA) on Ni (3 wt%)-TiO2 IO PCs
substrate were more obvious compared to bare-TiO2 and TiO2 IO
without Ni doping, indicating that the SERS signals can be
enhanced through increasing the amount of the dopant. As Fig. 22B
shown, the Ni (3 wt%)-doped TiO2 IO PCs exhibited sensitive
detection capability for 4-MBA with concentration even lower to
1  1011 mol/L.
The above studies demonstrated that TiO2 IO PCs is promising
for using as sensor substrates in SERS applications. However,
because the research in the field of SERS detection by TiO2 IO PCs is
in its infancy, this application still stays in the stage of laboratory
research at present.
4.3. Solar cells
Liu et al. [20] investigated the photoelectrochemical perfor-
mances of the TiO2 IO PCs photoanodes with different macropore
sizes in dye-sensitized solar cells (DSCs) systematically for the first
time. It is found that the energy conversion efficiency of the cell
could attain 2.22% by using the TiO2 IO PCs with a macropore size of
288 nm as photoanode and indoline dye as a sensitizer. The effi-
ciency increases was found to be attributed to the increased surface
area for dye loading with the decreasing lattice size of TiO2 IO PCs
electrode.
Cho et al. [40] applied CdSe quantum dots sensitized TiO2 IO PCs
to solar cells in the visible region. The maximum photocurrent
density per Cd mass of the material was 0.474 mA cm2, which is far
higher than that of other quantum dots sensitized solar cells re-
ported previously. Kim et al. [45] used Nb2O5-coated TiO2 IO PCs in
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757 753

Fig. 22. (A) Raman spectra of 4-MBA by using (a) bare TiO2 IO PCs, (b) Ni (1 wt%)-TiO2 IO PCs and (c) Ni (3 wt%)-TiO2 IO PCs; (B) SERS spectra of 4-MBA with (a) 1  105 M, (b)
1  107 M, (c) 1  109 M, (d) 1  1011 M by using Ni (3 wt%)-TiO2 IO PCs as the substrate [65].

dye-sensitized solar cells. The results of the photoelectric test
showed that the maximum photon-to-electric conversion effi-
ciency of the TiO2 IO PCs electrode containing 3.3 wt% Nb2O5 was
7.23%.
Using the plate-sliding coating method coupled with hot air
flow, Lee et al. [66] successfully deposited mesoscale colloidal
crystals onto the substrate as the template for the preparation of
TiO2 IO PCs. The TiO2 IO PCs with 70 nm pores was successfully
fabricated. This meso-IO structure with high surface area and faster
charge transport properties made the dye-sensitized solar cell
exhibit higher photocurrent than the traditional TiO2 electrode.
And the meso-IO structures have the potential to be used in various
photoelectrochemical devices. Park et al. [51] planted 1D nanorods
into 3D TiO2 IO PCs as electrodes for dye-sensitized solar cells.
Compared with pure TiO2 IO PCs, the implantation of nanorods can
further improve the performance of dye-sensitized solar cells
(Fig. 23). Xu et al. [67] increased the efficiency of dye-sensitized
solar cells to 10.35% with a high current density of 19.86 mA cm2
using TiO2 IO PCs with hierarchically porous structure. For com-
parison, using commercial ruthenium dye N719 as sensitizer, the

Fig. 23. (a) SEM image of the TiO2 IO PCs. (b) SEM image of the nanorod-planted TiO2 IO PCs. (c) Magnified SEM image of the nanorods. (d) Dye-adsorption density versus growth
time. (e) JeV curves of DSSCs comprising bare TiO2 IO PCs and nanorod-planted TiO2 IO PCs electrodes [51].
754 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
Fig. 24. (a) Photocatalytic degradation of AO7 under visible light irradiation and (b) Synergistic effect of Ti3þ doping and slow light effect [70].
power conversion efficiency (PCE) of solar cell was 6.23% and that of
pristine TiO2 IO PCs sensitized by YKP-88 without mesoporous
structure was 8.83%. These results demonstrated that the up to date
highest PCE of organic dye-sensitized solar cells should be attrib-
uted to both dye YKP-88 sensitization and hierarchically porous
structure.
4.4. Photocatalysis
Inverse opal structure is composed of ordered macropores with
large surface area and interconnected pore structure. Therefore, it
has more active catalytic sites and faster electronic transmission
speed for electrons. Meanwhile, the inverse opal structure can
enhance the light absorption of the material. Collectively, the in-
verse opal structure can greatly improve the photochemical prop-
erties of the material. As a result, the inverse opal structure has an
outstanding application in improving the photocatalytic activity of
TiO2. For example, Chen et al. [68] prepared a series of TiO2 IO PCs
with different band positions for photocatalytic degradation of dyes
and found that the ability of photocatalytic degradation can be
greatly improved when the position of photonic band gap closed to
the position of TiO2's intrinsic absorption. Sordello et al. [69]
investigated the photocatalytic activity of TiO2 IO PCs for the
degradation of phenol, and compared it with the activity of the
following materials: (1) TiO2 IO PCs powder; (2) macroporous TiO2
with disordered pores; (3) TiO2 IO PCs losing 3D ordered pores after
grinding and ultrasound. The results showed that the catalytic ac-
tivity of the original TiO2 IO PCs was higher than the others, proving
that its excellent photocatalytic activity mainly came from the 3D
ordered periodic structure. TiO2 IO PCs doped with Ti3þ were
Fig. 25. Schematic illustration on the preparation for carbon- and binder-free cathode. Ordered porous TiO2 by PS is straight-forwardly transformed into the hierarchically ordered
porous black TiO2 (HOP-b TiO2) IO PCs on a Ni mesh [75].
prepared by our group by vacuum activation for the photocatalytic
degradation of azo dyes Acid Orange 7 (AO7) in the visible light
[70]. The experimental results (Fig. 24a) showed that the catalytic
activity of the inverse opal photonic crystal doped with Ti3þ was
better than original opal photonic crystal and mesoporous TiO2
doped with Ti3þ, due to the synergistic effect of the slow light effect
of photonic crystal and Ti3þ doping, promoting the absorption of
visible light.
In addition to photocatalytic degradation of dyes, TiO2 IO PCs
was also used in photocatalytic hydrogen production and photo-
catalytic CH4 production. Liu et al. [33] investigated the photo-
catalytic activity of Pt loaded TiO2 IO PCs. The results showed that
the hydrogen production activity of the material was as 2 times as
that of ordinary TiO2 nanocrystals, mainly due to the slow light
effect and multiple scattering of inverse opal structure. Kim et al.
[71] loaded Au nanoparticles on the surface of TiO2 IO PCs and
studied the performance of photoelectrochemical hydrogen pro-
duction. The combination of inverse opal photonic crystal structure,
surface texture and Au nanoparticles significantly enhanced the
performance of photoelectrochemical hydrogen production. Jiao
et al. [72] applied Pt nanoparticles deposited TiO2 IO PCs for the
photocatalytic reduction of CO2 in the presence of water. Compared
to commercial P25, the enhancement of the CH4 production
amount was achieved due to the slow light effect. And Pt loading
further improved the photocatalytic activity of TiO2 IO PCs, pro-
ducing the highest CH4 amount (2.416 mmol), which was approx-
imately 3.2 and 2.4 times as high as the pure TiO2 IO PCs and P25,
respectively. The improved performance can be attributed to
enhanced absorbance for visible light and inhibited recombination
of the photogenerated electrons and holes.
 J. Yu et al. / Journal of Alloys and Compounds 769 (2018) 740e757
4.5. Battery electrodes
TiO2 IO PCs have been widely applied in the field of battery.
Liang et al. [73] applied hydrogen reduced TiO2 IO PCs as electrode
to lithium sulfur battery, encapsulating and combining the sulfur
and polysulfide physically. The electrode had high conductivity and
strong electrochemical cycle. The reversible capacity was still ~890
mAh/g after 200 cycles and the coulombic efficiency was main-
tained at about 99.5%, significantly improving the performance of
lithium sulfur battery. McNulty et al. [74] fabricated rutile TiO2 IO
PCs and applied it to Li-ion batteries, founding that the materials
exhibited long cycle life, high-rate capability, and high structural
stability. Due to the highly ordered, porous, 3D interconnected
mesoporous structure of rutile TiO2 IO PCs, at a specific current of
75 mA g1, the reversible capacities of batteries were z170 and
140 mA h g1 after the 100th and 1000th cycles, respectively with a
capacity retention of z82.4%. Kang et al. [75] reported the hierar-
chically ordered porous black TiO2 (HOP-bTiO2) IO PCs for stable Li-
O2 battery. As Fig. 25 shown, the TiO2 materials was obtained
through infiltration of Ti sources and H2 thermal treatment for 10 h
using self-assembled PS@Ni with the dimension of macropores
(z1 mm) as template. HOP-bTiO2 IO PCs electrode with LiI exhibited
high stability up to z340th cycle at a current of 500 mA g1. The
enhancement of the electrical conductivity can be attributed to the
large exposed surface of Li2O2 with a toroidal shape suspended on
the HOP-bTiO2 framework to the electrolyte and enhanced mass
transport from soluble catalyst to the Li2O2 surfaces. The design of
TiO2 IO PCs for stable Li-O2 battery avoids the premature cell death
due to the complex side reactions of conditional C-contained Li-O2
battery, expanding its practice application.
4.6. Other fields
TiO2 IO PCs also have great application value in photonic de-
vices, clinical medicine, and so on. Riedel et al. [76] reported a PbS
quantum dot-sensitized TiO2 IO PCs electrode. The biocatalytic re-
action at electrode interfaces was switched by visible light irradi-
ation, generating charge charges within the PbS quantum dots. The
electrons transferred from biologic enzyme to an Os-complex-
containing redox polymer via the quantum dots and finally to the
TiO2 IO PCs electrode, resulting in a photocurrent signal. If the light
source was switched off, there was no current flow due to the lack
of light-induced electrons. Thus the biocatalytic reaction for
glucose oxidation can be controlled by using the TiO2 IO PCs with
light as trigger. Xu et al. [77] reported a bionic TiO2 IO PCs that could
detect and capture circulating tumor cells by combination of a
magnetic Fe3O4@C6@silane nanoparticles with antiepithelial cell
adhesion molecule and 3D ordered pore structure. TiO2 IO PCs
substrate with pore diameter of 415 nm exhibited the highest
capture efficiency of 92% with 1 mL/h for MCF-7 cancer cells.
5. Summary and outlook
Since the concept of photonic crystals was proposed, the
experimental and theoretical research on photonic crystals has
been a hot concern in the field of material science. TiO2 IO PCs not
only has the advantages of the TiO2 including non-toxicity, high
refractive index (>2.5), good biocompatibility, and excellent prop-
erties in electrochemistry, photocatalysis etc., but also has optical
properties of the band gap, photonic localization, slow light effect,
super prism effect, negative refraction effect of the photonic crystal,
arousing wide concern of researchers in various fields. In recent
years, the preparation technology of TiO2 IO PCs has been maturing,
and the material can be modified by various methods, such as noble
metal modification, non-metal elements and metal ion doping,
755
quantum dot sensitization and semiconductor composite,
improving its performance or introducing new properties accord-
ing to the requirements. Therefore, its applications in many fields
such as chemical sensors, solar cells, photocatalysis, battery elec-
trodes are constantly expanding, showing the great prospects. For
the future development direction of TiO2 IO PCs, in the aspect of
preparations, in order to obtain the target product, it is necessary to
choose a proper method after a comprehensive consideration of the
advantages and disadvantages of different synthesis methods; in
the aspect of modifications, developing an economical and feasible
modification method with simple operation will be the right way;
and in the aspect of applications, it will become more and more
popular to combine with the unique physical and chemical char-
acteristics of photonic crystals to develop their applications in
many fields, since the current research is mainly confined to several
characteristics of photonic crystals such as photonic band gap, slow
light effect. With the development of basic research, TiO2 IO PCs
will be gradually come to practical application from laboratory
studies.
Acknowledgments
This work was financially supported by the National Natural
Science Foundation of China (21777044, 5171101651), the State Key
Research Development Program of China (2016YFA0204200), the
Science and Technology Commission of Shanghai Municipality
(16JC1401400, 17520711500), the China Postdoctoral Science
Foundation (2015T8049), and the Fundamental Research Funds for
the Central Universities (222201714061, 222201817009).
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