catalysts

Article
Studied Localized Surface Plasmon Resonance Effects
of Au Nanoparticles on TiO2 by FDTD Simulations
Guo-Ying Yao, Qing-Lu Liu and Zong-Yan Zhao *
Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093,
China; ygy0046@163.com (G.-Y.Y.); qluliu@kmust.edu.cn (Q.-L.L.)
* Correspondence: zzy@kmust.edu.cn; Tel.: +86-871-65109952; Fax: +86-871-65107922




Received: 7 April 2018; Accepted: 21 May 2018; Published: 5 June 2018


Abstract: Localized surface plasmon resonance (LSPR) plays a significant role in the fields of
photocatalysis and solar cells. It can not only broaden the spectral response range of materials,
but also improve the separation probability of photo-generated electron-hole pairs through local
field enhancement or hot electron injection. In this article, the LSPR effects of Au/TiO2 composite
photocatalyst, with different sizes and shapes, have been simulated by the finite difference time
domain (FDTD) method. The variation tendency of the resonance-absorption peaks and the intensity
of enhanced local enhanced electric field were systematically compared and emphasized. When the
location of Au nanosphere is gradually immersed into the TiO2 substrate, the local enhanced electric
field of the boundary is gradually enhanced. When Au nanoshperes are covered by TiO2 at 100 nm
depths, the local enhanced electric field intensities reach the maximum value. However, when Au
nanorods are loaded on the surface of the TiO2 substrate, the intensity of the corresponding enhanced
local enhanced electric field is the maximum. Au nanospheres produce two strong absorption peaks
in the visible light region, which are induced by the LSPR effect and interband transitions between Au
nanoparticles and the TiO2 substrate. For the LSPR resonance-absorption peaks, the corresponding
position is red-shifted by about 100 nm, as the location of Au nanospheres are gradually immersed
into the TiO2 substrate. On the other hand, the size change of the Au nanorods do not lead to a
similar variation of the LSPR resonance-absorption peaks, except to change the length-diameter
ratio. Meanwhile, the LSPR effects are obviously interfered with by the interband transitions
between the Au nanorods and TiO2 substrate. At the end of this article, three photo-generated
carrier separation mechanisms are proposed. Among them, the existence of direct electron transfer
between Au nanoparticles and the TiO2 substrate leads to the enhanced local enhanced electric
field at the boundaries, which is favorable for the improvement of photocatalytic performance of
TiO2 . These findings could explain the underlying mechanism of some experimental observations in
published experimental works, and helpful to design highly efficient composite photocatalysts that
contain noble metal co-catalyst nanoparticles.

Keywords: photocatalysis; localized surface plasmon resonance; Au nanoparticle; FDTD simulation

1. Introduction
TiO2 is a kind of fascinating photocatalyst that possesses the ability of splitting water, which
was first observed by Fujishima and Honda [1]. Afterwards, many scientists have also made many
contributions in photocatalytic technology, such as clarifying the intrinsic mechanism, improving
the photocatalytic performance, and exploring novel efficient photocatalysts. It is well known that
TiO2 can only be activated by UV-light irradiation, whose energy accounts for only 5% of the solar
spectrum. In order to make efficient use of solar energy, researchers have performed a large number
of studies to improve the photocatalytic performance of TiO2 . The most conventional strategy is

Catalysts 2018, 8, 236; doi:10.3390/catal8060236 www.mdpi.com/journal/catalysts

Catalysts 2018, 8, 236 2 of 15

doping with metals [2,3] or non-metals [4,5] into the TiO2 lattice. This approach can narrow the
band gap of TiO2 to absorb visible light. However, as the impurities are introduced, it inevitably
has some intrinsic shortcomings, and the effects of the modification are very limited. Meanwhile,
using a noble metal as a co-catalyst loaded onto the surface of TiO2 is another effective modification
strategy to choose [6,7]. The co-catalyst is used as an electron trap to suppress the recombination of
photo-generated electron-hole pairs, resulting in the improvement of photocatalytic performance.
The optical properties of metal nanoparticles are known to be characterized primarily by the
collective vibration of their free electrons, the so-called localized surface plasmon resonance (LSPR).
Initially, LSPR plays an important role in biosensors, which have a very high sensitivity in the detection
of biomolecular-specific interaction analysis. Until 2008, Awazu et al. placed the LSPR effects in the
field of photocatalysis and presented the concept of plasmonic photocatalysis [8], which attracted
more researchers to focus on this subject. For example, Tanaka et al. prepared spherical gold particles
supported on TiO2 , which exhibited excellent performance due to LSPR, and the apparent quantum
efficiency reached 7.2% in the visible-light region [9]. LSPR can directly extend the light absorption
range of TiO2 to the visible region without reducing the band gap value of TiO2 , which is different
with the doping modification method. For example, Feng et al. have found a new strong absorption
peak at 560 nm in the case of Cu/TiO2 composite photocatalyst under the visible-light region [10];
Mubeen et al. also observed that the absorption spectrum of Au/TiO2 composite photocatalyst extends
to 620 nm [11].
It is known that metal nanoparticles, such as gold (Au) [12–14], silver (Ag) [15–17], copper
(Cu) [18–20], and bismuth (Bi) [21], also show strong optical absorption due to LSPR in the visible-light
region. Among then, Au has attracted extensive concern, due to its excellent catalytic performance
and remarkable LSPR effects. Thus, it has been used as a catalyst/co-catalyst in many composite
photocatalysts, such as Au/Cu2 O [12,22], Au/TiO2 /g-C3 N4 [23], and Au/La2 Ti2 O7 [24]. In these cases,
the photocatalytic performance is significantly promoted because Au particles not only act as electron
traps and active sites, but also induce the LSPR effects. According to the generation mechanism of
LSPR, the size, shape, and composition of metallic nanoparticles are the key factors that predominately
determined the effects of LSPR. Therefore, many research groups have focused on how to regulate
and utilize the LSPR effect through the selection of materials and the design of micro/nano-structures.
On the other hand, the optical properties of metallic nanoparticles are also determined by the electron
interband transition with the substrate. However, energetic charge carriers created by the Au interband
transitions are frequently ignored in the field of photocatalysis. In the present work, Au nanoparticles
supported on a TiO2 substrate are chosen as the research subject. Herein, we report the change of the
size and shape of Au nanoparticles loaded on the different positions of the TiO2 substrate. Furthermore,
based on finite difference time domain (FDTD) simulated results, the electron interband transition
between Au nanoparticles and the TiO2 substrate are determined, and the potential influences on
LSPR effects are also discussed.

2. Results and Discussions

2.1. Au Nanospheres
In the present work, we considered four different locations of Au nanoparticle loading on the TiO2
substrate as shown in Figure 1: (a) the Au nanoparticle just contacts the surface of the TiO2 substrate,
which is labeled as “Model A”; (b) the Au nanoparticle is half-embedded into the TiO2 substrate,
and the center of the Au nanoparticle coincides with the surface of the TiO2 substrate, which is labeled
as “Model B”; (c) the Au nanoparticle is completely embedded in the TiO2 substrate, which is labeled
as “Model C”; and (d) the Au nanoparticle is embedded in the TiO2 substrate to a depth of 100 nm
beneath the surface, which is labeled as “Model D”. In these models, the configurations of Model C
and Model D are similar to the core-shell structure of Au/TiO2 composite photocatalysts in published
experimental work, so they can better model this special nano-structure.
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Figure Figure
1. The1. location
The location of Au
of Au nanoparticlesloaded
nanoparticles loadedonon the
the TiO
TiO22substrate:
substrate:(a)(a)
The AuAu
The nanoparticle just just
nanoparticle
in contact
in contact withwith the surface
the surface of the
of the TiOTiOsubstrate;
2 substrate; (b) the Au nanoparticle is half-embedded into the
(b) the Au nanoparticle is half-embedded into the
2
TiO2 substrate, and the center of the Au nanoparticle coincides with the surface of the TiO 2 substrate;
TiO2Figure
substrate,
1. Theand the center
location of Au of the Au nanoparticle
nanoparticles loaded on coincides with the(a)
the TiO2 substrate: surface
The Au ofnanoparticle
the TiO2 substrate;
just
(c) the Au nanoparticle is completely embedded in the TiO 2 substrate; and (d) the Au nanoparticle is
in contact
(c) the with the surface
Au nanoparticle of the TiO
is completely 2 substrate;
embedded in(b)
thethe Au
TiO nanoparticle
2 substrate; andis half-embedded into the is
(d) the Au nanoparticle
embedded in the TiO2 substrate to a depth of 100 nm beneath the surface.
TiO2 substrate,
embedded and2 the
in the TiO center of
substrate tothe Au nanoparticle
a depth of 100 nm coincides withsurface.
beneath the the surface of the TiO 2 substrate;
(c) the Au nanoparticle is completely embedded in the TiO 2 substrate; and (d) the Au nanoparticle is
Due to the high spherical symmetry of Au nanospheres, the plasma oscillations are isotropic,
embedded in the TiO2 substrate to a depth of 100 nm beneath the surface.
and only
Due to the exhibit
highaspherical
single LSPR absorptionofpeak
symmetry Auinnanospheres,
the wavelength range
the of 300–900
plasma nm, as shown
oscillations in
are isotropic,
Figure
and onlyDue 2. For
exhibit isolated
a single Au nanospheres
LSPR absorption with different radii, their corresponding resonance absorption
to the high spherical symmetrypeak of Auinnanospheres,
the wavelength range of
the plasma 300–900 nm,
oscillations as shown in
are isotropic,
Figure peaks areisolated
centeredAu at different positions in different
the extinction spectra: 517 nm (for R = 25 nm), 530 nm (for
and2.only
For exhibit a single nanospheres with
LSPR absorption peak in theradii, their corresponding
wavelength range of 300–900 resonance absorption
nm, as shown in
R = 50 nm), 581 nm (for R = 75 nm), and 610 nm (for R = 100 nm), respectively. Table 1 shows the
peaksFigure 2. For isolated Au nanospheres with different radii, their corresponding resonance absorption nm
are centered at different positions in the extinction spectra: 517 nm (for R = 25 nm), 530
corresponding electric near-field intensity at these resonance peaks for different radii of Au
(for peaks
R = 50arenm),centered
581 nm at different
(for R =positions
75 nm), in the610
and extinction
nm (for spectra:
R = 100 517nm),
nm (for R = 25 nm), 530
respectively. nm1(for
Table shows
nanospheres. It is obviously observed that these peaks are red-shifted with the increase of the radius
R = 50 nm), 581 nm
the corresponding (for Rnear-field
electric = 75 nm), intensity
and 610 nm at (for R =resonance
these 100 nm), respectively.
peaks for Table 1 shows
different radii the
of Au
of the Au nanospheres, which is in accordance with published results [13,25,26]. Furthermore, as the
corresponding
nanospheres. electric
It isnanospheresnear-field
obviously increases, intensity
observed the at these
thatextinction
these peaks resonance peaks
are red-shifted for different
with radii of Au
radius of Au coefficient also increases. In the
the increase
case of Au of the
nanospheres.
radius of the Au It is obviously observed
nanospheres, is that these peakswith are red-shifted with the [13,25,26].
increase of the radius
nanospheres with radii of 25which
nm, the in accordance
extinction coefficient ispublished results
the smallest (the black curve inFurthermore,
Figure
of the Au nanospheres, which is in accordance with published results [13,25,26]. Furthermore, as the
as the2),radius
which of is Au
almostnanospheres increases,
equal to zero, while thethe extinction coefficient
corresponding also increases.
electric near-field In the the
intensity reaches case of
radius of Au nanospheres increases, the extinction coefficient also increases. In the case of Au
maximum with the Au nanospheres with radii of 75 nm. These simulated
Au nanospheres with radii of 25 nm, the extinction coefficient is the smallest (the black curve in results suggest that the
nanospheres with radii of 25 nm, the extinction coefficient is the smallest (the black curve in Figure
Figurefeatures of resonance
2), which is almostabsorption of LSPR
equal to zero, can be
while thetuned by varying the
corresponding radiusnear-field
electric of the Au intensity
nanospheres. reaches
2), which is almost equal to zero, while the corresponding electric near-field intensity reaches the
the maximum
maximum with the Au nanospheres with radii of 75 nm. These simulated results suggest that the the
with the Au nanospheres with radii of 75 nm. These simulated results suggest that
features of resonance
features of resonance absorption
absorptionofofLSPR
LSPRcan canbebe tuned
tuned by by varying
varyingthe theradius
radius ofofthethe
AuAu nanospheres.
nanospheres.

Figure 2. The extinction spectra of isolated Au nanospheres with different radii.

Table 1. The electric near-field intensity of gold nanoshperes.

Figure 2. TheRadius/nm
extinction spectra of isolated Peak
The Absorption Au nanospheres
of LSPR/nmwithEdifferent
2 radii.
Figure 2. The extinction spectra of isolated Au nanospheres with different radii.
25 517 4.400
Table 1.50The electric near-field intensity
530 of gold nanoshperes.
5.983
Table 1. The electric near-field intensity of gold nanoshperes.
75 581 6.412
Radius/nm The Absorption Peak of LSPR/nm E2
100 610 4.883
25
Radius/nm The Absorption 517
Peak of LSPR/nm 4.400E2
50 530 5.983
25 517 4.400
75 581 6.412
50 530 5.983
75 100 610
581 4.883
6.412
100 610 4.883
Catalysts 2018, 8, 236 4 of 15

The absorption spectra of Au nanospheres loaded on the TiO2 substrate at different locations
are illustrated in Figure 3. The absorption spectrum of anatase TiO2 (the green curve) perfectly
reproduces those results of experimental measurements [1], implying the calculation method and
setting parameters are reliable. In the case of Au nanospheres with radii of 100 nm, there are four
absorption peaks that are respectively centered at ~350, ~420, ~520, and ~610 nm in Figure 3a for
“Model A”. The absorption peak centered at ~350 nm is undoubtedly produced by the TiO2 substrate,
which is labeled as “a” in Figure 3a. This further shows that there is a strong interaction between
Au and TiO2 . This interaction is mainly determined by the interfacial electronic states, resulting
in the electron transition from the high occupied states of Au nanoparticles to the valence band of
the TiO2 substrate [27]. Thus, the absorption peak centered at ~420 nm is ascribed to the electronic
transitions between Au nanospheres and the TiO2 substrate, which is labeled as “b” in Figure 3a.
As per published experimental measurements, the absorption peak centered at ~520 nm is induced
by the LSPR effects, which is labeled as “c” in Figure 3a. There is another shoulder absorption peak
centered at ~610 nm, which is labeled as “d” in Figure 3a. For nanoparticles, the electronic energy
levels are not continuous, compared to bulk materials, but discrete due to the quantum size effects of
thenanoparticles and this can result in a sharp and an intense absorption features corresponding to
interband transitions in nanoparticles [28]. According to Guerrisi’s conclusion and Liu’s experiment the
absorption edge in Au particles is located at ~1.94 eV (~640 nm), which is produced by the interband
electronic transition [29,30]. Thus, it can be speculated that this absorption peak is ascribed to the
interband transition in Au nanospheres. When the radius of Au nanospheres decreased from 100 to
25 nm, these four absorption peaks show different trends: (1) the absorption properties produced by
the TiO2 substrate do not present any obvious variation; (2) the absorption peak led by the electronic
transition between Au nanospheres and the TiO2 substrate are gradually blue-shifted and, finally,
integrated into the absorption of TiO2 substrate, which is possibly led by the quantum size effects of
the Au nanospheres; (3) the LSPR absorption peak of the Au nanospheres is gradually blue-shifted and
decreasing, which is also possibly led by the quantum size effects; (4) the absorption peaks produced
by the interband transition of Au nanospheres is gradually red-shifted and decreasing, indicating that
the optical absorption of Au nanosphere is severely affected by the interaction between LSPR and local
interband transitions [31]. Additionally, in the case of Au nanospheres with radii of 25 nm, the variation
of optical absorption properties induced by Au nanosphere loading are insignificant, implying that
small Au nanospheres do not respond to the incident light. The above characteristics are presented in
Au nanospheres with different particle radii, but there are some differences in the details. For example,
the absorption peaks “c” and “d” will be split into several distinct peaks, and vary with respect to the
blue-shifting as the sphere radius decreases. This simulated result indicates that LSPR and interband
transition will induce multi-peak absorption characteristics, especially in case of Au nanospheres
that are completely embedded into the TiO2 substrate. It has been experimentally demonstrated
that the position of plasmon resonance absorption is sensitively dependent on the particle size and
progressively shifts to the longer wavelengths with the increase of the particle size [12,32].
When Au nanospheres are gradually embedded into the TiO2 substrate, the optical absorption
properties present some obvious or not obvious variations, as shown in Figure 3 (1) the absorption
produced by the TiO2 substrate maintains the constant characteristics, which means the optical
properties of TiO2 substrate are not impacted by the size and location of Au nanosphere loading;
(2) the absorption intensity led by the electronic transition between Au nanospheres and the TiO2
substrate are gradually decreasing. It can be understood that the interaction between Au nanospheres
and TiO2 substrate is gradually weakened with the loading location immersing; (3) the resonance
absorption peak is firstly decreasing and then increasing, and split into several distinct peaks; and (4)
the absorption induced by the interband transition is gradually increasing, split into several distinct
peaks. These simulated results clearly demonstrate that the LSPR effects are also sensitively dependent
on the location of Au nanospheres in the TiO2 substrate. In addition, it can be clearly observed
that the absorption peak of LSPR is red-shifted, as Au nanospheres are gradually immersed in
Catalysts 2018, 8, 236 5 of 15

Catalysts 2018, 8, x FOR PEER REVIEW 5 of 15

the TiO2 substrate. These red-shifts arose due to an overall increase in the refractive index of
the dielectric
dielectric environment
environment surrounding
surrounding the Authenanospheres
Au nanospheres upon
upon TiO TiO2 coating.
2 coating. The core-shell
The core-shell Au-TiO2
Au-TiO 2 nanostructures,
nanostructures, with TiOwith TiOof
2 shells 2 shells
a highofrefractive
a high refractive index
index (2.5) on (2.5) on allofsides
all sides the of thecores,
gold gold
cores, experienced
experienced a larger
a larger red-shift,
red-shift, compared
compared with Model
with Model A and AB,
andin B, in which
which TiO2TiO was coated
was2 coated onlyonly on
on one
one side of the gold, leaving the other side exposed to air, which had a lower refractive
side of the gold, leaving the other side exposed to air, which had a lower refractive index of ≈1.4.index of ≈ 1.4.

(a) (b)

(c) (d)
Figure 3. The
The absorption
absorption spectra
spectra of
of Au
Au nanospheres loaded on
nanospheres loaded on the
the TiO
TiO2 substrate with different radii
Figure 3. 2 substrate with different radii
and locations: (a) Model A; (b) Model B; (c) Model C; and (d) Model D as labeled in Figure 1.
and locations: (a) Model A; (b) Model B; (c) Model C; and (d) Model D as labeled in Figure 1.

In FDTD simulations, the plane-wave source is incident on an Au nanosphere, and the induced
In FDTD simulations, the plane-wave source is incident on an Au nanosphere, and the induced
electric fields at the particular wavelength around Au nanospheres can be further obtained. In order
electric fields at the particular wavelength around Au nanospheres can be further obtained. In order to
to further demonstrate the roles of the LSPR effects, the electric field distribution of Au/TiO 2
further demonstrate the roles of the LSPR effects, the electric field distribution of Au/TiO2 composite
composite systems for the corresponding absorption peaks of LSPR and interband transitions (“c”
systems for the corresponding absorption peaks of LSPR and interband transitions (“c” and “d”)
and “d”) are respectively illustrated in Figure 4. Subgraph (a) corresponds with the electric field
are respectively illustrated in Figure 4. Subgraph (a) corresponds with the electric field distribution
distribution induced by LSPR, and subgraph (b) corresponds with that induced by the interband
induced by LSPR, and subgraph (b) corresponds with that induced by the interband transitions.
transitions. Their orders are arranged by the sphere radius and the location of the Au nanosphere.
Their orders are arranged by the sphere radius and the location of the Au nanosphere. These patterns
These patterns show the local enhanced electric field is enhanced around Au nanospheres. With the
show the local enhanced electric field is enhanced around Au nanospheres. With the increase in the
increase in the radius of the Au nanospheres, both enhanced electric fields are gradually increasing.
radius of the Au nanospheres, both enhanced electric fields are gradually increasing. The results show
The results show that larger Au nanospheres exhibit more obvious effects on the enhanced electric
that larger Au nanospheres exhibit more obvious effects on the enhanced electric fields. Therefore,
fields. Therefore, in order to avoid the interference of interband transitions with LSPR, it is
in order to avoid the interference of interband transitions with LSPR, it is experimentally attempted to
experimentally attempted to prepare Au nanospheres with suitable radii. It can be clearly observed
prepare Au nanospheres with suitable radii. It can be clearly observed that the electric field intensity
that the electric field intensity of the interband transitions is greater than that of LSPR by the electric
of the interband transitions is greater than that of LSPR by the electric field diagram of the large-sized
field diagram of the large-sized gold nanoparticles. Furthermore, it has been reported that the
gold nanoparticles. Furthermore, it has been reported that the interband transitions of Au correspond
interband transitions of Au correspond to the contribution of Au 5d electrons to the electronic
to the contribution of Au 5d electrons to the electronic structure of Au [33,34]. Under the excitation of
structure of Au [33,34]. Under the excitation of light, the 5d band of gold may generate a large number
light, the 5d band of gold may generate a large number of electronic transitions and show a strong
of electronic transitions and show a strong electric field. Through LSPR related decay through
interband transitions, both LSPR and interband transitions are favorable for light absorption and
enhanced the local electric field. When the location of the Au nanospheres is changing, the enhanced
electric fields present different variations: both enhanced electric fields firstly decrease, and then
Catalysts 2018, 8, 236 6 of 15

electric field. Through LSPR related decay through interband transitions, both LSPR and interband
transitions are favorable for light absorption and enhanced the local electric field. When the location
of the Au nanospheres is changing, the enhanced electric fields present different variations: both
enhanced electric fields firstly decrease, and then increase, as the location of Au nanospheres
Catalysts 2018, 8, x FOR PEER REVIEW 6 of 15
is
gradually embedded into the TiO2 substrate. In the case of LSPR, when Au nanospheres are completely
embedded
increase, into
as thethe TiO2 substrate
location (i.e., Model
of Au nanospheres is C), the enhanced
gradually embedded electric fieldTiO
into the is 2the smallest,
substrate. In astheshown
case
in of
Figure Especially in the cases of R
LSPR, when Au nanospheres are completely embedded into the TiO2 substrate (i.e., Model C), zero;
4a. = 25 and 50 nm, the enhanced electric field is equal to the
in enhanced
the other words,
electric the
fieldelectric field is not
is the smallest, as enhanced by the 4a.
shown in Figure LSPR effects, in
Especially while a similar
the cases of Rphenomenon
= 25 and 50
could
nm,be theobserved
enhancedwhen thefield
electric Au nanospheres
is equal to zero;is half embedded
in the other words, into the electric
TiO2 substrate
field is not(i.e.,enhanced
Model B),
as by the LSPR
shown effects,
in Figure 4b.while a similar phenomenon could be observed when the Au nanospheres is half
embedded
In the field intoofthephotocatalysis,
TiO2 substrate (i.e., Model B),of
the presence as the
shownlocalin enhanced
Figure 4b. electric field can effectively
separate In photo-generated
the field of photocatalysis,
electron-hole the pairs.
presence of the local
Therefore, exceptenhanced electric
the above field can for
discussions effectively
the local
separateelectric
enhanced photo-generated
fields enhanced electron-hole
by LSPRpairs.or theTherefore,
interbandexcept the above
transition, discussionsoffor
the distribution thethe local
strongest
enhanced electric fields enhanced by LSPR or the interband transition,
local enhanced electric field in the whole simulation region of 300–900 nm are provided in Figure the distribution of the 5,
strongest local enhanced electric field in the whole simulation region
in which the corresponding wavelength is also indicated. It can be determined that Au nanoparticles of 300–900 nm are provided in
haveFigure
strong5, interaction
in which the withcorresponding wavelength
the TiO2 substrate through is the
alsostrong
indicated. It can be determined
metal-support that Au
interaction compared
nanoparticles have strong interaction with the TiO 2 substrate through the strong metal-support
to the single Au nanoparticle by comparing the electric field intensity of a single Au nanoparticle
interaction compared to the single Au nanoparticle by comparing the electric field intensity of a single
(Table 1) with the electric field intensity of the Au/TiO2 composite structure (Figure 5). In the case of
Au nanoparticle (Table 1) with the electric field intensity of the Au/TiO2 composite structure (Figure
Au nanospheres loaded onto the TiO2 substrate (i.e., Model A), as the radius of the Au nanospheres
5). In the case of Au nanospheres loaded onto the TiO2 substrate (i.e., Model A), as the radius of the
increases, the local enhanced electric field also gradually increases, and only appears at the interface of
Au nanospheres increases, the local enhanced electric field also gradually increases, and only appears
the Au nanoshpheres and the TiO2 substrate. In the other cases of Models B–D, the phenomenon is just
at the interface of the Au nanoshpheres and the TiO2 substrate. In the other cases of Models B–D, the
the opposite: the local enhanced electric field gradually decreases as the radius of the Au nanospheres
phenomenon is just the opposite: the local enhanced electric field gradually decreases as the radius
increases. These simulated results suggest that the interface between Au nanospheres and the TiO2
of the Au nanospheres increases. These simulated results suggest that the interface between Au
substrate is the and
nanospheres key thefactor
TiOto determine the local enhanced electric field [12,19]. From the combined
2 substrate is the key factor to determine the local enhanced electric field
above discussions and the corresponding
[12,19]. From the combined above discussions wavelength
and theofcorresponding
the strongest wavelength
local enhanced of theelectric
strongestfield,
it can be concluded that the strongest local enhanced electric field is caused
local enhanced electric field, it can be concluded that the strongest local enhanced electric field is by the interband transition
in caused
the caseby ofthe
Model A, andtransition
interband it is moreinobvious
the caseinofthe largerA,Au
Model andnanospheres, while the
it is more obvious strongest
in the larger local
Au
enhanced
nanospheres, while the strongest local enhanced electric field is caused by LSPR in the cases obvious
electric field is caused by LSPR in the cases of Model B, C, and D, and it is more of Modelin
theB,smaller
C, and Au nanospheres.
D, and it is more obvious in the smaller Au nanospheres.

(a)

Figure 4. Cont.
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(b)
(b)
Figure
Figure 4. 4.
The
TheThe distributionof
distribution
distribution ofofthe
thelocal
the localenhanced
local enhancedelectric
enhanced electric field
electric field of
field of Au
Au nanospheres
of Au nanosphereson
nanospheres onaaaTiO
on TiO
TiO 2 substrate
substrate
Figure 4. 22 substrate
induced by different
induced by different wavelengths: (a) LSPR absorption peaks; and (b) interband transition peaks. The
induced differentwavelengths:
wavelengths:(a) (a)LSPR absorption
LSPR absorptionpeaks; andand
peaks; (b) (b)
interband transition
interband peaks.
transition The
peaks.
dashed line represents the interface between the Au nanospheres and the TiO2 substrate.
dashed
The line line
dashed represents the interface
represents the interface between the Au
between the nanospheres
Au nanospheres andandthe the
TiOTiO
2 substrate.
2 substrate.

Figure 5. The distribution of the strongest local enhanced electric field of Au nanospheres loaded on
the TiO
Figure 2 substrate in the whole simulation region of 300–900 nm. The dashed line represents the
5. The
Figure 5. The distribution
distributionofofthe
thestrongest
strongestlocal
localenhanced
enhanced electric field
electric of of
field AuAunanospheres
nanospheresloaded on
loaded
interface between the Au nanospheres and the TiO2 substrate.
thethe
on TiO 2 substrate
TiO 2
in
substrate the
in whole
the wholesimulation
simulation region
region of
of300–900
300–900 nm.
nm. The
The dashed
dashed line
line represents
represents the
the
interface between
interface between the
the Au
Au nanospheres
nanospheresand
andthe
theTiO
TiO22 substrate.
substrate.
2.2. Au Nanorods
2.2. Au
2.2. AuCompared
Nanorods with Au nanospheres, Au nanorods have different polarization degrees along
Nanorods
different directions, due to the structural anisotropy, as shown in Figure 6. If incident light is parallel
Comparedwith withAuAu nanospheres, Au nanorods have different polarization degrees along
to Compared
the axial direction nanospheres,
of Au nanorods
the Au nanorods, havefield
the electric different polarization
is perpendicular degrees
to along
the axial different
direction,
different directions,
directions, due to thedue to the structural
structural anisotropy,
anisotropy, as shown asin
shown
Figure in6.Figure 6. If incident
If incident light is light is parallel
parallel to the
to the axial direction of the Au nanorods, the electric field is perpendicular to the axial direction,
Catalysts 2018, 8, x FOR PEER REVIEW 8 of 15

Catalysts 2018, 8, 236 8 of 15

which induces the lateral resonance (LSPRT). If incident light is perpendicular to the axial direction
of the Au nanorods, the electric field is parallel to the axial direction, which induces the longitudinal
resonance (LSPR
axial direction ofL).theIn experiments,
Au nanorods,itthe is difficult
electricto fix Au
field nanorods along
is perpendicular toparticular
the axial directions.
direction, which Thus,
Au nanorods
induces are resonance
the lateral usually randomly (LSPRT ). orientated
If incident light on the TiO2 substrate,
is perpendicular to theandaxialproduce
directiontwoofdistinct
the Au
resonance absorption
nanorods, Catalysts
the electric peaks.
2018, 8, xfield
FOR In the theoretical
is parallel
PEER REVIEW simulation,
to the axial direction, it is induces
which easy to the fix longitudinal
Au nanorods along a
8 of 15resonance
particular
(LSPRL ). In direction.
experiments, In many it isexperiments,
difficult to fix it Au
is a nanorods
concern that along Auparticular
nanorodsdirections.
are flattened on the
Thus, Au
which induces the lateral resonance (LSPRT). If incident light is perpendicular to the axial direction
substrate
nanorods [35,36].
are usuallyThus, here we orientated
randomly also choose onthetheTiO TiO2 2substrate
substrate, toand
be parallel
producetotwo thedistinct
axial direction
resonanceof
of the Au nanorods, the electric field is parallel to the axial direction, which induces the longitudinal
the Au nanorods.
absorption peaks. In(LSPR
resonance the Lpresent
theoretical work, the
simulation,
). In experiments, axialitdirection
it is difficult istoeasy
fix Auto of
fixthe
AuAu
nanorods nanorods
nanorods
along along
particular isdirections.
parallel
a particularto thedirection.
Thus, surface
of
In the
manyTiOexperiments,
substrate,
2Au nanorods in itorder
are is torandomly
studythat
a concern
usually the effects
Au of
on LSPR
nanorods
orientated T with
are
the TiO respect
2 flattened
substrate, onto
and thedifferent
produce two length-diameter
substrate [35,36]. Thus,
distinct
ratios
here we(L/D)resonance
also of absorption
the TiO2peaks.
Au nanorods
choose with In thetotheoretical
diameters
substrate of 100
be parallel simulation,
nm.
to the it shown
Asaxialis easy to
infixFigure
direction Au
of nanorods
the7,Au along
for nanorods. a
the isolated In Au
the
particular direction. In many experiments, it is a concern that Au nanorods are flattened on the
nanorods,
present work,when thetheaxial L/D varies of
direction fromthe one to three, is
Au nanorods theparallel
intensity of surface
to the resonance peak
of the TiOof2 substrate,
LSPR T is
substrate [35,36]. Thus, here we also choose the TiO2 substrate to be parallel to the axial direction of
increased, while
in order tothestudy the
thepeak
Au nanorods. In position
effects theof LSPR
present is Talmost
work,with unchanged
respect
the axial of(centered
to different
direction at ~560
length-diameter
the Au nanorods nm),towhich
is parallel ratios is consistent
(L/D)
the surface of Au
with published
nanorods with experimental
diameters
of the TiO 2 substrate, measurements
ofin100 nm.
order As shown
to study the [13,35,37].
inofFigure
effects These
LSPR 7, for
T with results suggest
the isolated
respect to different that
Au the shape when
nanorods,
length-diameter of the Au
the
nanorods
L/D varies ratios
is the (L/D)
from oneoftoAuthree,
non-critical nanorodsthe with
factor for diameters
the
intensity LSPR ofeffects.
100 nm. As
of resonance
T shown
peak of in Figureis
LSPR 7, increased,
for the isolatedwhileAu the peak
T
nanorods, when the L/D varies from one to three, the intensity of resonance peak of LSPR T is
position is almost unchanged (centered at ~560 nm), which is consistent with published experimental
increased, while the peak position is almost unchanged (centered at ~560 nm), which is consistent
measurements [13,35,37].
with published These results
experimental suggest
measurements that the
[13,35,37]. shape
These of suggest
results the Authat nanorods
the shape is of the
the Aunon-critical
factor for the LSPRisT the
nanorods effects.
non-critical factor for the LSPRT effects.

Figure 6.
6. Figure
Schematic of two
twooftypes
6. Schematic
Schematic of types of LSPR
two types
of LSPR ofofmetallic
of LSPRof metallic nanorods:
metallic nanorods:
nanorods: (a) LSPR
(a) LSPR
(a) LSPR
T; and T; and
(b) LSPR(b) LSPRL.
Figure T ; and (b) LSPRL.
L.

Figure 7. The extinction spectra of isolated Au nanorods with different length-diameter ratios.

The absorption spectra of the Au nanorods with different L/D and locations are plotted in Figure
8 Compared with the clean TiO2 substrate, as shown in Figure 8a, Au nanorod loading produces some

Figure 7. The extinction spectra of isolated Au nanorods with different length-diameter ratios.
Figure 7. The extinction spectra of isolated Au nanorods with different length-diameter ratios.

The absorption spectra

spectra of
ofthe
theAuAunanorods
nanorodswith
withdifferent
differentL/D
L/Dand
andlocations
locationsare
areplotted
plottedininFigure
Figure8
8Compared
Comparedwith
withthe
theclean
cleanTiO
TiO 2 2substrate,
substrate,as
asshown
showninin Figure
Figure 8a,
8a, Au
Au nanorod loading produces some
Catalysts 2018, 8, 236 9 of 15
Catalysts 2018, 8, x FOR PEER REVIEW 9 of 15

new
new absorption
absorption bands
bands inin the
the visible-light
visible-light region.
region. As
As thethe ratio
ratio of
of L/D increases, the
L/D increases, the positions
positions of
of peaks
peaks
b, c, and d are red-shifted. On the other hand, the phenomena are very
b, c, and d are red-shifted. On the other hand, the phenomena are very similar with those ofsimilar with those of Au
Au
nanosphere
nanosphere loading.
loading.Moreover,
Moreover,thesetheseobservations
observationsareareconsistent with
consistent experimental
with experimentalmeasurements
measurements[35].
When the location
[35]. When of the Au
the location nanorods
of the changes,changes,
Au nanorods the absorption propertiesproperties
the absorption present some variation.
present some
Among these absorption bands, the intensity of the c peak that is induced
variation. Among these absorption bands, the intensity of the c peak that is induced by the by the LSPR effect
LSPRis
obviously strong in
effect is obviously the case
strong of case
in the Au nanorods loadedloaded
of Au nanorods on theonsurface of theofTiO
the surface substrate.
the2 TiO As the
2 substrate. As
Au nanorods are gradually embedded into
the Au nanorods are gradually embedded into the TiO the TiO substrate, the intensity of different absorption
2 2 substrate, the intensity of different absorption
bands
bands is,
is, first,
first, gradually
gradually decreasing,
decreasing, andand then
then increasing,
increasing, andand the
the position
position is
is gradually
gradually red-shifted.
red-shifted.
These simulated results indicate that the intensity and position of LSPR effects
These simulated results indicate that the intensity and position of LSPR effects are impacted by are impacted by the
the
shape and location of Au nanorods.
shape and location of Au nanorods.

(a) (b)

(c) (d)

Figure 8.
Figure 8. The
The absorption
absorption spectra
spectra of
of Au
Au nanorods
nanorods loaded on the
loaded on the TiO
TiO22 substrate
substrate with
with different
different radii
radii and
and
location: (a) Model A, (b) Model B, (c) Model C, and (d) Model D as labeled in Figure
location: (a) Model A, (b) Model B, (c) Model C, and (d) Model D as labeled in Figure 1. 1.

The distribution of the strongest local enhanced electric field in the whole simulation region of
The distribution of the strongest local enhanced electric field in the whole simulation region of
300–900 nm of Au nanorods with different L/D ratios and different locations is illustrated in Figure
300–900 nm of Au nanorods with different L/D ratios and different locations is illustrated in Figure 9.
9. Similarly, the local enhanced electric fields are presented at the interface between the Au nanorods
Similarly, the local enhanced electric fields are presented at the interface between the Au nanorods
and the TiO2 substrate. As the L/D ratio is increasing, the local enhanced electric field is gradually
and the TiO2 substrate. As the L/D ratio is increasing, the local enhanced electric field is gradually
weakening. This phenomenon is very obvious in the case of Au nanorods embedded into the TiO2
weakening. This phenomenon is very obvious in the case of Au nanorods embedded into the TiO2
substrate (i.e., Model D). On the other hand, when Au nanorods are gradually embedded into the
substrate (i.e., Model D). On the other hand, when Au nanorods are gradually embedded into the TiO2
TiO2 substrate, the local enhanced electric field is, first, weakening, and then enhancing. This
substrate, the local enhanced electric field is, first, weakening, and then enhancing. This phenomenon
phenomenon is very obvious in the case of Au nanorods with an L/D = 1. Moreover, the case of Au
is very obvious in the case of Au nanorods with an L/D = 1. Moreover, the case of Au nanorods
nanorods covered by the TiO2 substrate at 100 nm depths, like the situation of the Au/TiO2 core–shell
covered by the TiO2 substrate at 100 nm depths, like the situation of the Au/TiO2 core–shell system,
system, can remarkably enhance the local enhanced electric field, and this phenomenon is more
can remarkably enhance the local enhanced electric field, and this phenomenon is more obvious with
obvious with the increase in the thickness of the TiO2 shell [13,14]. In the photocatalytic activity
the increase in the thickness of the TiO2 shell [13,14]. In the photocatalytic activity testing, this effect
testing, this effect can significantly promote the photocatalytic performance of TiO 2.
can significantly promote the photocatalytic performance of TiO2 .
Catalysts 2018, 8, 236 10 of 15
Catalysts 2018, 8, x FOR PEER REVIEW 10 of 15

Figure9.9.The
Figure Thedistribution
distributionof
ofthe
thestrongest
strongestlocal
localenhanced
enhancedelectric
electricfield
fieldof
ofAuAunanorods
nanorodsloaded
loadedononthe
the
TiO 2 substrate in the whole simulation region of 300–900 nm. The dashed line represents the interface
TiO2 substrate in the whole simulation region of 300–900 nm. The dashed line represents the interface
between
betweenAu Aunanorods
nanorodsandandthe
theTiO
TiO2 2substrate.
substrate.

2.3.
2.3. Au
AuNanospheres
NanospheresVersus
VersusAu
AuNanorods
NanorodsLoaded
Loadedon
onthe
theTiO
TiO2 2Substrate
Substrate
Due
Duetotothethedifferent
differentshape
shapeand and
size, size,
the corresponding
the corresponding LSPR of Au nanoparticles
LSPR present different
of Au nanoparticles present
effects. As the radius of Au nanospheres increases, the LSPR peaks are
different effects. As the radius of Au nanospheres increases, the LSPR peaks are red-shifted, whilered-shifted, while as the L/D as
ratio increases,
the L/D the LSPR
ratio increases, T peaks
the LSPRTremain in almost
peaks remain the same
in almost the position. WhenWhen
same position. the location of the
the location ofAuthe
nanoparticles
Au nanoparticles are gradually
are gradually embedded
embedded from fromthethesurface
surfaceto to
thethebulk
bulkofofthetheTiO
TiO2 substrate,
2 substrate,the
theLSPR
LSPR
exhibit
exhibit multi-peak absorption characteristics, especially in the case of Au nanoparticles covered by
multi-peak absorption characteristics, especially in the case of Au nanoparticles covered by
the
the TiO
TiO22 substrate (i.e.,
(i.e., Model
Model D). D).In Inthe
thepresent
presentwork, work,it itis is found
found thatthat adjusting
adjusting thethe location
location of theof
the
Au Au nanoparticles
nanoparticles in in
thethe TiO
TiO 2 substrate
2 substrate couldproduce
could producemore moreobvious
obviousand and rich
rich LSPR effects
effects than
than
changing
changing the size of the Au nanoparticles. If the size and location of the Au nanoparticles are
the size of the Au nanoparticles. If the size and location of the Au nanoparticles are fixed,
fixed,
the
theLSPR
LSPReffects
effectscould
couldappear
appear more
moresignificant
significant on onthethesurface
surface of ofthe
theTiO
TiO22 substrate.
substrate. In In other
other words,
words,
Au
Au nanoparticle loading onto the surface of the TiO22 photocatalyst may be better to enhance the
nanoparticle loading onto the surface of the TiO photocatalyst may be better to enhance the
corresponding
correspondingperformance.
performance.Furthermore,
Furthermore,the thestructural
structural anisotropy
anisotropy andand complexity
complexity of of
AuAu nanorods
nanorods is
the root
is the forfor
root thethe
non-regular
non-regular properties
properties ofofthe theLSPR
LSPR effects.
effects.ForForexample,
example,Wang Wangetetal. al.have
havereported
reported
that
thatthe
thetruncated
truncatednanorods
nanorodsexhibit
exhibitaablue-shift
blue-shiftof ofthe
theLSPR
LSPReffects
effectsinin comparison
comparisonwith with the
the rectangular
rectangular
nanorods
nanorods [22].
[22]. It is worth
worth noting
noting thatthat changing
changing the the location
location of of the
the AuAu nanoparticles
nanoparticles in in the
the TiO
TiO22
substrate can vary the LSPR effects, varying from the visible-light region
substrate can vary the LSPR effects, varying from the visible-light region to the near-infrared-light to the near-infrared-light
region,
region,while
whilechanging
changingthe thesize
sizeofofthe
theAuAunanoparticles
nanoparticlesonly onlyproduces
producesaboutabout100-nm
100-nmred-shifting.
red-shifting.
The
The local enhanced
enhanced electric
electricfields
fieldsonly
onlypresent
presentatat thethe interface
interface between
between thetheAu Au nanoparticles
nanoparticles and
and the TiO substrate.
the TiO2 substrate.
2 When the Au nanoparticles are completely
When the Au nanoparticles are completely covered by the TiO2 substrate covered by the TiO substrate
2 at a 100-
at
nm a 100-nm
depth, thedepth,
localthe local enhanced
enhanced electric
electric field is thefield is the strongest.
strongest. In the field In of
thephotocatalysis,
field of photocatalysis,
LSPR can
LSPR
promotecanthe
promote the photocatalytic
photocatalytic performance performance (enhance visible-light
(enhance visible-light harvesting, harvesting,
and separateand the separate
electron-
the electron-hole pairs efficiently) by the following effects: direct electron
hole pairs efficiently) by the following effects: direct electron transfer, LSPR-mediated local transfer, LSPR-mediated
electromagnetic fields, and plasmon-induced resonance energy transfer [12,19,32]. However, a recent
study suggests that the intensity of the electron transfer is not necessarily correlated with an Au LSPR
Catalysts 2018, 8, 236 11 of 15
Catalysts 2018, 8, x FOR PEER REVIEW 11 of 15

local electromagnetic fields, and plasmon-induced resonance energy transfer [12,19,32]. However,
band [38]. Govorov and co-workers have reported that photo-generated holes in the interband
a recent study suggests that the intensity of the electron transfer is not necessarily correlated with
transition are created far from the Fermi surface (2.4 eV relative to EF), while holes in the plasmonic
an Au LSPR band [38]. Govorov and co-workers have reported that photo-generated holes in the
wave are distributed near the Fermi surface [39]. This means that the 5d band of gold generates a
interband transition are created far from the Fermi surface (2.4 eV relative to EF ), while holes in the
large amount of electrons, and these electrons transition to the conduction band of Au and then to
plasmonic wave are distributed near the Fermi surface [39]. This means that the 5d band of gold
the conduction band of TiO2. This promotes efficient separation of electron-hole pairs. In the present
generates a large amount of electrons, and these electrons transition to the conduction band of Au
work, it can be found that the local enhanced electric fields of the LSPR effect are easily impacted by
and then to the conduction band of TiO2 . This promotes efficient separation of electron-hole pairs.
the shape, size, and location of the Au nanoparticles, compared to the LSPR absorption. Furthermore,
In the present work, it can be found that the local enhanced electric fields of the LSPR effect are easily
there is the complex interaction between the interband transition and LSPR absorption. Thus, how to
impacted by the shape, size, and location of the Au nanoparticles, compared to the LSPR absorption.
effectively utilize LSPR effect needs careful consideration to reasonably choose these determined
Furthermore, there is the complex interaction between the interband transition and LSPR absorption.
factors according to the enhanced mechanism for the photocatalytic performance.
Thus, how to effectively utilize LSPR effect needs careful consideration to reasonably choose these
determined
3. factorsMethods
Computational according to the enhanced mechanism for the photocatalytic performance.

3. Computational
In recent years,Methods
with the aid of computers and various numerical processing methods to solve
Maxwell’s equations, great achievements have been made in the field of LSPR, such as the FDTD
In recent years, with the aid of computers and various numerical processing methods to solve
method, discrete dipole approximation (DDA), T-matrix method, discrete source method (DSM), and
Maxwell’s equations, great achievements have been made in the field of LSPR, such as the FDTD
so on. Among these methods, the FDTD method can directly simulate the near and far field
method, discrete dipole approximation (DDA), T-matrix method, discrete source method (DSM), and so
distribution, and can use a non-uniform meshing grid for the irregular models, resulting in relatively
on. Among these methods, the FDTD method can directly simulate the near and far field distribution,
high simulation accuracy. The FDTD method is based on the calculation of the Maxwell equations
and can use a non-uniform meshing grid for the irregular models, resulting in relatively high simulation
using the Yee cellular discretization shown in Figure 10. It can be seen from Figure 9 that each
accuracy. The FDTD method is based on the calculation of the Maxwell equations using the Yee
electric/magnetic field component is surrounded by four magnetic/electric field components. The
cellular discretization shown in Figure 10. It can be seen from Figure 10 that each electric/magnetic
electric field and the magnetic field are alternately sampled in time. The sampling time interval is
field component is surrounded by four magnetic/electric field components. The electric field and
half a time step, and solved iteratively in time. Combined with the initial conditions and the boundary
the magnetic field are alternately sampled in time. The sampling time interval is half a time step,
conditions, the electromagnetic field distribution in space can be obtained. Through the obtained
and solved iteratively in time. Combined with the initial conditions and the boundary conditions,
electric field, the reflectivity, transmissivity, and absorption of incident electromagnetic waves can
the electromagnetic field distribution in space can be obtained. Through the obtained electric field,
also be obtained.
the reflectivity, transmissivity, and absorption of incident electromagnetic waves can also be obtained.

Figure
Figure10.
10.The
TheYee
Yee cells
cells of
of electromagnetic
electromagnetic field
field in
in FDTD
FDTD simulations.
simulations.

Usually, we used
Usually, we used the
the scattering
scattering cross-section
cross-section (Q
(Qscat),), the absorption cross-section (Qabs), and the
scat the absorption cross-section (Qabs ), and the
extinction cross-section(Q(Qexti) )toto
extinction cross-section characterize
characterize the the
LSPRLSPR
effects effects
of Auof Au nanoparticles
nanoparticles on the
on the TiO TiO 2
exti 2 substrate.
substrate. The scattering cross-section characterizes the effective radiation enhancement
The scattering cross-section characterizes the effective radiation enhancement range of the LSPR, range of the
LSPR,
and theand the absorption
absorption cross-section
cross-section is the effective
is the effective absorption absorption energy
energy space of space of theelectrons
the surface surface
electrons for forming the LSPR. While the extinction cross-section is the combined
for forming the LSPR. While the extinction cross-section is the combined effect of the above effect of the above
two
two phenomena, which can be used to characterize the integrated effect of the
phenomena, which can be used to characterize the integrated effect of the surrounding medium surrounding medium
and metal nanoparticles on the incident electromagnetic field, and observe the effective resonance
wavelength between the LSPR and the incident light field. The peak wavelength corresponds to the
Catalysts 2018, 8, 236 12 of 15

and metal nanoparticles on the incident electromagnetic field, and observe the effective resonance
wavelength between the LSPR and the incident light field. The peak wavelength corresponds to the
LSPR wavelength of Au particles. The above physical quantities are related to the size and shape of
the gold particles and the surrounding media environment and are defined as follows:

εm − ε0
Qabs = kIm{α} = 4ka3 Im{ } (1)
ε m − 2ε 0

k4 8 4 6  ε m − ε 0 2
 
2
Qscat = | |
α = k πa  ε m + 2ε  (2)
6π 3 0

Qexti = Qabs + Qscat (3)

where k is the wave vector of the incident light, α is the polarizability of the Au nanoparticles, a is
the radius of the Au nanoparticles, εm and ε0 are the permittivity of the Au nanoparticles and the
environmental medium, respectively, and Im is the imaginary part. In order to simplify the published
experimental work [40,41], only one Au nanoparticle in the periodic boundary is considered for the
numerical simulation of free electrons’ collective oscillation bringing about the LSPR phenomenon in
the present work.
In the present work, the dielectric constant of Au can be described using Johnson and Christy’s
report [42], and the dielectric constant of TiO2 (anatase) can be introduced using our previous density
functional theory calculated results. Other FDTD parameters, descriptions, and settings to extract the
optical properties in the present work are listed in Table 2.

Table 2. FDTD parameter descriptions and settings to investigate the optical properties of the proposed
Au-based nanoparticles.

Parameter Isolated Au Nanoparticle Au/TiO2 Composites

Spatial cell sizes(dx = dy = dz) 2.5 nm 2.5 nm
Number of time steps 6000 6000
Source Total-field scattered-field Plane wave
Wavelength 300–1500 nm 300–1500 nm
Background index 1 1
Boundary conditions PML PML
Number of PML layers 8 12

4. Conclusions
In the present work, the effects of LSPR of Au nanoparticle loading onto a TiO2 substrate were
simulated by the FDTD method. Especially, the variation tendency of the resonance-absorption peaks
and the intensity of local enhanced electric field were systematically compared and emphasized.
The features of the resonance absorption of LSPR can be tuned by varying the size, shape, and location
of Au nanoparticles. When Au nanoparticles are completely embedded into the TiO2 substrate up
to 100-nm, LSPR and interband transition will induce multi-peak absorption characteristics. In these
determined factors, the LSPR effects are sensitively dependent on the location of Au nanoparticles in the
TiO2 substrate. When the location of Au nanospheres are gradually immersed into the TiO2 substrate,
the local enhanced electric field of the boundary is gradually enhanced. When it is covered by TiO2
into 100 nm depths, the local enhanced electric field intensities reach the maximum value. However,
when Au nanorods are loaded onto the surface of the TiO2 substrate, the intensity of the corresponding
local enhanced electric field is the maximum. Au nanospheres produce two strong absorption peaks in
the visible light region, which are induced by the LSPR effect and interband transitions between Au
nanoparticles and the TiO2 substrate. For the LSPR resonance-absorption peaks, the corresponding
position is red-shifted by about 100 nm, as the location of the Au nanospheres is gradually immersed
into the TiO2 substrate. On the other hand, the size change of the Au nanorods does not lead to a
Catalysts 2018, 8, 236 13 of 15

similar variation of the LSPR resonance-absorption peaks, except to change the length-diameter ratio.
Meanwhile, the LSPR effects are obviously interfered with by the interband transitions between the
Au nanorods and the TiO2 substrate. In the Au/TiO2 composite structure, there is a strong interaction
between the Au nanoparticles and the TiO2 substrate, which is compared to the electric field intensity
of the Au single-nanoparticle and the composite structure. Furthermore, although interband transitions
will interfere with the LSPR, both the interband transitions and the LSPR of Au will have an electric
field enhancement effect. Finally, hot electrons are likely to be generated in the 5d band of Au instead
of LSPR. The local enhanced electric fields of the LSPR effect are easily impacted by the shape, size,
and location of Au nanoparticles, compared to the LSPR absorption. Furthermore, there is the complex
interaction between the interband transition and LSPR absorption. Thus, how to effectively utilize
the LSPR effect needs careful consideration in order to reasonably choose these determined factors
according to the enhanced mechanism of the photocatalytic performance.

Author Contributions: G.-Y.Y. carried out the FDTD calculations, analyzed the calculated results, and prepared
the manuscript; Q.-L.L. helped analyze the calculated results and revised the manuscript. Z.-Y.Z. designed and
planed the research work, guided G.-Y.Y. to complete the present work, and revised the manuscript.
Acknowledgments: The authors would like to acknowledge the financial support from the National Natural
Science Foundation of China (grant no. 21473082), and the 18th Yunnan Province Young Academic and Technical
Leaders Reserve Talent Project (grant no. 2015HB015).
Conflicts of Interest: The authors declare no conflict of interest.

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