Journal of ELECTRONIC MATERIALS

https://doi.org/10.1007/s11664-018-6717-4
Ó 2018 The Minerals, Metals & Materials Society

Structural Design of Near-Infrared Light-Active Cu/TiO2/

NaYF4:Yb,Er Nanocomposite Photocatalysts

DUONG VAN HAU,1,2 DANG THI THANH NHAN,3 NGUYEN VAN DUC,2
VU PHI TUYEN,4 THANH-DINH NGUYEN,5 TRAN THAI HOA,1
and NGUYEN DUC CUONG1,6,7

1.—University of Sciences, Hue University, 77 Nguyen Hue, Hue 530000, Vietnam. 2.—University
of Agriculture and Forestry, Hue University, 102 Phung Hung, Hue, Vietnam. 3.—University of
Education, Hue University, 34 Le Loi, Hue 530000, Vietnam. 4.—Institute of Research and
Development, Duy Tan University, 03 Quang Trung, Da Nang, Vietnam. 5.—Department of
Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC V6T 1Z1, Canada.
6.—School of Hospitality and Tourism, Hue University, 22 Lam Hoang, Hue, Vietnam. 7.—e-mail:
nguyenduccuong@hueuni.edu.vn

Photocatalysis under low energy light is of great importance for study of

environmental pollution impact. There is an increasing demand for preparing
integrated photocatalysts to show their potential in persistent organic com-
pound degradation under visible and near-infrared light. In this work, we
have reported the structural combination of three functional components of
NaYF4:Yb,Er, TiO2, Cu into photocatalytic nanocomposites for near-infrared
light (NIR) photocatalysis. Uniform and monodisperse NaYF4:Yb,Er nano-
cubes prepared by hydrothermolysis were used as a photon converter and they
were combined with TiO2 semiconductor and Cu co-catalysts by sequential
deposition to fabricate NIR-active photocatalysts. The Cu/TiO2/NaYF4:Yb,Er
nanocomposites were investigated for the organic degradation under NIR
light. The Cu/TiO2/NaYF4:Yb,Er photocatalysts were photoactive with NIR
light and full decomposition of methylene blue was reached for 90 min. These
nanocomposites exhibit the NIR photocatalytic response caused by the NIR
light absorption and photon electron transfer over NaYF4:Yb,Er, TiO2, and Cu
components.

Key words: Upconversion nanocrystals, upconversion photoluminescence,

semiconductors, nanocomposite photocatalysts, near-infrared
light-active photocatalysts

INTRODUCTION enhancement of photoactive materials is of key

importance to push the performance efficiency
Functional energy materials are leading candi-
frontier ever outwards.1,6 Optical physics combined
dates to develop emerging technological applica-
with nanochemistry offer an interesting way to
tions in the energy sector.1–3 Photo-induced energy
inspire functional energy materials.7 Thus, of par-
and electron-transfer processes of photocatalysts
ticular interest is to control the composition and
and photovoltaics are renowned as a sustainable
nanoscale of these composites with enhanced per-
way to deal with the impact of the environmetal
formance for photocatalysis,8,9 solar cells,10 and
crisis.4 The major goal of this strategy is to develop
photoswitches.11
new light-absorbing materials also known as pho-
Luminescence upconversion process has attracted
toactive components.5 The light absorbance
the attention of scientists to investigate the energy
transfer through electron transitions.12–16 NaYF4
doped with lanthanide dopants (e.g., Yb, Er) is a
(Received June 16, 2018; accepted September 28, 2018) promising upconversion material useful as a photon
 Van Hau, Nhan, Van Duc, Tuyen, Nguyen, Hoa, and Cuong
converter for energy application.17 The homoge-
neous incorporation of Yb and Er additives into
NaYF4 crystals affords photoluminescent compos-
ites that can absorb near-infrared light by Yb3+ sites
and then emit visible light by Er3+ sites.18–20 The
NaYF4:Yb,Er nanomaterials are able to convert low-
energy light to higher-energy light along with
structural stability and low toxicity.21 These phys-
ical and chemical properties endow NaYF4:Yb,Er
nanocrystals with potential in energy storage and
conversion, bioimaging and photocatalysis.1,22,23
Photocatalysis is a photoreaction in which a
catalyst is used to adsorb light in order to activate
a substance.24 The overall acceleration of photore-
action is dominated by structural and surface
properties of photocatalysts such as bandgap, inter-
faces, sizes and pores.25,26 The low-energy light
from visible and near-infrared ranges is preferable
in photocatalysis to meet practical applications.
Considering this, NaYF4:Yb,Er nanomaterials can
be used as a promising component for the design of
visible light-active photocatalysts.27–29 Notably,
NaYF4:Yb,Er cannot be active as a photocatalyst
by itself when alone, but it provides the photoactive
sites in their integrated composites to create the
emitted upconversion light needed for photocat-
alytic reactions. This property encourages a possible
way of creating near-infrared light-active nanocom-
posite photocatalysts by combining lanthanide-
doped NaYF4 with semiconductors and co-cata-
lysts.29,30 In this three-component photocatalytic
system, semiconductors can function as a charge-
transfer component to relocalize the emitted upcon-
version light from upconverters to co-catalytic sites
to accelerate oxidation and reduction processes.31
The proper selection of semiconductors to combine
with NaYF4:Yb,Er nanocrystals also determines the
reaction performance of the photocatalytic
nanocomposites.32–34 TiO2 is an outstanding semi-
conductor in photoelectrochemical processes.35
Along with inherent characteristics, such as struc-
tural stability and feasibility, TiO2 is unable to
adsorb full sunlight as its photocatalytic activity
often occurs in the ultraviolet spectral region, owing
to its wide bandgap ( 3.2 eV).36,37 The expansion of
the adsorption region of titania to near-infrared or
visible light is a goal to design efficient photocata-
lysts for environment studies.38 Different methods
were proposed to make low energy light-absorbed
TiO2 photocatalysts.39 The controlled synthesis of
photocatalysts with doping-induced tunable band-
gap, junction-driven electron transfer and struc-
ture-created defects is a well-known method for
photocatalytic enhancement.6,40–43 Given that
nanocomposites are made up of a heterogeneous
mixture of NaYF4:Yb,Er upconverter, TiO2 semi-
conductors and metallic co-catalysts are anticipated
to be a near-infrared active photocatalysts useful for
environmental pollutant control. Some recent
efforts were made to prepare TiO2/NaYF4:Yb,Er
nanocomposites,27 but only few investigations are
available for three-component metal/TiO2/NaYF4:Y-
b,Er photocatalysts.29
Herein, we describe the structural design of Cu/
TiO2/NaYF4:Yb,Er nanocomposites for near-in-
frared light-driven photocatalysis. The monodis-
perse and uniform NaYF4:Yb,Er nanocrystals were
hydrothermally synthesized, and then they were
used as a support for sequential deposition of TiO2
and Cu nanoparticles to generate nanocomposites.
The structural properties of as-made Cu/TiO2/
NaYF4:Yb,Er nanocomposites were investigated to
design into the integrated photocatalysts for the
photodegradation of methylene blue under near-
infrared light.
EXPERIMENTAL SECTION
Chemicals
Lanthanide salts, including yttrium(III) nitrate
hexahydrate (Y(NO3)3Æ6H2O), ytterbium(III) nitrate
pentahydrate Yb(NO3)3Æ5H2O, erbium(III) nitrate
pentahydrate Er(NO3)3Æ5H2O, sodium fluoride
(NaF), oleic acid (C18H34O2), sodium hydroxide
(NaOH), titanium (IV) isopropoxide (Ti(OiPr)4),
sodium borohydride (NaBH4), Cu(NO3)2Æ2H2O and
ethanol were used as received without further
purification. Purity rate and supplier should be
reported on for each starting reagent.
Preparation of NaYF4:Yb,Er Upconversion
Nanocubes
An aqueous solution of 150 mg Y(NO3)3Æ6H2O,
108 mg Yb(NO3)3Æ5H2O, and 10.6 mg
Er(NO3)3Æ5H2O in 1 mL distilled water was pre-
pared. Another mixture containing 5 mL oleic acid,
400 mg NaOH, and 116 mg NaF in 20 mL ethanol
was prepared and then added dropwise to this
solution. The resulting mixture was magnetically
stirred at ambient conditions for 30 min and then
transferred into a Teflon-lined autoclave with an
internal volume of 80 mL, sealed, and heated to
180°C for 18 h. The solid product of NaYF4:Yb,Er
upconversion nanocrystals was collected by cen-
trifugation at 6500 rpm min1 and washed with
ethanol.
Preparation of TiO2/NaYF4:Yb,Er
Nanocomposites
The as-prepared NaYF4:Yb,Er nanocrystal pow-
ders (50 mg) were dispersed in an aqueous solution
of 20 mL ethanol and 1 mL water under stirring.
Titanium (IV) isopropoxide (1 mL) was added drop-
wise to this solution under stirring at ambient
conditions and then transferred into a Teflon-lined
autoclave with an internal volume of 80 mL, sealed,
and heated to 180°C for 12 h. The solid product of
TiO2/NaYF4:Yb,Er nanocomposites was diluted
with ethanol and collected by centrifugation and
then dried in an oven at 60°C.
Structural Design of Near-Infrared Light-Active Cu/TiO2/NaYF4:Yb,Er Nanocomposite Pho-
tocatalysts
Preparation of Cu/TiO2/NaYF4:Yb,Er
Nanocomposite Photocatalysts
The as-prepared TiO2/NaYF4:Yb,Er nanocompos-
ites (50 mg) were dispersed in 20 mL ethanol and
then mixed with a Cu(NO3)2 0.25 M aqueous solu-
tion (5 mL) under stirring. A NaBH4 0.25 M aque-
ous solution (5 mL) was added dropwise to the
above resulting mixture under stirring at 50°C for
30 min. The Cu/TiO2/NaYF4:Yb,Er nanocomposite
samples were purified by centrifugation at
6500 rpm min1 for 10 min, washed three times
with ethanol and dried in an oven at 60°C for 6 h.
NIR-Responsive Photocatalytic Study
Photocatalytic activity of the as-prepared Cu/
TiO2/NaYF4:Yb,Er nanocomposites was evaluated
by photocatalytic decolorization of methylene blue
(MB) under NIR irradiation using a 10 W 980 nm
infrared laser diode at ambient conditions. In each
experiment, 20 mg of the Cu/TiO2/NaYF4:Yb,Er
catalyst powder was added to 10 mL of a MB
solution (10 mg L1). Before illumination, the mix-
ture was magnetically stirred in the darkness for
30 min to ensure the adsorption–desorption equi-
librium between catalyst and MB. The solution was
then exposed to NIR light irradiation under mag-
netic stirring. At given time intervals, 0.5 mL of the
MB aqueous mixture was sampled, centrifuged and
filtered to remove the photocatalyst particles. The
UV–Vis absorption spectrum of the centrifuged MB
solution was then recorded using a Jasco V-550 UV–
Vis spectrophotometer.
Structural Characterization
Transmission electron microscopy (TEM) images
of the samples were recorded on a JEOL 1010
electron microscope. A drop ( 0.1 mL) of the
nanoparticle solution was placed onto a carbon-
coated copper grid and then dried at ambient
conditions. The powder x-ray diffraction (PXRD)
patterns of the samples were recorded on a D8
Advance x-ray diffractometer. The energy-disper-
sive x-ray (EDX) spectra and EDX elemental map-
ping were collected using a Hitachi S2300 scanning
electron microscope. The room-temperature UC
photoluminescence spectra were obtained on a
Hitachi F-4500 fluorimeter using a 800 mW lamp
as a source with the excitation wavelength of
980 nm. The UV–Vis absorption spectra were
obtained on a Jasco V-550 UV–Vis
spectrophotometer.
RESULTS AND DISCUSSION
The preparation of NaYF4:Yb,Er UC nanocrystals
and the sequential deposition of TiO2 and Cu
nanoparticles on the UC nanoparticles were
designed to generate Cu/TiO2/NaYF4:Yb,Er
nanocomposites. The hydrothermal reaction was
used to prepare NaYF4:Yb,Er UC nanocrystals with
uniform and monodisperse features. The hydrolysis
of titanium alkoxide was carried out by hydrother-
molysis to attach anatase TiO2 nanoparticles to
NaYF4:Yb,Er nanocrystals. The subsequent deposi-
tion of Cu nanoparticles was carried out by reducing
Cu ions in a TiO2/NaYF4:Yb,Er ethanol mixture to
generate Cu/TiO2/NaYF4:Yb,Er nanocomposites.
The structural and optical properties of these
nanocomposites were analyzed at each step of the
synthesis to design them into near-infrared photo-
catalysts for methylene blue degradation.
The hydrothermal reaction of an aqueous mixture
of lanthanide nitrates, sodium fluoride, oleic acid,
ethanol and water at a quantitated ratio yielded
oleic acid-capped NaYF4:Yb,Er nanocrystals.
Because of the particle surfaces passivated by
hydrophobic oleic acid, the NaYF4:Yb,Er nanocol-
loids can be dispersed in non-polar solvents (e.g.,
toluene) and precipitate in ethanol. The surface
hydrophobicity allowed us to purify oleic acid-ad-
sorbed NaYF4:Yb,Er nanoparticles in a colloidal
form of monodispersity and stability. The transmis-
sion electron microscopy (TEM) images (Fig. 1a)
reveal that the as-made colloidal solutions contain
relatively uniform and monodisperse cubic-shaped
nanoparticles with an average particle size of
around 30 nm. The powder x-ray diffraction pat-
terns (Fig. 2a) of the nanocrystaline products show
distinct diffraction peaks assigned to two structural
modifications b (hexagonal) and a (cubic) in NaY-
F4:Yb,Er nanocrystals.44 The hexagonal b-phase has
higher diffraction intensity than the cubic a-phase,
verifying that the NaYF4:Yb,Er nanocube is a
binary mixture of major b-phase and minor a-phase.
All diffraction peaks are strong and sharp and this
indicates high crystallinity of the as-prepared
NaYF4:Yb,Er nanocubes. No diffraction peaks
assigned to Er3+ and Yb3+ compounds could be
detected, indicating the homogeneous incorporation
of these lanthanide guests into the NaYF4 host
lattice. The previous studies proved that the forma-
tion of the NaYF4:Yb,Er upconversion nanocrystals
is caused by homogeneous substitution of Er3+ and
Yb3+ for Y3+ in NaYF4 crystal lattice.18,45
The as-made NaYF4:Yb,Er nanocrystals in the
colloidal solution and solid forms did not show any
color under visible or ultraviolet light. However,
under illumination with near-infrared laser
(980 nm), the samples possess green luminescent
color. The colloidal and solid nanoparticles both
show the similar emission intensity, reflecting that
their optical upconversion properties retained dur-
ing the purification and solidification. The pho-
tographs shown in Fig. 3a present the upconversion
photoluminescence of the solid NaYF4:Yb,Er
nanocrystals excited at 980 nm. The photolumines-
cence (PL) spectra (Fig. 3d) of the NaYF4:Yb,Er
nanocrystals were recorded under 980 nm laser
excitation. It is apparent from the PL spectra that
the NaYF4:Yb,Er nanocubes show three main emis-
sion peaks at 522.5 nm, 541.5 nm and 655.5 nm as a

(a)
100 nm
100 nm
(c)
100
100 nm
nm
Fig. 1. TEM images of (a) NaYF4:Yb,Er nanocubes, (b) TiO2/NaYF4:Yb,Er nanocomposite, and (c, d) Cu/TiO2/NaYF4:Yb,Er nanocomposite.
result of the 4H11/2-4I15/2 (green), 4S3/2-4I15/2 (green)
and 4F9/2-4I15/2 (red) UC transitions, respectively, of
Er3+ dopants. These structural and optical results
are consistent with the previously reported proper-
ties.44,46,47 The uniformity, crystallinity and photon
efficiency open the way for the as-made NaYF4:Y-
b,Er nanocubes to serve as a near-infrared active
component for designing integrated photocatalysts.
The NaYF4:Yb,Er nanocubes were applied as an
upconversion support for the TiO2 nanocomponent
deposition. Titanium (IV) isopropoxide was used a
titanium precursor to hydrolyze to amorphous TiO2
that condensed on the NaYF4:Yb,Er nanocubes in
water–ethanol. Under hydrothermal treatment,
titania polymorphs crystallized to form TiO2/NaY-
F4:Yb,Er crystalline nanocomposites. The TEM
image shown in Fig. 1b reveals the retention of
the cubic shape and particle size of the NaYF4:Yb,Er
nanocrystals in the TiO2/NaYF4:Yb,Er nanocompos-
ites. The NaYF4:Yb,Er nanocrystals became slightly
aggregated, possibly due to the surface deposition of
titania. By viewing under near infrared light, the
TiO2/NaYF4:Yb,Er nanocomposites still show the
green luminescent color, but its intensity decreases
(Fig. 3b). The PL spectra (Fig. 3d) reveal that the
TiO2/NaYF4:Yb,Er nanocomposites exhibit three
main emission peaks with the similar wavelength
positions as in the pristine NaYF4:Yb,Er nanocubes,
but the intensity is strongly decreased.
At the next step, we deposited Cu nanocompo-
nents on the TiO2/NaYF4:Yb,Er nanocomposites. A
Van Hau, Nhan, Van Duc, Tuyen, Nguyen, Hoa, and Cuong
(b)
100 nm
100 nm
(d)
100nm
100 nm
mixture of TiO2/NaYF4:Yb,Er nanocomposites dis-
persed in ethanol containing Cu ions was prepared
to perform the reduction-induced deposition of Cu
nanoparticles and generate the Cu/TiO2/NaYF4:Y-
b,Er nanocomposites. After the combination with
Cu species, the white TiO2/NaYF4:Yb,Er nanocom-
posite turned to black one. Even in the black color
solid form, the Cu/TiO2/NaYF4:Yb,Er nanocompos-
ite still provides the green luminescence color of the
upconversion components after two combinations
with TiO2 and Cu nanocomponents (Fig. 3c). The
TEM images (Fig. 1c and d) show the nanocubes are
strongly aggregated with each other that may be
due to surface interactions between NaYF4:Yb,Er,
TiO2, Cu components at the nanoscale level. The
surface analysis [energy dispersive x-ray (EDX)]
(Fig. 2b) indicates the presence of main elements
Na, Y, F, Yb, Er, Ti, Cu in the Cu/TiO2/NaYF4:Yb,Er
composites. The PXRD patterns (Fig. 2a) of the
TiO2/NaYF4:Yb,Er nanocomposites show peaks at
25°, 38°, 48°, and 62° 2h attributed to anatase TiO2
alongside of distinct peaks related to NaYF4:Yb,Er
nanocrystals. The PL spectra (Fig. 3d) of the Cu/
TiO2/NaYF4:Yb,Er nanocomposites show the reten-
tion of the shape and position features of the distinct
emission signals of the upconversion nanocrystals.
However, after the simultaneous integration of TiO2
and Cu, these nanocomposites exhibit the consider-
ably reduced emission that can be distinguished
from the intensity of the emission spectra and
luminescent color. This decreased photon efficiency
Structural Design of Near-Infrared Light-Active Cu/TiO2/NaYF4:Yb,Er Nanocomposite Pho-
tocatalysts
(a)
Intensity (a.u.)
Cu/TiO2/NaYF4:Yb,Er
UC: JCPDS No 28-1192
TiO2: JCPDS No 85-1326
10 20 30 40
2-Theta (degrees)
Counts
0 2 4 6
Energy (KeV)
Fig. 2. (a) PXRD patterns of NaYF4:Yb,Er nanocubes and Cu/TiO2/
NaYF4:Yb,Er nanocomposite, and standard XRD patterns of a,b-
NaYF4:Yb,Er (JCPDS 28-1192, anatase TiO2 (JCPDS 85-1326), and
metallic Cu (JCPDS 21-1271) and (b) EDX spectrum of Cu/TiO2/
NaYF4:Yb,Er nanocomposite (Color figure online).
is relevant to the electron transfer occurring
between NaYF4:Yb,Er, TiO2, Cu under near-in-
frared laser excitation. Thus, we can conclude that
the as-made nanocomposites are a heterogeneous
mixture of NaYF4:Yb,Er, TiO2, Cu nanocomponents
and this simultaneous combination still retains the
optical upconversion properties of the NaYF4:Yb,Er
nanosupports.
The photocatalytic activity of the Cu/TiO2/NaY-
F4:Yb,Er nanocomposites was studied by the degra-
dation of methylene blue (MB) as a model pollutant
under 980 nm NIR irradiation. The three-compo-
nent photocatalysts were expected to exhibit the
high reaction performance. To evaluate the photo-
catalytic activity, the photocatalytic reaction was
carried out in a quartz-glass batch reactor under
NIR light and the photodegradation of MB was
recorded by UV–Vis absorption spectroscopy after
NIR illumination at different time intervals. The
β-hexagonal Cu/TiO2/NaYF4:Yb,Er catalyst powder (20 mg) was
α-cubic dispersed in a MB aqueous solution (10 mL,
NaYF4:Yb,Er 10 mg L1). Before illumination, the mixture was
kept in darkness under stirring for 30 min to
establish the adsorption–desorption equilibrium
between the nanocatalyst and MB. The MB/catalyst
aqueous mixture was then exposed to NIR light
irradiation under magnetic stirring. At given time
intervals, 0.5 mL of the reaction mixture was taken
for UV–Vis absorbance measurements. Figure 4
shows the optical spectra related to the NIR light-
driven decomposition of MB by the Cu/TiO2/NaY-
F4:Yb,Er nanocomposite photocatalysts, as recorded
after different irradiation times. The absorption
double peaks at 609 nm and 667 nm are character-
istics of MB. The intensity of these peaks gradually
50 60 70 decreases as a function of irradiation time, indicat-
ing the decomposition of MB. After 90 min of
reaction time, these absorbance peaks mostly dis-
appear, verifying the full photodegradation of MB.
(b) This result is also consistent with the visible
disappearance of blue color of MB in the aqueous
reaction mixture observed during photocatalysis.
Our control experiments show that TiO2 and Cu
alone were inactive under NIR light and MB was
stable without degradation in the absence of the Cu/
TiO2/NaYF4:Yb,Er nanocomposite at NIR illumina-
tion. This comparative assessment supports the
heterogeneous combination of three functional
nanocomponents into the integrated catalyst to be
the origin of the photocatalytic enhancement.
8 10 The NIR-responsive photocatalytic properties of
the Cu/TiO2/NaYF4:Yb,Er nanocomposites arise
from the energy transfer over three different com-
ponents in the NIR-photoactive composites. A pos-
sible photocatalytic mechanism of the Cu/TiO2/
NaYF4:Yb,Er system is proposed in Fig. 5. Under
the 980 nm laser irradiation, the NaYF4:Yb,Er
nanocrystals absorbed NIR light to excite the elec-
trons of Yb3+ dopants from the 2F7/2 to 2F5/2 level.
The photoexcited electrons of Yb3+ were transferred
to Er3+ dopants at the 4I11/2 level owing to their
energy similarity. These transferred electrons
sequentially jumped up to the higher energy level
(4I11/2) by secondary photon absorption by Er3+.
These highly excited electrons of Er3+ then relaxed
to the neighbor states with little lower energy levels
(2H11/2, 4S3/2, 4F9/2) and lastly decayed from these
levels to the ground energy state (4I15/2) with
photoluminescence emission in the visible spectral
region.48 The overall photon upconversion process
led to the visual appearance of the brilliant green
emission in the pure NaYF4:Yb,Er nanocrystals and
their composites under NIR light.
In the Cu/TiO2/NaYF4:Yb,Er composite, the semi-
conducting TiO2 component was excited by the
emitted upconversion light of NaYF4:Yb,Er. This
indirect excitation process led to the sequential
excitation of electrons in the valence band (VB) of
TiO2 to the conductive band (CB) with simultaneous
generation of the same amount of holes (h+) left
 Van Hau, Nhan, Van Duc, Tuyen, Nguyen, Hoa, and Cuong

(a) (b)

NaYF4:Yb,Er TiO2/NaYF4:Yb,Er

(1)

→ 4I15/2 (green)
(c) (d) (1) NaYF4:Yb,Er
4 (2) TiO2/NaYF4:Yb,Er
(3) Cu/TiO2/NaYF4:Yb,Er

PL Intensity (a.u.)

→ 4I15/2 (red)
(green)
3/2
4S
2

11/2→ I15/2
4

9/2
4F
(2)
4H

Cu/TiO2/NaYF4:Yb,Er 0
(3)

468 507 546 585 624 663 702

Wavelength (nm)
Fig. 3. Photographs of the solidified powders of (a) NaYF4:Yb,Er nanocubes, (b) TiO2/NaYF4:Yb,Er nanocomposite, (c) Cu/TiO2/NaYF4:Yb,Er
nanocomposite taken under 980 nm NIR light and (d) upconversion photoluminescence spectra of these corresponding samples under 980 nm
diode laser excitation (Color figure online).

2.5
(1) NIR light
2.0
Absorbance (a.u.)

(1) 0 min
1.5
(2) 15 mins
(3) 30 mins (2)
1.0 (4) 45 mins
(5) 60 mins
Emitted
(6) 90 mins (3) upconversion
0.5 (5)
light
(4) (6)
Fig. 5. A scheme of showing photon energy transfer process over
0.0 three components of NaYF4:Yb,Er, TiO2, Cu in the heterostructured
nanocomposite to propose a NIR-responsive photocatalytic mecha-
450 500 550 600 650 700 750 nism of the Cu/TiO2/NaYF4:Yb,Er system for MB decomposition.

Wavelength (nm)
Fig. 4. UV–Vis absorption spectra of the photocatalytic degradation
of methylene blue by the Cu/TiO2/NaYF4:Yb,Er nanocomposite un-
der 980 nm laser excitation at variable irradiation times (Color figure
online).
behind. The Cu component serves as a metallic co-
catalyst to trap the photoexcited electrons in the CB
of TiO2. This electron transfer process led to the
increase of the lifetime of the photogenerated pairs
Structural Design of Near-Infrared Light-Active Cu/TiO2/NaYF4:Yb,Er Nanocomposite Pho-
tocatalysts
and the reduction of the charge recombination. The
electrons accumulated at Cu particles or in the CB
of TiO2 can be transferred to oxygen molecules
adsorbed on the catalyst surfaces to form free
oxygen radicals, such as O  
2 , HO2 and HO , while
the photoinduced holes react with surface-bound
H2O to generate hydroxyl radical species (HO ).
These HO species are an extremely strong oxidant
for the oxidation-induced decomposition of MB.49,50
This interpretation assumes that the NIR photocat-
alytic phenomenon is caused by the NIR light
absorption and electron transfer occurring on three
components of NaYF4:Yb,Er, TiO2, Cu at the inter-
faces of the nanocomposites. The key photocatalytic
reactions was presented in Eqs. 1–6.51
TiO2 ! hþ þ e ð1Þ
H2 O þ hþ ! HO þ Hþ ð2Þ
O2 þ e ! O
2 ð3Þ
O þ 
2 þ H ! HO2 ð4Þ
2HO2 ! H2 O2 þ O2 ð5Þ
H2 O2 þ e ! HO þ HO ð6Þ
CONCLUSIONS
In summary, we have shown the heterogeneous
combination of NaYF4:Yb,Er upconverter, TiO2
semiconductor, and Cu co-catalyst into nanocom-
posite photocatalysts for near-infrared light-driven
degradation of methylene blue. The monodispersity,
uniformity, crystallinity of hydrothermally pre-
pared NaYF4:Yb,Er nanocubes lead to the visible
appearance of brilliant green photoluminescence
when shining with near-infrared light. The unique
structured features allowed NaYF4:Yb,Er nanocrys-
tals to serve as a photon upconverting support to
attach with functional additives of TiO2- and Cu
nanocomponents. This wet-chemical integration
yielded Cu/TiO2/NaYF4:Yb,Er nanocomposite that
basically retains their photon upconverting
response after multi-step deposition. The Cu/TiO2/
NaYF4:Yb,Er nanocomposite was designed as an
integrated photocatalyst for NIR-responsive photo-
catalysis. In the Cu/TiO2/NaYF4:Yb,Er nanocom-
posite, under NIR irradiation, the NaYF4:Yb,Er
nanocrystals created the upconversion light that
was absorbed by TiO2 semiconductor to generate
photoexcited electrons, and, then, they trapped by
Cu co-catalysts. By dealing with the NIR light
( 46% of solar spectrum) absorption and photon
electron transfer over converter, semiconductor and
co-catalyst, we designed a efficient route to create
the NIR-active photocatalyst for low-energy pho-
todecomposition of persistent organic pollutants.
ACKNOWLEDGMENTS
This research is funded by Vietnam National
Foundation for Science and Technology Develop-
ment (NAFOSTED) under Grant Number 104.06-
2017.311. HVD thanks to financial support from the
Hue University Foundation Programme (DHH
2016-02-83).
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