Journal of Colloid and Interface Science 486 (2017) 16–26

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Journal of Colloid and Interface Science

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

Microfluidic synthesis of Ag@Cu2O core-shell nanoparticles with

enhanced photocatalytic activity
Sha Tao a,b, Mei Yang a,⇑, Huihui Chen a,b, Mingyue Ren a,b, Guangwen Chen a,⇑
a
Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
b
University of Chinese Academy of Sciences, Beijing 100049, China

g r a p h i c a l a b s t r a c t

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

Article history: A microfluidic-based method for the continuous synthesis of Ag@Cu2O core-shell nanoparticles (NPs) has
Received 23 August 2016 been developed. It only took 32 s to obtain Ag@Cu2O core-shell NPs, indicating a high efficiency of this
Revised 15 September 2016 microfluidic-based method. Triangular Ag nanoprisms were employed as the cores for the overgrowth
Accepted 23 September 2016
of Cu2O through the reduction of Cu(OH)2
4 with ascorbic acid. The as-synthesized samples were charac-
Available online 24 September 2016
terized by XRD, TEM, SEM, HAADF-STEM, EDX, HRTEM, UV–vis spectra and N2 adsorption-desorption. The
characterization results revealed that the as-synthesized Ag@Cu2O core-shell NPs exhibited a well-
Keywords:
defined core-shell nanostructure with a polycrystalline shell, which was composed of numbers of Cu2O
Core-shell
Ag@Cu2O
domains epitaxially growing on the triangular Ag nanoprism. It was concluded that the synthesis param-
Microreactor eters such as the molar ratio of trisodium citrate to AgNO3, H2O2 to AgNO3, NaOH to CuSO4, ascorbic acid
Continuous to CuSO4 and AgNO3 to CuSO4 had significant effect on the synthesis of Ag@Cu2O core-shell NPs.
Photocatalytic Moreover, Ag@Cu2O core-shell NPs exhibited superior catalytic activity in comparison with pristine
Cu2O NPs towards the visible light-driven degradation of methyl orange. This enhanced photocatalytic
activity of Ag@Cu2O core-shell NPs was attributed to the larger BET surface area and improved charge
separation efficiency. The trapping experiment indicated that holes and superoxide anion radicals were
the major reactive species in the photodegradation of methyl orange over Ag@Cu2O core-shell NPs. In
addition, Ag@Cu2O core-shell NPs showed no obvious deactivation in the cyclic test.
Ó 2016 Elsevier Inc. All rights reserved.

⇑ Corresponding authors.
E-mail addresses: yangmei@dicp.ac.cn (M. Yang), gwchen@dicp.ac.cn (G. Chen).

http://dx.doi.org/10.1016/j.jcis.2016.09.051
0021-9797/Ó 2016 Elsevier Inc. All rights reserved.
 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26
1. Introduction
Cuprous oxide (Cu2O), as a p-type semiconductor with a
direct band gap of 2.17 eV, has attracted much attention due
to its distinguished optical, electronic and catalytic properties
[1–3]. Various morphologies of Cu2O such as nanospheres, nano-
wires, nanocubes and hollow spheres have been successfully
synthesized [4–9]. The as-prepared Cu2O shows great potential
in the fields of catalysis, medicine, and electrochemistry and so
on [10–13]. In particular, Cu2O has been explored as an efficient
photocatalyst for the degradation of organic compounds owing
to its perfect match with the visible spectrum, low cost and
environmental friendliness [14–16]. Unfortunately, the easy
recombination of photo-generated electron-hole pairs on Cu2O
surface decreases the efficiency of the photodegradation of
organic compounds dramatically, which occurred in the semi-
conductor materials generally [17,18]. In order to get a better
performance, noble metals such as Au, Pt, Pd and Ag have been
employed to satisfy this demand [19,20]. The noble metal-Cu2O
heterostructures always exhibit intriguing co-operative and syn-
ergistic interaction which are different from the single compo-
nent (noble metal or Cu2O) due to the nanoscale interaction
between noble metal and Cu2O [21]. For the photocatalytic pro-
cess, the photon-induced electrons in the conduction band of
Cu2O can transfer to the noble metal because of the Schottky
barrier formed at the noble metal-Cu2O interface, inhibiting the
recombination of the electron-hole pairs [22–24]. Therefore, the
noble metal can act as an electron sink, which can improve
the charge separation efficiency and thereby enhance the photo-
catalytic activity of Cu2O.
From the published literatures dedicated to the noble metal-
Cu2O heterostructures, core-shell nanostructure has been exten-
sively investigated due to the geometrically tailorable synergistic
properties and performances. Up to now, a large number of noble
metal@Cu2O core-shell NPs have been fabricated such as Au@Cu2O,
Pt@Cu2O, Pd@Cu2O and Ag@Cu2O, etc. [25–28]. Generally, noble
metal@Cu2O core-shell NPs can be formed through the epitaxial
or non-epitaxial growth of Cu2O over noble metal nanoparticles
[26,29]. Almost all noble metal@Cu2O core-shell NPs show superior
photocatalytic activities in comparison with the pristine Cu2O,
which are mainly ascribed to the larger surface area and improved
charge separation efficiency. It has been found that the photocat-
alytic activities of noble metal@Cu2O core-shell NPs can be fine
tuned through the precise control over the geometries of core
(shape and size) and shell (crystallinity, thickness and porosity).
For example, Kong et al. found that the photocatalytic activity of
Au@Cu2O core-shell NPs was significantly affected by the thickness
of Cu2O shell [30]. Wang et al. reported that Au hollow
nanospheres@Cu2O core-shell NPs exhibited a much better perfor-
mance than Au solid nanospheres@Cu2O core-shell NPs in the pho-
todegradation of methyl orange [31].
Conventionally, the synthesis of noble metal@Cu2O core-shell
NPs is carried out in a batch reactor. Unfortunately, it is difficult
for the conventional process to offer a uniform precipitation condi-
tion owing to the limitation of mixing in the batch reactor, which
inevitably leads to a wide particle size distribution and poor repro-
ducibility. Recently, microreactors have been widely used for the
continuous synthesis of micro/nano materials such as nickel oxide,
magnetic iron oxide, layered double hydroxides, BaSO4, CdSe/ZnS,
Si@TiO2, c-Fe2O3@SiO2 and hedgehog-like Ag-ZnO nanostructure
[32–40]. In comparison with the conventional batch reactors,
microreactors have many advantages such as large surface-to-
volume ratio, high heat and mass transfer rate resulting from its
characteristic scale of submillimeter size [41–44]. When microre-
actors are used to synthesize micro/nano materials, they can offer
a uniform environment, which is beneficial for the preparation of
17
micro/nano materials with narrow particle size distribution. Addi-
tionally, the continuous operation and easy scale-up of microreac-
tors are both helpful for the large-scale production of micro/nano
materials. To the best of our knowledge, there was no report con-
cerning the continuous synthesis of noble metal@Cu2O core-shell
NPs in the microreactor.
Among the noble metals aforementioned above, Ag has incom-
parable advantages such as low cost and strong LSPRs [45]. Hence,
Ag NPs such as nanowires, nanospheres and nanocubes are widely
used as cores for the overgrowth of Cu2O [25,27,46]. As a typical
example of anisotropic morphologies, triangular Ag nanoprisms
are almost composed of atomically flat (1 1 1) facets [47–50],
which make triangular Ag nanoprisms ideal cores for the over-
growth of Cu2O. Furthermore, the unique LSPR feature of triangular
Ag nanoprisms can be expected to bring about interesting optical
properties of Ag@Cu2O core-shell NPs. Therefore, triangular Ag
nanoprisms were selected as cores for the overgrowth of Cu2O in
this paper. More importantly, a two-stage microfluidic system
which consisted of two capillary microreactors was employed to
synthesize Ag@Cu2O core-shell NPs. The overgrowth of Cu2O shells
on triangular Ag nanoprisms was successfully achieved through a
precise control over the synthesis parameters in the two-stage
microfluidic system.
2. Experimental section
2.1. Materials
Silver nitrate (AgNO3), trisodium citrate (Na3C6H5O72H2O),
sodium dodecyl sulfate (C12H25SO4Na, SDS), hydrogen peroxide
(H2O2), sodium borohydride (NaBH4), copper sulfate pentahydrate
(CuSO45H2O), sodium hydrate (NaOH), ascorbic acid (C6H8O6) and
methyl orange (C14H14N3SO3Na, MO), triethanolamine (C6H15NO3,
TEOA), p-benzoquinone (C6H4O2, PBQ) and isopropanol (C3H8O,
IPA) were purchased with analytical grade. All chemicals were
used as received without further treatment. Deionized water was
used in all experiments.
2.2. The synthesis of triangular Ag nanoprisms
The monodispersed triangular Ag nanoprisms were prepared
following a modified protocol reported by Carboni et al. [51].
AgNO3 and NaBH4 were used as the precursor and reducing agent,
respectively. In a typical experiment, a solution (50 mL) of
0.5 mmol/L AgNO3 with an appropriate amount of trisodium
citrate (1.8 mmol/L), SDS (10 mmol/L) and H2O2 (0.1 mol/L) was
prepared firstly. Next, a solution (50 mL) of 1 mmol/L NaBH4 with
suitable pH (10–12) was prepared by adding adequate NaOH. Sub-
sequently, this NaBH4 solution was injected into the solution con-
taining AgNO3 under stirring. The color of the mixed solution
changed to yellow at once and finally blue, indicating that triangu-
lar Ag nanoprisms were formed. When we investigated the effect
of the molar ratio of trisodium citrate to AgNO3 (trisodium
citrate/AgNO3) and H2O2 to AgNO3 (H2O2/AgNO3) on the synthesis
of Ag@Cu2O core-shell NPs, the concentration of trisodium citrate
or H2O2 varied while other parameters kept unchanged.
2.3. The synthesis of Ag@Cu2O core-shell NPs
Ag@Cu2O core-shell NPs were continuously synthesized in a
two-stage microfluidic system at room temperature. As shown in
Fig. 1, the two-stage microfluidic system was composed of two
consecutive capillary microreactors (T-type and cross-type), which
were both fabricated by polytetrafluoroethylene. T-type and cross-
type capillary microreactors had the same inner diameter of
18 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26
1st Stage
CuSO4
NaOH
Cu(OH)42-
Triangular Ag nanoprisms
Ascorbic Acid
Fig. 1. Experimental arrangements used for the continuous synthesis of Ag@Cu2O core-shell NPs.
0.6 mm and length of 0.7 m. In the first stage, CuSO4 solution and
NaOH solution were simultaneously injected into T-type capillary
microreactor by two syringe pumps with the same flow rate of
0.25 mL/min. The concentration of CuSO4 was fixed at 8 mmol/L,
and the molar ratio of NaOH to CuSO4 (NaOH/CuSO4) varied from
75:1 to 250:1. At the outlet of T-type capillary microreactor, a solu-
tion containing Cu(OH)2
4 was obtained. This Cu(OH)2
4 solution
was directly fed into the cross-type capillary microreactor. At the
same time, the solutions containing triangular Ag nanoprisms
and ascorbic acid were injected into the cross-type capillary
microreactor with the same flow rate of 0.5 mL/min, respectively.
The molar ratio of ascorbic acid to CuSO4 (ascorbic acid/CuSO4)
varied from 1.4:1 to 4.2:1. The yellow-green precipitate out of
the cross-type capillary microreactor was collected by centrifuga-
tion and washed three times with deionized water. Ag@Cu2O
core-shell NPs were finally obtained by drying the precipitate in
the vacuum oven at 60 °C for 5 h. Additionally, Cu2O NPs were also
prepared following the same protocol in this two-stage microflu-
idic system. The solution containing triangular Ag nanoprisms
was replaced by SDS solution with a concentration of 5 mmol/L.
Cu2O NPs were synthesized under a condition of NaOH/
CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1.
2.4. Characterizations
The powder X-ray diffraction (XRD) patterns of the as-prepared
samples were recorded by an X-ray diffractometer (PANalytical
X’pert Pro) at a scanning rate of 5°/min for 2h ranging from 30°
to 90°. The morphologies of the as-prepared samples were charac-
terized by transmission electron microscopy with the accelerating
voltage of 120 kV (TEM, JEOL JEM-2000EX) and scanning electron
microscopy with the accelerating voltage of 1 kV (SEM, JEOL JSM-
7800F). The high-resolution transmission electron microscopy
(HRTEM) image, high-angle annular dark-field scanning transmis-
sion electron microscopy (HAADF-STEM) image and selected area
electron diffraction (SAED) of the as-prepared samples were char-
acterized by JEOL JEM-2100F microscopy equipped with an energy
dispersive X-ray spectrometer (EDS). The UV–vis diffuse reflec-
tance spectra were measured by a PerkinElmer UV/VIS/NIR spec-
trometer. The specific surface areas of the samples were
measured by the BET method on a Quadrasorb SI instrument using
nitrogen adsorption isotherms at 77 K (the cross section of the
nitrogen molecule was taken to the 0.162 nm2).
2nd Stage
Ag@Cu2O core-shell NPs
2.5. Photocatalysis test
The photocatalytic performance of the as-prepared Ag@Cu2O
core-shell NPs was evaluated by the photodegradation of MO as
a representative dye pollutant. A 300 W Xenon lamp (Ushio-
CERMAXLX300) with a 420 nm cutoff filter provides the visible
light irradiation. In a typical procedure, 60 mg catalyst was dis-
persed into 100 mL MO solution with a concentration of 20 mg/L.
The suspensions were placed in a water bath (20 °C) with a con-
stant stirring rate under the Xenon lamp. During the photodegra-
dation, the samples were withdrawn every 10 min and Ag@Cu2O
core-shell NPs were separated from the suspension by centrifug-
ing. The residual MO in the solution was measured by the UV–vis
spectroscopy (Unico UV4802) to evaluate the photodegradation
process. The reusability of Ag@Cu2O core-shell NPs was measured
by three successive repeated cycles of the photodegradation of MO.
3. Results and discussion
3.1. The characterization of Ag@Cu2O core-shell NPs
As stated in the experimental section, Ag@Cu2O core-shell NPs
were continuously synthesized in a two-stage microfluidic system.
In the first stage (T-type capillary microreactor), Cu(OH)2

4 was
formed through the reaction between Cu2+ and OH
. In the second
stage (cross-type capillary microreactor), Ag@Cu2O core-shell NPs
were obtained by the reduction of Cu(OH)2
4 with ascorbic acid in
the presence of triangular Ag nanoprisms, which served as the
cores for the overgrowth of Cu2O. According to the flow rate of
CuSO4 (0.25 mL/min), NaOH (0.25 mL/min), triangular Ag nanopr-
isms (0.5 mL/min) and ascorbic acid (0.5 mL/min) solutions, the
residence time in T-type and cross-type capillary microreactors
was calculated to be 24 s and 8 s, respectively. Compared with
the conventional batch method which usually took 10–60 min, it
was evident that the synthesis of Ag@Cu2O core-shell NPs in the
two-stage microfluidic system spent much less time due to the fas-
ter mixing and was proved to be a highly efficient method to pre-
pare core-shell nanoparticles.
3.1.1. XRD
Fig. 2 shows the XRD patterns of the as-prepared Cu2O NPs and
Ag@Cu2O core-shell NPs. The diffraction peaks at 36.521°, 42.423°,
61.552° and 73.739° in the XRD pattern of the as-prepared Cu2O
 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26 19

(1 1 1)
found in the XRD pattern of the as-prepared Ag@Cu2O core-shell
Cu2 O NPs. Moreover, it can be found that the diffraction peaks of cubic
Ag Cu2O of Ag@Cu2O core-shell NPs broaden in comparison with those
of Cu2O NPs, indicating a smaller crystalline size of cubic Cu2O in
Ag@Cu2O core-shell NPs. This implies that the formation of core-
(2 0 0) shell nanostructure inhibits the further growth of Cu2O NPs.
Intensity /a.u.

(2 2 0) According to the Sherrer’s equation, the crystalline size of cubic

(3 1 1)
(1 1 0) Cu2O is 57 nm and 24 nm in Cu2O NPs and Ag@Cu2O core-shell
NPs, respectively. In addition, no other diffraction peaks are found
A
in the XRD patterns of Cu2O NPs and Ag@Cu2O core-shell NPs, indi-
cating a high purity of the as-prepared samples.

(1 1 1) (3 1 1)
3.1.2. TEM, SEM, STEM-EDS and HRTEM
B
Transmission electron microscopy (TEM) and scanning electron
10 30 50 70 90 microscopy (SEM) were employed to visually observe the morphol-
ogy of the as-prepared samples. Figs. S1 and 3 display the TEM and
SEM images of the as-prepared Ag cores, Cu2O NPs and Ag@Cu2O
Fig. 2. The XRD patterns of (A) Cu2O NPs (B) Ag@Cu2O core-shell NPs synthesized at
trisodium citrate/AgNO3 = 3.6:1, H2O2/AgNO3 = 16:1, NaOH/CuSO4 = 125:1, ascorbic
core-shell NPs. As shown in Fig. S1A, Ag cores are mainly composed
acid/CuSO4 = 2.1:1, CuSO4/AgNO3 = 16:1. of truncated triangular Ag nanoprisms with the edge length rang-
ing from 20 nm to 50 nm. Correspondingly, the UV–vis spectra of
NPs can be indexed to the (1 1 0), (1 1 1), (2 0 0), (2 2 0) and (3 1 1) Ag cores exhibits two absorption peaks at 330 nm and 931 nm,
facets of cubic Cu2O, respectively (JPCDS-077-0199). Two crys- which can be attributed to the weak but sharp out-of-plane
talline phases of cubic Cu2O and cubic Ag (JPCDS-087-0717) are quadruple resonance and the strong dipole resonance of triangular

Fig. 3. (A, B) TEM image (C) SEM image (D) HADDF-STEM image (E) Ag mapping (F) Cu mapping (G) O mapping of Ag@Cu2O core-shell NPs synthesized at trisodium citrate/
AgNO3 = 3.6:1, H2O2/AgNO3 = 16:1, NaOH/CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/Ag = 16:1. (H) TEM image (I) HRTEM image (J) SAED pattern of Ag@Cu2O core-
shell NPs synthesized at trisodium citrate/AgNO3 = 3.4:1, H2O2/AgNO3 = 16:1, NaOH/CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/Ag = 11.2:1.
20 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26
Ag nanoprisms, respectively (Fig. S2). The as-prepared Cu2O NPs
possess a cubic morphology with an average diameter of 50 nm,
which is in good accordance with the XRD result (Fig. S1B). The
TEM image in Fig. 3A shows that the as-prepared Ag@Cu2O core-
shell NPs display a triangular nanoprism shape, suggesting that
the morphology of triangular Ag nanoprisms is well preserved.
The bright/dark contrast of TEM image clearly reveals that core-
shell nanostructure is successfully achieved. The triangular Ag
nanoprisms are encapsulated by Cu2O shells with the thickness
of ca. 34 nm and each core-shell nanoparticle contains one triangu-
lar Ag nanoprism in the center. The enlarged TEM image of an indi-
vidual Ag@Cu2O core-shell NP reveals that the outer surface
exhibits a rough feature (Fig. 3B), which is further verified by
SEM analysis. As shown in Fig. 3C, it is obvious that Ag@Cu2O
core-shell NPs own extremely rough outer surfaces which are com-
posed of a large number of nanoscale protrusions. To better con-
firm the core-shell nanostructure, HAADF-STEM and
corresponding EDX mapping of Cu, Ag and O elements were con-
ducted. It can be seen that the HAADF-STEM image shows a much
clearer contrast between the core and shell than the TEM image
(Fig. 3D). As depicted in Fig. 3E–G, the signal of Ag element appears
only in the center of the nanoparticle, while the signals of Cu and O
elements are distributed uniformly across the entire nanoparticle.
Obviously, the result of EDX elemental mapping matches well with
the core-shell nanostructure.
To study more structural information about the Ag core, Cu2O
shell and interface between the core and shell, HRTEM and SAED
were carried out. To clearly resolve the lattice fringes of the core
and shell, Ag@Cu2O core-shell NPs with a thinner shell were syn-
thesized at a smaller molar ratio of CuSO4 to AgNO3 (Fig. 3H, Sec-
tion 3.2.5). As shown in Fig. 3J, the lattice fringes with an
interplanar spacing of 0.23 and 0.24 nm can be attributed to the
(1 1 1) facet of Ag and (1 1 1) facet of Cu2O, respectively. Appar-
ently, the (1 1 1) facet of Cu2O epitaxially grows on the (1 1 1) facet
of Ag with a lattice mismatch of 4.2%. Fig. 3I depicts the SAED pat-
tern of the core-shell nanoparticle in Fig. 3H. The SAED pattern is
indicative of distinct diffraction rings, indicating that Cu2O shell
is in a polycrystalline nature. Generally speaking, taking into
account the formation mechanism of core-shell nanostructure,
the noble metal@Cu2O core-shell NPs can be classified into three
types (1) Cu2O shell is mono-crystalline and epitaxially grows on
the noble metal nanoparticle [46]; (2) Cu2O shell is polycrystalline
and composed of many mono-crystalline Cu2O domains epitaxially
growing on the noble metal nanoparticle [52]; (3) Cu2O shell is
polycrystalline which grows on the noble metal nanoparticle via
non-epitaxial mechanism [26]. The HRTEM and SAED results
implied that the as-prepared Ag@Cu2O core-shell NPs possess a
polycrystalline Cu2O shell which was composed of many mono-
crystalline domains epitaxially growing on the triangular Ag
nanoprisms with random orientations. On the basis of aforemen-
tioned results, a plausible formation mechanism of Ag@Cu2O
core-shell NPs is proposed and summarized in Fig. 4. Initially, Cu
(OH)2
4 was reduced by the ascorbic acid to generate Cu2O which
heterogeneously nucleated on triangular Ag nanoprisms to form
Cu(OH)42-
Cu(OH)42- Cu(OH)42-
2- 2-
Cu(OH)4 Cu(OH)4
Cu(OH)42- Cu(OH)42-
Ag
Cu(OH)42- Cu(OH)42-
Cu(OH)42- Cu(OH)42-
2- 2-
Cu(OH)42- Cu(OH)4 Cu(OH)4
Fig. 4. Schematic illustration of the plausible formation mechanism of Ag@Cu2O core-shell NPs.
B
Abs /a.u.
A
300 400 500 600 700 800
Wavelength /nm
Fig. 5. UV–vis diffuse reflectance spectra of (A) Cu2O NPs and (B) Ag@Cu2O NPs
synthesized at trisodium citrate/AgNO3 = 3.6:1, H2O2/AgNO3 = 16:1, NaOH/
CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/AgNO3 = 16:1.
nucleation sites for subsequent epitaxial growth of Cu2O domains.
As the reaction time prolonged, the Cu2O domains contacted with
each other to form a shell surrounding the triangular Ag
nanoprism.
3.1.3. UV–vis diffuse reflectance spectra
UV–vis diffuse reflectance spectra were performed to study the
optical properties of the as-prepared Cu2O NPs and Ag@Cu2O core-
shell NPs. As shown in Fig. 5, the absorption spectra of pristine
Cu2O NPs lights up at ca. 630 nm, which matches well with the
characteristic value of Cu2O. Compared with the pristine Cu2O
NPs, Ag@Cu2O core-shell NPs display a strong absorption in the
range of 300–800 nm. The absorption peak between 300 nm and
500 nm is caused by the presence of Cu2O, while the absorption
peak above 600 nm can be ascribed to the presence of triangular
Ag nanoprisms.
3.2. The effect of the synthesis parameters on the synthesis of Ag@Cu2O
core-shell NPs
3.2.1. The molar ratio of trisodium citrate to AgNO3
It is well known that trisodium citrate plays a crucial role in the
synthesis of triangular Ag nanoprisms. As a capping agent, citrate
ions can selectively bind to the (1 1 1) facets and inhibit the Ag
nuclei growing along the direction which is perpendicular to the
(1 1 1) facets and form triangular Ag prisms [53]. In this section,
the molar ratio of trisodium citrate to AgNO3 was found to have
a significant effect on the synthesis of Ag@Cu2O core-shell NPs.
The TEM images of Ag@Cu2O core-shell NPs synthesized at differ-
ent molar ratios of trisodium citrate to AgNO3 are shown in
Fig. 6. When the molar ratio of trisodium citrate to AgNO3 equals
to 3.6:1, well-defined Ag@Cu2O core-shell NPs are obtained.
Cu2O nuclei Cu2O shell
2- 2-
Cu(OH)4 Cu(OH)4
Cu(OH)42- Ag Cu(OH)42- Ag
Cu(OH)42- Cu(OH)42-
Cu(OH)42- Cu(OH)42-Cu(OH)42-
 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26 21

Fig. 6. TEM images of Ag@Cu2O core-shell NPs synthesized at different molar ratio of trisodium citrate to AgNO3 (A) 3.4:1 (B) 3.6:1 (C) 4:1 (D) 4.4:1 H2O2/AgNO3 = 16:1,
NaOH/CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/Ag = 16:1.

Increasing the molar ratio of trisodium citrate to AgNO3 to 4.0:1
and 4.4:1 leads to the formation of free Cu2O NPs. Generally, the
key factor for the preparation of core-shell nanoparticles is to
obtain heterogeneous nucleation of the shell on the core and inhi-
bit homogeneous nucleation of the shell in the solution. Therefore,
the morphology of Ag-Cu2O heterostructure is dependent on the
competition between the heterogeneous and homogeneous nucle-
ation of Cu2O. It can be predicted that the amount of citrate ions
binding to (1 1 1) facets of triangular Ag nanoprisms increases with
the increasing molar ratio of trisodium citrate to AgNO3. To some
extent, the large amount of citrate ions binding to (1 1 1) facets
may suppress the heterogeneous nucleation of Cu2O on triangular
Ag nanoprisms and thereby result in the presence of free Cu2O NPs.
Additionally, the surface of Ag@Cu2O core-shell NPs synthesized at
4.0:1 and 4.4:1 is found to become more rougher than the sample
synthesized at 3.6:1. It can be clearly seen that Cu2O shell is com-
posed of many small nanocrystals, which further confirms the
plausible formation mechanism of Ag@Cu2O core-shell NPs.
3.2.2. The molar ratio of H2O2 to AgNO3
Apart from trisodium citrate, H2O2 is also found to be of great
importance in the synthesis of triangular Ag nanoprisms H2O2
can work as an oxidizing agent as well as etching agent, removing
the less stable seeds and inducing to generate seeds with stacking
faults which finally grow into triangular nanoprisms [51]. If there
is no H2O2 in the solution, Ag+ ions will trend to grow into Ag nano-
spheres by the reduction of NaBH4. In this section, moderate
amount of H2O2 was found to be crucial for the synthesis of
Ag@Cu2O core-shell NPs. The TEM images of Ag@Cu2O synthesized
at different molar ratio of H2O2 to AgNO3 are depicted in Fig. 7. It
can be seen that free Cu2O NPs coexist with Ag@Cu2O core-shell
NPS when the molar ratio of H2O2 to AgNO3 is smaller than 12:1.
The free Cu2O NPs possess a cubic morphology which is similar
with those synthesized in the absence of triangular Ag nanoprisms.
As the molar ratio of H2O2 to AgNO3 goes up to 16:1, only Ag@Cu2O
core-shell NPs are found. It is supposed that H2O2 can help produce
triangular Ag nanoprisms with stacking faults, which are beneficial
for the heterogeneous nucleation of Cu2O. Further increasing the
molar ratio of H2O2 to AgNO3 to 24:1 results in the appearance
of free Cu2O NPs. This can be attributed to the smaller amount of
triangular Ag nanoprisms which is caused by the strong oxidizing
power of excessive H2O2.
3.2.3. The molar ratio of NaOH to CuSO4
The effect of the molar ratio of NaOH to CuSO4 on the synthesis
of Ag@Cu2O core-shell NPs was also investigated. Fig. 8 shows the

Fig. 7. TEM images of Ag@Cu2O core-shell NPs synthesized at different molar ratio of H2O2 to AgNO3 (A) 8:1 (B) 12:1 (C) 16:1 (D) 20:1 (E) 24:1. Trisodium citrate/
AgNO3 = 3.6:1, NaOH/CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/Ag = 16:1.
22 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26

Fig. 8. TEM images of Ag@Cu2O core-shell NPs synthesized at different molar ratio of NaOH to CuSO4 (A) 75:1 (B) 125:1 (C) 175:1 (D) 250:1. Trisodium citrate/AgNO3 = 3.6:1,
H2O2/AgNO3 = 16:1, ascorbic acid/CuSO4 = 2.1:1, CuSO4/AgNO3 = 16:1.

TEM images of Ag@Cu2O core-shell NPs synthesized at different
molar ratio of NaOH to CuSO4. It is observed that an exceedingly
high molar ratio of NaOH to CuSO4 is necessary for the synthesis
of well-defined core-shell nanoparticles. Theoretically, a molar
ratio of NaOH to CuSO4 of 4 is needed to form Cu(OH)2
4 . However,
Cu(OH)2 is not a typical amphoteric hydroxide and can be only
transformed to Cu(OH)2
4 in extremely strong basic condition. For
instance, a molar ratio of OH
to Cu2+ of 375 and 224 was required
for the formation of Cu(OH)2
4 in the studies of Cao et al. and Jing
et al. [46,54], respectively. When the molar ratio of NaOH to CuSO4
is 75:1, a large number of free Cu2O NPs with cubic shape are
found. As the molar ratio of NaOH to CuSO4 rises to 125:1, only
well-defined Ag@Cu2O core-shell NPs are detected.
3.2.4. The molar ratio of ascorbic acid to CuSO4
Ascorbic acid, as a weak dibasic acid, owns two enolic hydroxyl
groups, which can easily lose two hydrogen atoms and turn to
dehydroascorbic acid. Consequently, ascorbic acid was employed
to be a mild reducing agent for the formation of Cu2O from
Cu(OH)2
4 . Fig. 9 depicted the TEM images of Ag@Cu2O core-shell
NPs synthesized at different molar ratio of ascorbic acid to CuSO4.
It can be seen that well defined Ag@Cu2O core-shell NPs are formed
with the molar ratio of ascorbic acid to CuSO4 ranging from 1.4:1 to
2.8:1. When the molar ratio of ascorbic acid to CuSO4 increase to
4.2:1, a small number of free Cu2O NPs are found. It is evident that
the molar ratio of ascorbic acid to CuSO4 has a significant effect on
the synthesis of Ag@Cu2O core-shell NPs. As the molar ratio of
ascorbic acid to CuSO4 went up, the reducing rate of Cu(OH)2
4 to
Cu2O became higher. Excessively high reducing rate could result
in a homogenous nucleation of Cu2O in the solution instead of
heterogeneous nucleation of Cu2O over triangular Ag nanoprisms.
Therefore, free Cu2O NPs are formed with the molar ratio of ascor-
bic acid to CuSO4 of 4.2:1.
3.2.5. The molar ratio of CuSO4 to AgNO3
The thickness of Cu2O shell is one of the most important geo-
metrical parameters of noble metal@Cu2O core-shell NPs, which
dramatically affects the optical properties and photocatalytic

Fig. 9. TEM images of Ag@Cu2O core-shell NPs synthesized at different molar ratio of ascorbic acid to CuSO4 (A) 1.4:1 (B) 2.1:1 (C) 4.2:1. Trisodium citrate/AgNO3 = 3.6:1,
H2O2/AgNO3 = 16:1, NaOH/CuSO4 = 125:1, CuSO4/AgNO3 = 16:1.
 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26 23

Fig. 10. TEM images of Ag@Cu2O core-shell NPs synthesized at different molar ratio of CuSO4 to AgNO3 (A) 8:1, trisodium citrate/AgNO3 = 3.2:1 (B) 10.8:1, trisodium citrate/
AgNO3 = 3.4:1 (C) 16:1, trisodium citrate/AgNO3 = 3.6:1 H2O2/AgNO3 = 16:1, NaOH/CuSO4 = 125:1, ascorbic acid/CuSO4 = 2.1:1.

performances. Generally, the thickness of Cu2O is controlled by

altering the molar ratio of noble metal to Cu2+ ions. In this section, 1.2
the concentration of CuSO4 varied from 4.8 to 8 mmol/L while the A
concentration of AgNO3 kept unchanged. Fig. 10 shows the TEM 1
images of Ag@Cu2O core-shell NPs synthesized at different molar blank
ratio of CuSO4 to AgNO3. It is found that the molar ratio of triso- 0.8 pure 1Cu2O NPs
dium citrate to AgNO3 should decrease with the decreasing molar Ag@Cu2 2O NPs-24
ratio of CuSO4 to AgNO3 to obtain well-defined Ag@Cu2O core-shell Ag@Cu4 2O NPs-27
0.6
NPs. For example, the molar ratio of trisodium citrate to AgNO3 is Light on Ag@Cu2O NPs-34

C/C0
5
3.6:1 at the molar ratio of CuSO4 to AgNO3 of 16:1, while a molar
ratio of trisodium citrate to AgNO3 of 3.2:1 is needed at the molar 0.4
ratio of CuSO4 to AgNO3 of 8:1. It can be seen from Fig. 10 that the
thickness of Cu2O increases from 24 nm to 34 nm with the increas- 0.2
ing molar ratio of CuSO4 to AgNO3.
0
3.3. Photodegradation of MO -30 -20 -10 0 10 20 30 40 50 60 70
Time /min
3.3.1. Photocatalytic activity and stability
The photodegradation of MO as a model reaction was carried 1.2
B 1st run 2nd run 3nd run
out under visible-light irradiation to evaluate the photocatalytic
performance of Ag@Cu2O core-shell NPs [55]. Herein, the photocat- 1
alytic activities of the as-prepared pristine Cu2O NPs and Ag@Cu2O
core-shell NPs with different shell thicknesses were compared. 0.8 Light on Light on Light on
Fig. S3 shows the temporal evolution of UV–vis absorption spectra
of MO during the photodegradation over pristine Cu2O NPs and
C/C0

0.6
Ag@Cu2O core-shell NPs. It can be clearly seen that the character-
istic absorption peak of MO at 464.5 nm decreases gradually as the
irradiation time is prolonged, indicating the efficient degradation 0.4
of MO. As depicted in Fig. 11A, where C represents the concentra-
tion of MO remaining in the solution after irradiation and C0 repre- 0.2
sents the initial concentration of MO, the photodegradation of MO
does not occur in the absence of a catalyst. When pristine Cu2O NPs 0
are added to the MO solution, fast photodegradation of MO is -30 0 30 60 90 120 150 180 210 240 270
achieved. 81% MO is degraded within 70 min. According to the Time /min
study of Li et al. [56], Ag@Cu2O core-shell NPs with the shell
Fig. 11. (A) Photocatalytic activity of the as-prepared pristine Cu2O NPs and
thickness around 11–30 nm exhibited best performance in the Ag@Cu2O NPs (B) reusability of the as-prepared Ag@Cu2O NPs for the degradation of
photodegradation of MO. Therefore, the as-prepared Ag@Cu2O MO under visible light irradiation.
core-shell NPs with the similar shell thickness (24–34 nm) in our
study were expected to exhibit excellent performance in the
Table 1
photodegradation of MO. As expected, Ag@Cu2O core-shell NPs all
The BET surface area of the as-prepared Cu2O NPs and Ag@Cu2O core-shell NPs.
show superior photocatalytic activities than pristine Cu2O NPs.
After 40 min of irradiation, 89.2%, 92.5% and 88.0% MO is degraded Sample Cu2O Ag@Cu2O-24 Ag@Cu2O-27 Ag@Cu2O-34
over Ag@Cu2O core-shell NPs with the shell thickness of 24, 27 and BET surface 7.8 12.5 14.6 14.4
34 nm, respectively. Evidently, Ag@Cu2O core-shell NPs with the area (m2/g)
shell thickness of 27 nm exhibit the highest catalytic activity. In
order to study the mechanism of the enhanced photocatalytic
activity over Ag@Cu2O core-shell NPs, N2 adsorption-desorption Correspondingly, Ag@Cu2O core-shell NPs outperform pristine
was conducted and the BET surface area of the as-prepared sam- Cu2O NPs. It is noticeable that Ag@Cu2O core-shell NPs with the
ples are summarized in Table 1. Pristine Cu2O NPs maintain the shell thickness of 34 nm has a higher BET surface area of
lowest BET surface area of 7.81 m2/g. The formation of Ag@Cu2O 14.6 m2/g, whereas the photocatalytic activity is close to Ag@Cu2O
core-shell nanostructures results in an increase in BET surface area. core-shell NPs with the shell thickness of 24 nm and lower BET
24 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26

1.2
A
1

0.8

Light on
0.6

C/C0
0.4 3
No scavenger
TEOA4
PBQ5
0.2 IPA 1

0
-30 -20 -10 0 10 20 30 40 50 60 70
Time/min

Fig. 12. (A) Photocatalytic activity of the as-prepared Ag@Cu2O NPs in the presence of scavengers (B) schematic diagram of the electron-hole pairs separation and catalysis
mechanism of the as-prepared Ag@Cu2O NPs under visible light irradiation.

surface area of 12.5 m2/g. This indicates that the BET surface area is
not the only factor with respect to the enhanced catalytic activity.
As is well known, the improved charge separation efficiency over
noble metal@Cu2O core-shell NPs is another key factor for the
enhanced photocatalytic activity. The shell thickness has been
found to affect the charge separation efficiency in terms of the life
time and recombination of photo-induced electron-hole pairs due
to the various surface states. Therefore, a moderate shell thickness
is desirable for the efficient photodegradation of MO. On the basis
of the above results, Ag@Cu2O core-shell NPs with the shell thick-
ness of 24 nm seem to own the highest charge separation effi-
ciency. To sum up, the superior photocatalytic activity of
Ag@Cu2O core-shell NPs in this study can be attributed to the lar-
ger surface area and higher charge separation efficiency, in good
accordance with previous studies. To evaluate the durability of
as-synthesized Ag@Cu2O NPs, cycled test was carried out over
Ag@Cu2O core-shell NPs with the shell thickness of 34 nm. As
shown in Fig. 11B, the photocatalytic activity exhibits no obvious
distinction in the third run, compared with that of the first run.
The TEM image of the used core-shell NPs (Fig. S4) displays that
the core-shell nanostructure is well preserved in the photodegra-
dation of MO.
3.3.2. Plausible mechanism
It is generally accepted that reactive species such as holes (h+),


O2 and OH play a vital role in the photodegradation of MO. To
study the plausible mechanism of MO photodegradation over
Ag@Cu2O core-shell NPs, the effect of scavengers on the pho-
todegradation was investigated and the results are depicted in
Fig. 12A. Triethanolamine (TEOA), p-benzoquinone (PBQ) and iso-
propanol (IPA) were employed as the scavengers of h+, O
2 and

OH, respectively. As shown in Fig. 12A, the photodegradation of
MO is completely inhibited by the addition of TEOA, indicating that
h+ is the major reactive species for the photodegradation of MO.
The presence of PBQ also significantly decreases the efficiency of
MO degradation, implying O
2 plays an important role in the pho-
todegradation of MO. Compared with TEOA and PBQ, the effect of
IPA is less obvious, but OH is also crucial in the photodegradation
of MO. Based on the effect of scavengers, a plausible mechanism of
the photodegradation of MO over Ag@Cu2O core-shell NPs was
proposed and present in Fig. 12B. Under the visible-light irradia-
tion, the electrons in the valence band of Cu2O can be excited to
the conduction band, leaving an equal number of holes in the
valence band. Since the energy level of the conduction band of
Cu2O is higher than the Fermi energy level of Ag@Cu2O core-shell
NPs, the photoinduced electrons in the conduction band of Cu2O
transfer to triangular Ag nanoprisms. As a result, the recombina-
tion of photoinduced electrons and holes was inhibited, prolonging
the lifetime of electron-hole pairs and improving the charge sepa-
ration efficiency. During the photodegradation of MO, the electrons
in the conduction band of Cu2O or trapped by triangular Ag
nanoprisms can be captured by the adsorbed oxygen on the surface
to form superoxide anion radical (O
2 ). At the same time, the holes
left in the valence band of Cu2O can be trapped by the surface
hydroxyl to form the hydroxyl radicals (OH) which is an extraordi-
nary strong oxidant for the degradation of MO. The relevant reac-
tions were summarized as follows.
þ
Cu2 O þ hv ! e
ðCBÞ þ h ðVBÞ ð1Þ


e
ðCBÞ þ O2 ! O2 ð2Þ
þ
h þ OH
!  OH ð3Þ

OH þ MO ! degradation products ð4Þ

O
2 þ MO ! degradation products ð5Þ
 S. Tao et al. / Journal of Colloid and Interface Science 486 (2017) 16–26
4. Conclusion
In summary, Ag@Cu2O core-shell NPs were successfully synthe-
sized in a two-stage microfluidic system at room temperature. In
the first stage, Cu(OH)2

4 was formed through the reaction between
Cu2+ and OH
. In the second stage, Ag@Cu2O core-shell NPs were
obtained by the reduction of Cu(OH)2
4 with ascorbic acid in the
presence of triangular Ag nanoprisms, which served as the cores
for the overgrowth of Cu2O. In order to achieve a well-defined
core-shell nanostructure, moderate molar ratios of trisodium
citrate to AgNO3, H2O2 to AgNO3, NaOH to CuSO4, ascorbic acid to
CuSO4 and AgNO3 to CuSO4 were necessary. The photocatalytic
experiments showed that the as-synthesized Ag@Cu2O core-shell
NPs exhibited a much better performance than pristine Cu2O NPs
in the degradation of MO, which could be attributed to the larger
BET surface area and improved charge separation efficiency. On
basis of the trapping experiment, a plausible mechanism for the
photodegradation of MO over Ag@Cu2O core-shell NPs was
proposed. The microfluidic-based method for the synthesis of
Ag@Cu2O core-shell NPs was highly efficient and expected to be
used in the synthesis of other kinds of core-shell NPs.
Acknowledgements
The authors gratefully acknowledge the financial support from
National Natural Science Foundation of China (Nos. 21406226,
21225627).
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2016.09.051.
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