Ethylenediamine-modulated synthesis of highly monodisperse copper sulfide microflowers with excellent photocatalytic performance

Article abstract of DOI:10.1039/c4ta04232h

Highly monodisperse CuS microflowers with uniform size and shape were successfully constructed by a simple one-pot solvothermal approach assisted by EDA and PVP. When used as photocatalysts, the as-obtained CuS materials exhibited excellent photocatalytic activity and good selectivity for the degradation of organic contamination in waters.

Full text of DOI:10.1039/c4ta04232h

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Journal of Materials Chemistry A
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DOI: 10.1039/C4TA04232H
Journal of Materials Chemistry A
Ethylenediamine-Modulated Synthesis of Highly Monodisperse Copper Sulfide
Microflowers with Excellent Photocatalytic Performance†
Zheng Kun Yang,a,b, Le Xin Song *a,b,c,Yue Tengb,c and Juan Xiab,c
Received 13th August 2014, Accepted Xth XXXXXXXXX 2014
First published on the web Xth XXXXXXXXX 2014
DOI: 10.1039/b000000h
5
Highly monodisperse CuS microflowers with uniform size and 55 black monodispersed CuS microflower material with highly uniꢀ
shape were successfully constructed by a simple one-pot
solvothermal approach assisted by EDA and PVP. When used as
10 photocatalysts, the as-obtained CuS materials exhibited excellent
photocatalytic activity and good selectivity for the degradation of
organic contamination in waters.
form dimensions was successfully synthesized in high yield
(CuSꢀ1, 0.042 g, 87%) using a sealed Teflonꢀlined stainless steel
autoclave (50 mL) at 433 K for 12 h. To the best of our knowledge,
this is the first example of a wellꢀmonodispersed and highly uniꢀ
60 form CuS microflower structure produced from a competitive
equilibrium state between a coordination process19 of Cu2+ with
EDA and a precipitation process of Cu2+ with S2−, in which the
effect of EDA was introduced as a competing reaction for availaꢀ
ble Cu2+ ions. The synthesis is repeated but with 60 µL EDA,
65 giving another monodispersed CuS microflower material (CuSꢀ2).
Finally, the CuS microflowers show an excellent photocatalytic
activity for methylene blue (MB) and rhodamine 6G (R6G) (>98%)
and a very low activity for methyl orange (MO) (<10%), thereby
implying a high selectivity for these pollutants. We consider this
70 work not only provides a new successful method for the creation of
monodisperse CuS microflowers, but also help us to gain more
insight into the formation of other metal sulfide materials.
The crystallographic structure and phase purity of the CuSꢀ1
was determined by Xꢀray diffraction (XRD, Fig. 1a). All of the
75 diffraction peaks were assigned to hexagonal CuS with a space
group of P63/mmc (JCPDS 06−0464).20 No peak of impurity was
found in the XRD patterns. The highꢀresolution transmission
electron microscopy (HRꢀTEM) image of CuSꢀ1 in Fig. 1b exꢀ
hibits a lattice spacing of 0.302 nm, which corresponds to the (102)
80 planes of the hexagonal CuS. The inset in Fig. 1b displays the
selectedꢀarea electron diffraction (SAED) pattern, clearly exhibꢀ
iting polycrystalline diffraction rings due to the (102), (107) and
(202) planes of hexagonal CuS material.21 The typical morphology
and detailed structure of the asꢀprepared CuS material were shown
85 by scanning electron microscope (SEM) analysis. Fig. 1c provides
an undistorted panoramic view of the CuSꢀ1 material, consisting of
uniform flowerꢀlike particles. It is worth stressing that the
wellꢀdefined CuS microflowers with a diameter of 2.5~3 µm are
disposed separately from each other, representing a unique monꢀ
90 odisperse structure in dimension and shape. Furthermore, the
detailed structure of a single CuS microflower (Fig. 1d) looks like
a carnation flower (see the inset of Fig. 1c), indicating that the
flower surface is comprised of a large number of nanosheet petals
with a thickness of approximately 30 nm (Fig. 1e).
Copper sulfide (CuS), a typical metal sulfide, has been shown to
have wide applications in many fields, such as photocatalysis,1
15 electrochemistry sensors,2 solar cells,3 lithium ion batteries,4 and
biomedicine,5 because of its outstanding optical, electronic, and
other physical and chemical properties.6,7 It was found that the
functional performance of CuS is closely associated with its size
and morphology.8 Recently, there are numerous reports on the
20 synthesis of micro/nanostructured CuS through the usage of difꢀ
ferent methods including in situ sourceꢀtemplateꢀinterface reaction
route,9 polymerꢀassisted solvothermal process,10 and solvothermal
reaction in ethylene glycol.11 These studies were focused on the
construction of CuS particles of various morphologies such as
25 nanosheets,12 nanotubes,13 concaved cuboctahedra14 and
ballꢀflowers.1 Many synthesis strategies have been reported to
work well in generating ordered assembledꢀstructures of CuS,15,16
but most of them are operationally tedious, and especially cannot
produce highly monodisperse particles with substantially uniform
30 size and shape in a large scale. Undoubtedly, it is a challenge to
devise a straightforward method to solve this problem.
The framework of the present study is an attempt to synthesize
highly monodisperse CuS crystals with a uniform size and shape
by an efficient and facile oneꢀstep solvothermal reaction using
35 ethylene glycol (EG, 35 mL) as solvent. Copper chloride dihydrate
(CuCl2·2H2O, 0.085 g, 0.5 mmol) and sulfur powder (0.045 g, 1.4
mmol) were used as the copper source and sulfur source, respecꢀ
tively, while poly(vinylpyrrolidone) (PVP, 0.4 g) and ethyleneꢀ
diamine (EDA, 20 µL) were used as the structureꢀdirecting agent17
40 and coordination ligand,18 respectively. Our results indicated that a
aDivision of Nanomaterials and Chemistry, Hefei National Laboratory for
Physical Sciences at Microscale, University of Science and Technology of
China, Hefei 230026, P. R. China.
45 bDepartment of Chemistry, University of Science and Technology of China,
Jin Zhai Road 96, Hefei 230026, P. R. China.
95
The formation of the monodisperse CuS microflowers can be
described by Equations 1~5 and Fig. 2. First, EDA coordinates
with Cu2+ in EG solution to form [Cu(EDA)2]2+, as seen from
Equation 1 and step I. In the solvothermal process, acetaldehyde is
produced from the EG decomposition (Equation 2) and may doꢀ
cCAS Key Laboratory of Materials for Energy Conversion, Department
of Materials Science and Engineering, University of Science and
Technology of China, Jin Zhai Road 96, Hefei 230026, P. R. China
50 Eꢀmail: solexin@ustc.edu.cn; Fax: +86ꢀ551ꢀ63601592; Tel:
+86ꢀ551ꢀ63492002
† Electronic supplementary information (ESI) available: Experimental sections, 100 nate hydrogen atoms22 by Equation 3 to a potential hydrogen
FEꢀSEM, XRD, DRS, BET, PL and photocatalytic measurement. See DOI:
10.1039/b000000h.
acceptor sulfur, forming hydrogen sulfide by Equation 4 (step II).
XXXX | J. Mater. Chem. A, 2014, XXXX–YYYY
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Fig. 1 a) XRD patterns of CuSꢀ1 (A) and CuSꢀ2 (B); b) HRꢀTEM image of a nanopetal; c) FEꢀSEM image of CuSꢀ1; d) a single microflower of CuSꢀ1; e) an
enlargement of the area indicated by the white frame in (d); f) FEꢀSEM image of CuSꢀ2; g) a single microflower of CuSꢀ2; h) an enlargement of the area
indicated by the white frame in (g). The insets in Fig. 1b, 1c and 1f show the SAED pattern of a nanopetal, the picture of a carnation flower and the picture of
a rattan ball, respectively.
5
Then, the hydrogen sulfide further reacts with Cu2+ (step III),
leading to the nucleation of CuS crystals (Equation 5, step IV).
Subsequently, the crystals further grew to nanopetal and were
perse flowerꢀlike shape (Fig. S6e and f). The SEM image with
large scale flowery array (Fig. 1f) efficiently demonstrates the
uniformity of this distribution. The surface feature of a single
assembled into the hierarchical flowerꢀlike structure of CuS (step 40 CuSꢀ2 microflower (Fig. 1g) looks like a rattan ball (see the inset
10 V).
of Fig. 1f), revealing that the surface structure of the CuSꢀ2 was
formed by selfꢀassembly of a large number of nanosheets, and the
thickness of the nanosheets (approximately 50 nm, Fig. 1h) is
much larger than that of the nanosheets on the surface of the CuSꢀ1
45 in Fig. 1e. Moreover, the area gap between the nanosheets was
further decreased.
Cu2+ + 2EDA
2HOCH2CH2OH
2CH3CHO
[Cu(EDA)2]2+
2CH3CHO + 2H2O
CH3COCOCH3 + 2H
H2S
(1)
(2)
(3)
(4)
S + 2H
Interestingly, when the amount of EDA was increased to 80 µL,
only a little precipitation of CuS (Fig. S7, ESI†) with an irregular
structure and a mean particle size of 1.2 ꢁm (Fig. S8, ESI†) was
50 observed.
Cu2+ + H2S
CuS + 2H+
(5)
We assume that the construction process of the asꢀprepared CuS
microflowers may be associated with the gradual dissociation of
the coordination ion [Cu(EDA)2]2+ to produce Cu2+ ions, which
15 allows slow growth of CuS. In order to test this hypothesis, as well
as determine the effect of PVP, we carried out a series of control
experiments by changing the reaction conditions during the solꢀ
vothermal process. It is demonstrated that the synthesis method is
efficient and versatile in a simple oneꢀstep procedure and the
20 morphology and size of the resulting CuS is easily controlled by
simply varying the amounts of PVP and EDA.
Initially, in the absence of PVP and EDA, the pure hexagonal
CuS material (Fig. S1, ESI†) obtained at the same conditions
shows a nanosheetꢀlike morphology (Fig. S2, ESI†), strongly
25 suggesting that the creation of the 3D flowers is entirely dependent
on the contribution of PVP and/or EDA. When only PVP (0. 4 g)
was applied, we surprisingly found that the hexagonal CuS sample
(Fig. S3, ESI†) has a regular spherical structure (Fig. S4, ESI†),
but shows a much larger particle size and sheet thickness, reꢀ
30 flecting that the addition of EDA can not only modify the structure
of CuS particles but also decrease their size. Moreover, we obꢀ
served that the structure evolvement of CuS was associated with
the amount of EDA used (Fig. 2) from 10 to 60 µL (Fig. S5 and S6,
ESI†).
Taken together, the observations mean that PVP seems to act as
a soft template23 and stabilizer24 in the creation and growth for
spherical crystals (Fig. S9 and S10, ESI†), preventing the agꢀ
glomeration of particles by regulating the viscosity and diffusion
55 coefficient of the reaction system, while EDA contributes to surꢀ
face modification of the microflowers by modulating the coordiꢀ
nation process in the competitive equilibrium state between
Equations 1 and 5. When EDA was insufficient (eg, in the cases of
10, 20, and 40 µL) to coordinate with all the Cu2+ ions derived
60 from CuCl2·2H2O, some free Cu2+ ions would directly react with
H2S to generate CuS. When 60 µL EDA was used, all the Cu2+ ions
could coordinate with EDA. Meanwhile, CuS can be formed only
by the reaction of H2S and those Cu2+ ions released from the coꢀ
ordination ion [Cu(EDA)2]2+ (Equation 5, Step III and IV). This
65 may lead to a slower creation of CuS microflowers, allowing to
construct an assembled structure with more intensive arrangement
of the nanopetals. Therefore, our results provide a straightforward
method for the synthesis of monodispersion materials of CuS.
UV–Vis diffuse reflectance spectroscopy (DRS) measurements
70 were performed to compare the optical properties of the CuSꢀ1 and
CuSꢀ2 (Fig. S11). It is obvious that the two materials present a
similar broad absorption band centered at about 640 nm (CuSꢀ1 at
649 nm and CuSꢀ2 at 631 nm) in visible region, which is
35
Notably, when 60 µL of EDA was used, the CuSꢀ2 material (Fig.
1f) was obtained with highly uniform and wellꢀdefined monodisꢀ
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Fig. 2 Schematic illustration describing the formation of the CuS materials. The white scale bars were 2 ꢁm.
ascribed to the bandꢀgap absorption peak of CuS.25 This band
Further study indicates that the CuSꢀ1 leads to a higher photoꢀ
45
5
shows a significant red shift in comparison with that of the bulk
CuS crystals.26 This is an indication of the effect of particle size on
light absorption. Furthermore, the CuSꢀ1 seems to have a higher
optical absorption for visible light than the CuSꢀ2. This increase of
more than 10% in absorption intensity could be associated with the
degradation degree (ξ, %) of MB than the CuSꢀ2 at the same conꢀ
ditions (Fig. S14, ESI†). The values of ξ were determined based on
Equation 6:
ξ = [(C0 - C)/C0] × 100%
(6)
50 In this equation, C0 is the initial concentration of MB, and C is the
real concentration of MB after light irradiation for a certain period.
For example, the ξ values of MB in the cases of the CuSꢀ1 and
CuSꢀ2 after an irradiation of 25 min are 98.1% and 95.2% respecꢀ
tively, suggesting that both the CuS materials have excellent
55 photocatalytic efficiency for the degradation of MB, and this
efficiency is related to their surface areas and pore sizes. Further,
photoluminescence (PL) emission measurements of the obtained
CuS materials (CuSꢀ1 and CuSꢀ2) were performed. Fig. S15 disꢀ
plays the PL spectra of the two CuS materials at room temperature.
60 As seen from this figure, a sharp strong emission band, centered at
about 358 nm (3.46 eV), was observed in the PL curves of the two
CuS materials, which is in agreement with the previous report by
Xue and coꢀworker.31 A weak emission peak occurred at 462 nm
(2.68 eV), which is different from the result of Jiang′s group,32
65 where there is no emission peak for CuS in the range of 400~800
nm. We suggest that the two emission peaks may be related to
surface defects (corners, edges, steps, etc) of the CuS microflower
materials, which may be a reason for their relatively high level of
photocatalytic activity since the defects can act as electron acꢀ
70 ceptors and benefit the efficient separation of photogenerated
electrons and holes.33
10 rough and open surface and smaller size of nanosheets.
The surface area and porous structure of the CuS materials are
investigated by gas adsorption/desorption measurement conducted
in liquid nitrogen. The nitrogen sorption isotherms (Fig. S12 and
S13, ESI†) of the two CuS samples present a similar type IV
15 isotherm27 with a small hysteresis loop at a relative pressure range
of 0.4~1.0, implying the mesoporous structure of the materials.
Moreover, the CuSꢀ1 and CuSꢀ2 have the Brunauꢀ
er–Emmett–Teller28 specific surface areas of 9.27 and 2.46 m2g−1,
respectively. This result indicates that the CuSꢀ1 material posꢀ
20 sesses a much larger surface area than the CuSꢀ2. It may be one of
the reasons for the higher optical absorption. In addition, the avꢀ
erage pore diameters of the CuSꢀ1 and CuSꢀ2 were determined to
be 23 and 16 nm, respectively, based on the Barꢀ
rett–Joyner–Halenda method.29
25
All these factors, such as high optical absorption, large surface
area and mesoporous structure, inspire us to further advance our
efforts towards applying the CuS materials in the field of photoꢀ
catalytic removal of organic pollutants. Therefore, the CuSꢀ1 was
chosen to examine the photodegradation process of MB, a typical
30 organic dye widely used in the textile industry, at room temperaꢀ
ture and under atmospheric pressure. In the light catalytic experꢀ
iment, the dosage of the CuS catalyst was 5 mg, the initial volume
of MB solution was fixed at 30 mL (5 mg·L−1).
Additionally, the result of recycling experiments reveals that the
CuSꢀ1 exhibits high structure stability (Fig. S16, ESI†) and cataꢀ
lytic sustainability (Fig. S17, ESI†). For example, no change in
75 phase behaviour and crystal morphology was observable after
three consecutive photodegradation testing cycles. Also, the ξ
value of MB over the first three cycles can still be maintained
above 90%, which is considerably more competitive than the
previously reports (Table S1).
Fig. 3A shows the UV–Vis absorption spectra of a series of MB
35 solutions after being treated by the CuSꢀ1 with different light
irradiation time in the presence of hydrogen peroxide (H2O2). It
can be seen that MB exhibits a characteristic absorption peak
centered at the wavelength of about 664 nm in visible region.30 Its
degradation process was monitored by UV–Vis spectrophotometer
40 measuring this absorption band. With the increase of light irradiꢀ
ation time, the band became smaller and smaller, and finally alꢀ
most completely disappeared after an irradiation of 25 min. The
colour change process of the series solutions was clearly reflected
by a photograph (the inset of Fig. 3A).
80
It should be noted that when MB was substituted by MO and
R6G (Fig. S18 and S19, ESI†), the CuSꢀ1 shows quite distinct
catalytic activities, resulting in a low degradation of MO and a
high degradation of R6G. For instance, the ξ values of MO and
R6G on the CuS-1 are 8% and 98%, respectively, after irradiated
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Fig. 3 A) UV–Vis absorption spectra of the MB solutions after being treated by the CuSꢀ1 using different time intervals: 0 (a), 3 (b), 5 (c), 10 (d), 15 (e), 20
(f) and 25 min (g). The inset shows a colour change of the solutions from a to g. B) Schematic illustration depicting the photocatalytic selectivity for the
degradation of different kinds of dyes in the presence of the CuSꢀ1.
5
for 25 min (Fig. S20, ESI†). The latter gives a similar performance
as that of MB. This may be explain by the fact that both MB and
R6G are cationic dyes,34 but MO is an anionic dye,35 the former
two having a higher affinity for the surface of the CuS with negaꢀ
degradation of several organic dyes. It is expected that the present
synthetic strategy can be extended to construct other flowerꢀlike
metal sulphides with highly monodisperse character for photoꢀ
catalytic degradation of organic contamination in waters.
10 tive charges.36 Therefore, the CuS-1 catalyst can lead to a signifꢀ
icant selective degradation of these dyes.
45 This project was supported by NSFC (No. 21071139).
Herein, we will attempt to give a possible interpretation of the
photocatalytic degradation of dyes in the presence of the CuS
microflowers. It is demonstrated by other reports that the surface
15 of CuS have negative charges.36 As shown in Fig. 3B, MB, a
cationic dye, could initially be efficiently adsorbed on the surface
of the CuS catalyst in a dark environment after being fully mixed.
The nature of this adsorption process might be ascribed to an
ionꢀdipole interaction between the partial negative charges on the
20 sulfur ions (Sδ−) on the CuS surface and the N+ atoms on the MB.
On the contrary, MO, an anion dye, could not efficiently be adꢀ
sorbed on the surface of the catalyst, resulting in a very low degꢀ
radation. In the photocatalytic degradation process, electrons and
holes located in the conduction band (CB) and valence band (VB)
25 of the CuS, respectively, can interact with H2O2 molecules near the
surface of the CuS, inducing the formation of highly reactive
hydroxyl radicals (ꢂOH, Equations 7~9).24,37 Finally, the MB
molecules were oxidized by the ꢂOH radicals into small molecules
such as CO2 and H2O,38 as shown in Equation 10.
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H+ + CuOOH+
(7)
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vothermal approach to fabricate highly monodisperse CuS microꢀ
flowers with uniform size and morphology. This preparation
method has advantages of simplicity and convenience, rather mild
35 reaction conditions, effectiveness and ability to generate monoꢀ
disperse structure. Control experiments demonstrated that the
presence of PVP and especially EDA played a crucial role in the
formation of the microstructures. Further, the CuSꢀ1 microflowers
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DOI: 10.1039/C4TA04232H
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