Angewandte

Chemie

Nanostructures pollutants and toxic water pollutants. ZnS nanomaterials have

been used for the photocatalytic degradation of organic
Mass Production and High Photocatalytic pollutants such as dyes, p-nitrophenol, and halogenated
Activity of ZnS Nanoporous Nanoparticles** benzene derivatives in wastewater treatment.[8] However,
the applications of ZnS NCs in photocatalysis are limited to a
considerable degree because of the high cost of their large-
Jin-Song Hu, Ling-Ling Ren, Yu-Guo Guo, Han-
scale production, coupled with the tremendous difficulties in
Pu Liang, An-Min Cao, Li-Jun Wan,* and Chun-Li Bai*
separation, recovery, and recycling in industrial applications.
Nevertheless, the studies have demonstrated that nanoporous
Environmental problems associated with organic pollutants materials with high surface-to-volume ratios can be success-
and toxic water pollutants provide the impetus for sustained fully used in various catalysis, environmental engineering, and
fundamental and applied research in the area of environ- sensor systems.[9] Some nanoporous materials with regular
mental remediation. Semiconductor photocatalysis offers the shapes such as porous nanowires, nanotubes, spheres, and
potential for complete elimination of toxic chemicals through nanoparticles have been successfully prepared by chemical or
its efficiency and potentially broad applicability.[1] Various physical methods,[10] most of which use templates that are
new compounds and materials for photocatalysis have been intrinsically high in cost and with low production yield.
synthesized in the past few decades. A successful example is Therefore, the development of cost-effective methods suit-
TiO2, a metal oxide often used as a catalyst in photochemistry, able for the large-scale synthesis of ZnS nanoporous nano-
electrochemistry, environmental protection, and in the bat- structures with high catalytic activity and easy separation
tery industry.[2] represents a critical challenge to their practical applications.
Recently, transition-metal sulfides, in particular ZnS and Herein, we report a simple procedure for mass production
CdS, have been intensively studied because of their unique by using a low-cost, self-assembly synthetic route to produce
catalytic functions compared to those of TiO2.[2, 3] These ZnS nanoporous nanoparticles (NPNPs) composed of build-
studies have revealed that ZnS nanocrystals (NCs) are good ing blocks comprising hexagonal wurtzite ZnS nanocrystals of
photocatalysts as a result of the rapid generation of electron– several nanometers in diameter. The advantages of the
hole pairs by photoexcitation and the highly negative present protocol are: 1) high surface-to-volume ratios with
reduction potentials of excited electrons. The photocatalytic effective prevention of further aggregation of the nano-
properties occur not only in the photoreductive production of particles, so as to retain high catalytic activities; 2) the
H2 from water and the photoreduction of CO2,[4] but also in profitability of size-quantized, nanometer-sized semiconduc-
the phototransformation of various organic substrates such as tor particles with higher redox potentials as a result of the
the oxidative formation of carbon–carbon bonds from organic increase in band-gap energy (the energy difference between
electron donors, cis–trans photoisomerization of alkenes, and the lowest unoccupied and highest occupied molecular
the photoreduction of aldehydes and their derivatives.[5] The orbitals),[1, 2] which in turn enhances the charge-transfer
notable finding in nonmetalized ZnS photocatalysis is an rates in the system and drastically reduces the volume
irreversible two-electron-transfer photoreduction of organic recombination, that is, radiationless recombination of the
substrates.[6] A favorable shift of the optical response into the electron–hole pair within the semiconductor particle;[11]
visible region occurs subsequent to the doping of transition 3) easier separation and recycling than those obtainable
metal or rare-earth metal ions, such as Ni2+ and Cu2+; with common NCs because of the larger diameters of
therefore, ZnS NCs can also be used as effective catalysts NPNPs; and 4) good dispersity and useful dimension without
for photocatalytic evolution of H2 and photoreduction of toxic the requirement of constant stirring or a “dark” reaction for
ions under visible-light irradiation.[7] adsorption of substrates. In addition, we demonstrate that the
An important application of ZnS is as a photocatalyst in ZnS NPNP is an excellent photocatalyst with higher photo-
environmental protection through the removal of organic degradation efficiency of eosin B in environmental protection
than that of TiO2 nanoparticles.
ZnS NPNPs were prepared by a facile solution-phase
[*] J.-S. Hu,[+] L.-L. Ren, Y.-G. Guo,[+] H.-P. Liang,[+] A.-M. Cao,[+]
Prof. Dr. L.-J. Wan, Prof. Dr. C.-L. Bai thermal decomposition route in the presence of poly(N-vinyl-
Institute of Chemistry 2-pyrrolidone) (PVP). The fine structural details of ZnS
Chinese Academy of Sciences (CAS) NPNPs were investigated by using TEM. Figure 1 a shows a
Beijing 100080 (China) low-magnification TEM image of a ZnS sample, which
Fax: (+ 86) 10-6255-8934 indicates that the sample is composed of a large quantity of
E-mail: [email protected]
well-dispersed spherical nanoparticles with uniform size and
[email protected]
shape. The average size of these particles estimated from the
[+] Also in the Graduate School of the CAS, Beijing (China)
TEM image is about 60 nm, which is in good agreement with
[**] This work was supported by the National Natural Science
the result measured by dynamic light scattering (not shown).
Foundation of China (Nos. 20025308 and 20177025), the National
Key Project on Basic Research (Grant G2000077501), and the A typical scanning electron microscope (SEM) image of the
Chinese Academy of Sciences. We thank Dr. L. Jiang for his help in sample is presented in Figure 1 b, in which the morphology of
the writing of this manuscript. spherical nanoparticles is also clearly visible. The surface of
Supporting information for this article is available on the WWW every particle is rough and with many smaller particles. The
under http://www.angewandte.org or from the author. high-magnification TEM image in Figure 1 c shows many

Angew. Chem. Int. Ed. 2005, 44, 1269 –1273 DOI: 10.1002/anie.200462057
2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1269
Communications

Figure 2. X-ray diffraction pattern of ZnS NPNPs acquired at a) 150 8C

Figure 1. a) Low-magnification TEM image, b) SEM image, c) high- and b) 180 8C.
magnification TEM image, and d) HRTEM image of ZnS NPNPs. The
inset in (c) is the electron diffraction pattern. The inset in (d) shows
the enlarged lattice fringes.

spots with a clear contrast difference in each individual

nanoparticle. This observation further confirms that these
NPNPs consist of smaller NCs with a size of 3–5 nm which are
assembled in a nanoporous structural configuration. A
selected-area electron diffraction (ED) pattern of ZnS
NPNPs is presented in the inset of Figure 1 c. The ED pattern
shows a set of concentric rings instead of sharp spots as a
result of the small crystallites. The diffraction rings have been
indexed to (002), (110), and (112) planes of the hexagonal
ZnS phase (JCPDS No. 80-0007). A representative high-
resolution TEM (HRTEM) image of ZnS NPNPs in Fig-
ure 1 d, with an inset image taken on the outside of the
particles, shows the lattice fringes of nanocrystals in nano-
Figure 3. Nitrogen adsorption/desorption isotherm and Barrett–
particles with a spacing of 0.31 nm, which corresponds to an
Joyner–Halenda (BJH) pore size distribution plot (inset) of ZnS
interplanar distance of the (002) plane of hexagonal ZnS. NPNPs.
The XRD patterns shown in Figure 2 are for ZnS NPNPs
obtained at 150 and 180 8C. The diffraction patterns of the two
samples are very similar and are in good agreement with The isotherms are identified as type IV, which is characteristic
hexagonal ZnS (space group: P63/m (186)) with lattice con- of mesoporous materials. The pore-size distribution obtained
stants a = 3.777 and b = 6.188
(JCPDS No. 80-0007). This from the isotherm indicates a number of pores less than 5 nm
result illustrates that a heating temperature of 150 8C is in the sample. These pores presumably arise from the spaces
sufficient to produce a high-temperature-stable hexagonal among the small nanocrystallites within a ZnS NPNP. The
ZnS phase in this system. The significant broadening of the large pores of around 30 nm are attributed to the interparticle
diffraction peaks is ascribed to the very small crystallite size spaces. The sharp distribution of the mesopores around 30 nm
within ZnS NPNPs, similar to the case reported in the suggests that the NPNPs have high monodispersity. The BET
literature.[12] Moreover, energy-dispersive X-ray (EDX) anal- specific surface area of the sample was calculated from N2
ysis of ZnS NPNPs (see the Supporting Information) shows isotherms at 196.6 8C, and was found to be as much as about
two peaks for the elements Zn and S, in addition to the C, O, 156.1 m2 g 1. The single-point total volume of pores at P/P0 =
and Cu derived from the carbon-coated copper TEM grid. 0.9926 was 0.59 cm 3 g 1. The extremely high BET surface
These observations show the product is composed of hex- area and large total pore volume strongly support the fact that
agonal ZnS. the nanoparticles have a nanoporous structure.
Brunauer–Emmett–Teller (BET) gas sorptometry meas- In a series of further experiments we discovered that PVP
urements were conducted to examine the porous nature of the not only contributed to stabilizing the NPNP assembly but
ZnS NPNPs. Figure 3 shows the N2 adsorption/desorption also exerted vigorous control over the formation of the
isotherm and the pore-size distribution (inset) of ZnS NPNPs. spherical geometry. If no PVP was in the reaction solution,

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 Angewandte
Chemie

the small nanoparticles generated initially by the decompo- absorption spectrum of an aqueous solution of eosin B (initial
sition of complex precursors tended to rapidly aggregate in a concentration: 5.0  10 5 m, 30 mL) in the presence of ZnS
random manner, thus leading to the formation of an NPNPs (10 mg) under exposure to UV light for various
agglomerate cross-linked by numerous irregular particles durations. The absorption peaks corresponding to the eosin B
(see the Supporting Information). As such, no distinct molecule, such as the sharp peak at 517 nm, diminish
spherical nanoparticles could be observed. The addition of gradually as the exposure time increases and completely
PVP into the reaction system at a molar ratio of PVP to zinc disappear after about 40 minutes. No new absorption bands
precursor of 0.04:1 resulted in the sample being mainly appear in either the visible or ultraviolet regions, which
composed of spherical particles with plenty of defects that indicates the complete photodegradation of eosin B. The
were only partially cross-linked. This finding indicates that color-change sequence in the sample during this process is
the initial nanoparticles tend to assemble into spherical shown in the inset of Figure 4, from which it is clear that the
aggregates in the presence of PVP, and any further agglom- intense pink color of the starting solution gradually disap-
eration is essentially inhibited by PVP. An increase in the pears with increasingly longer exposure times.
amount of PVP improved the ability to form spherical A further comparative experiment was carried out to
aggregates and effectively prevented the aggregates from investigate the catalytic activity. The solution of eosin B was
agglomeration. In a typical example in which the molar ratio subjected to a series of experimental conditions: a) with
of PVP to zinc was increased to 0.08, the sample consisted Degussa P25 titania (10 mg), in the dark; b) without catalyst,
substantially of nanoparticles with regular spherical shape. with UV light; c) with ZnS NCs (10 mg), in the dark; d) with
Therefore, it is clear from the formation process that each ZnS NPNPs (10 mg), in the dark; e) with Degussa P25 titania
spherical particle was produced by aggregation of many (10 mg) and UV light; f) with ZnS NCs (10 mg) and UV light;
smaller nanometer-scale crystallites with a diameter of about and g) with ZnS NPNPs (10 mg) and UV light. The results are
3–5 nm. These spherical nanoparticles were well-separated illustrated in Figure 5. Under the experimental conditions
and had uniform size and shape, such as those shown in
Figure 1 a and b.
ZnS has been used as a semiconductor-type photocatalyst
for the photoreductive dehalogenation of halogenated ben-
zene derivatives, photocatalytic degradation of water pollu-
tants, and photocatalytic reduction of toxic metal ions.[4–7] To
demonstrate the potential applicability of the present ZnS
NPNPs in these applications we investigated their photo-
catalytic activity relative to those of ZnS NCs prepared by a
literature method[4c] and of a commercial photocatalyst
(Degussa P25 titania), with the photocatalytic degradation
of eosin B as a test reaction. The characteristic absorption of
eosin B at 517 nm was chosen as the monitored parameter for
the photocatalytic degradation process. Figure 4 shows the

Figure 5. Photodegradation of eosin B (5.0
10 5 m, 30 mL) under

different conditions: a) with Degussa P25 titania (10 mg), in the dark;
b) without any catalyst, with UV light; c) with ZnS NCs (10 mg), in the
dark; d) with ZnS NPNPs (10 mg), in the dark; e) with Degussa P25
titania (10 mg) and UV light; f) with ZnS NCs (10 mg) and UV light;
g) with ZnS NPNPs (10 mg) and UV light.

from (a) to (d), the photocatalytic effect on the solution

degradation without catalysts but under exposure to UV light
is almost the same as that with catalyst but no exposure to UV
light. For example, a slight decrease in the concentration of
eosin B was detected in the absence of any catalyst (curve b).
Exposure to UV light for 1.5 h resulted in only 5 %
degradation of this compound. A slight decrease in the
concentration of eosin B took place in the presence of ZnS
NPNPs (curve d) and ZnS NCs (curve c) in the dark,
compared to that in the presence of Degussa P25 (curve a)
Figure 4. Absorption spectrum of a solution of eosin B (5.0
10 5 m, in the dark. This decrease may be mainly ascribed to the
30 mL) in the presence of ZnS NPNPs (10 mg) under exposure to UV adsorption of eosin B on the porous nanostructures, although
light. without exposure to UV light. The concentration of he

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2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1271
Communications
eosin B solution hardly changed after mixing the solution with impurities and PVP. Finally, the ZnS NPNPs were dried in a vaccum
catalysts for 15 minutes, which indicates that the adsorption of oven (ca. 0.1 MPa) for 6 h prior to being characterized.
eosin B on nanostructured catalysts reached an equilibrium Preparation of ZnS NCs: ZnS nanocrystallites were prepared by
using the method described in the literature.[4c] Briefly, the ZnS NC
state. However, from the data in curves e (Degussa P25), f
samples were prepared in an argon atmosphere by mixing equal
(ZnS NCs), and g (ZnS NPNPs), it is clearly seen that, under amounts of aqueous 0.05 m solutions of ZnSO4 and Na2S in an ice bath
identical conditions with exposure to UV light, the ZnS with stirring. TEM images showed that the so-prepared ZnS NCs had
NPNP photocatalyst shows much greater activity than that of a diameter ranging from 3 to 5 nm, and easily aggregated.
Degussa P25 or ZnS NCs. The degradation of eosin B in the Characterization: For TEM observation, the samples were
ZnS NPNPs follows first-order kinetics. Exposure of the redispersed in water or ethanol by ultrasonic treatment and dropped
on carbon–copper grids. TEM images were collected by using a JEOL
solution of eosin B to UV light for about 40 minutes resulted
JEM 2010F microscope working at 200 kV and equipped with an
in complete decolorization. This difference in the photo- energy-dispersive X-ray analyzer (Phoenix). A Hitachi S-4300F
catalytic activity between ZnS NPNPs and Degussa P25 can scanning electron microscope (SEM) was used to investigate the
be explained by the larger specific surface area of the former morphology of the hollow spheres.
(ca. 156.1 m2 g 1 versus Degussa P25 powder ca. 45 m2 g 1), X-ray powder diffraction (XRD) measurements were carried out
and hence the stronger adsorption of the ZnS NPNPs to the with a Rigaku D/max-2500 instrument using filtered CuKa radiation.
molecules of eosin B. The photocatalytic superiority of ZnS The nitrogen adsorption and desorption isotherms at 77 K were
measured using a Micrometrics ASAP 2010 system after the sample
NPNPs over ZnS NCs may be influenced by the unwanted
was degassed in vacuum at 130 8C overnight. A Shimadzu UV-1601PC
aggregation of ZnS NCs during the reaction, which leads to a spectrophotometer was used to record the UV/Vis spectra of various
rapid decrease in the active surface area, while ZnS NPNPs samples.
maintain an excellent porous nanostructure and are effec- Photocatalytic activity measurement: A cylindrical pyrex flask
tively prevented from aggregating. A more detailed under- (capacity ca. 40 mL) was used as the photoreactor vessel. The
standing of the photocatalytic activity of ZnS NPNPs is reaction system containing eosin B (C20H6Br2N2Na2O9, Sigma-
currently under way. Aldrich Chemical Co.; 5.0  10 5 m, 30 mL) and ZnS NPNP catalyst
(10 mg) was magnetically stirred in the dark for 15 min to reach the
In conclusion, we have developed a simple and robust
adsorption equilibrium of eosin B with the catalyst, and then exposed
method to produce ZnS nanoporous nanoparticles on a large to light from a Philips HPK high-pressure Hg lamp (125 W).
scale. These NPNPs are uniform spheres, monodispersed in Commercial TiO2 (Degussa P25, Degussa Co.) was adopted as the
size at around 60 nm in diameter, and are formed by a self- reference with which to compare the photocatalytic activity under the
assembly process of hexagonal ZnS nanocrystals of 3–5-nm same experimental conditions. UV/Vis absorption spectra were
size as building blocks. They possess a specific surface area on recorded at different intervals to monitor the reaction.
the order of 156 m2 g 1, which leads to substantially more
Received: September 21, 2004
effective photocatalytic performance compared to that of
Published online: January 14, 2005
Degussa P25 titania or ZnS NCs, as demonstrated in the
photodegradation of eosin B at ambient temperature. A
combination of their unique features of high surface-to-
volume ratios, monodispersion, and rich photocatalytic and
.
Keywords: nanostructures · photocatalysis · self-assembly ·
semiconductors · zinc
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