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Journal of Colloid and Interface Science 301 (2006) 116122 www.elsevier.

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Synthesis and characterization of ZnS-montmorillonite nanocomposites and their application for degrading eosin B
Shiding Miao, Zhimin Liu , Buxing Han, Haowen Yang, Zhenjiang Miao, Zhenyu Sun
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid, Interfacial and Chemical Thermodynamics, Center for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, Peoples Republic of China Received 29 September 2005; accepted 30 April 2006 Available online 5 May 2006

Abstract Nanocomposites of zinc sulde (ZnS) and montmorillonite (MMT) were prepared via a hydrothermal route. In this method, the MMT treated with hexadecyltrimethyl ammonium bromide (HTAB) aqueous solution was dispersed in the aqueous solution of thiourea and Zn(OOCHCH3 )2 2H2 O, and heated at 170 C for about 4 h, resulting in ZnS-MMT composites. The as-prepared nanocomposites were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen sorption analysis. It was demonstrated that the interlayer space of MMT was enlarged from 0.98 to 3.77 nm after the treatment with HTAB aqueous solution, and the ZnS nanoparticles were deposited on the layers of MMT. Nitrogen sorption analysis demonstrated that the specic surface area of the samples decreased from 39.2 m2 /g of the pristine MMT to 5.9 m2 /g of the nal ZnS-MMT composites. The resulting ZnS-MMT nanocomposites (50.0 mg) could degrade eosin B completely in aqueous solution (75 ml, 3.2 105 M) within 20 min under UV irradiation. 2006 Elsevier Inc. All rights reserved.
Keywords: Montmorillonite; ZnS; Nanocomposites; Eosin B; Degradation

1. Introduction Recently, ZnS has attracted much attention because of its potential applications in electron devices, catalysis, etc. Different ZnS nanostructures including nanoparticles, nanorods, nanowires, and nanospheres, have been prepared and characterized extensively [16]. An important application of ZnS is in photocatalysis due to the rapid generation of electronhole pairs by photoexcitation and the highly negative reduction potentials of excited electrons. Although ZnS has been utilized for the degradation of organic pollutants such as dyes, p-nitrophenol, and halogenated benzene derivatives in wastewater treatment [710], its applications in photocatalysis are very limited owing to the high cost of its production in large scale, coupled with the tremendous difculties in separation, recovery, and recycling. More recently, Wan and co-workers developed a low-cost, selfassembly synthetic route to mass-produce ZnS nanoparticles, which exhibited highly efcient activity for the degradation of
* Corresponding author. Fax: +86 10 62562821.

E-mail address: liuzm@iccas.ac.cn (Z. Liu). 0021-9797/$ see front matter 2006 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2006.04.080

eosin B, one of nitryl dye, under UV irradiation [11]. Development of low-cost effective methods suitable for the masssynthesis of ZnS nanostructures with high catalytic activity and easy separation represents an interesting topic [12,13]. Montmorillonite (MMT) is a kind of aluminosilicate clay with layered 2:1 primany unit, which consists of two tetrahedral silicate layers sandwiching a central metal octahedral layer. Up to date, MMT has been found many applications in heterogeneous catalysis as catalyst support [1416]. It has been reported that many metal [1719] and metal compound (oxides, suldes, etc.) [2023] nanoparticles have been deposited on MMT with some nanoparticles intercalated into its interlayers. These MMT-based catalysts combined the functions of the nanoparticles and MMT together, and exhibited synergetic effects [2426]. Several methods have been adopted to prepare MMT-based composites, among which surfactant or polymerassisted methods are often applied [2730]. For example, PdMMT nanocomposites were prepared with the aid of surfactants, which showed high selectivity for the partial hydrogenation of 1-phenyl-1-pentyne to 1-phenyl-cis-1-pentene [17]. Han et al. developed a one-step route for the synthesis of the CdS-

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Fig. 1. The chemical structure of eosin B.

MMT nanocomposites via the combination of an ion exchange process and an in situ hydrothermal decomposition process of a complex precursor [31]. Dkny et al. deposited ZnS particles on the surface of MMT in an aqueous solution [32]. In this work, we prepared ZnS-MMT nanocomposites via a hydrothermal route. In this method, MMT was rst treated with hexadecyltrimethyl ammonium bromide (HTAB) aqueous solution at room temperature, resulting in HTAB exchanged MMT, named HTAB-MMT. Then the HTAB-MMT was treated in the aqueous solution of thiourea and Zn(OOCHCH3 )2 2H2 O at 170 C for 4 h, forming ZnS-MMT nanocomposites. The resulting nanocomposites were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen sorption analysis. The catalytic activity of the ZnS-MMT composites was detected by the photocatalytic degradation of eosin B (4 ,5 dibromo-2 ,7 -dinitrouorescein, C20 H8 Br2 N2 O9 2Na, shown in Fig. 1) under UV irradiation. The characteristic absorption of eosin B at 517 nm was chosen to monitor the photocatalytic degradation process. 2. Materials and methods 2.1. Materials HTAB, Zn(OOCHCH3 )2 2H2 O and thiourea are all A.R. grade, which were provided by Beijing Chemical Reagent Ltd., and used as received. Eosin B (A.R. grade) was purchased from SigmaAldrich Chemical Co. The MMT used in this work was supplied by Hongyan Mining Co., and its chemical composition (in mass percentage) was as follows: SiO2 63.25, Al2 O3 14.35, Fe2 O3 0.96, FeO 0.12, MgO 4.90, CaO 1.62, Na2 O 0.091, K2 O 1.12, H2 O+ 8.32, H2 O 4.94, TiO2 0.16, P2 O5 0.027, MnO 0.028. Prior to use, the MMT was ground into particles with size smaller than 45 m, and then treated with Na2 CO3 aqueous solution, followed by successive centrifugation-washing treatment with distilled water, leading to the clay of high purity. The cation exchange capacity (CEC) of the obtained Na-MMT was 1.0 meq g1 , determined by copper bisethylenediamine complex method reported previously [33]. 2.2. Preparation of ZnS-MMT composites Prior to the preparation of Zn/MMT composites, the pristine MMT was rst treated with HTAB aqueous solution. 2.00 g

of MMT (exchangeable cation = 2.0 mmol) was dispersed in HTAB (0.82 g, 2.25 mmol) aqueous solution (100 ml) with stirring for about 4 h. After ltrated and washed several times with distilled water, the THAB-MMT was obtained. The product was dried in a vacuum oven at 60 C for 10 h. In a typical experiment to prepare ZnS-MMT composites, 1.00 g of THAB-MMT was dispersed in 10 ml of thiourea (0.1102 g, 1.45 mmol) and Zn(OOCHCH3 )2 2H2 O (0.3000 g, 1.37 mmol) aqueous solution under continuous stirring for about 30 min. Then the well-mixed suspension was moved into a high-pressure stainless steel autoclave of 15 ml. The autoclave was sealed and maintained at 170 C for 4 h, and then cooled to around 0 C in icewater. The resulting product was separated via centrifugation, and was washed ve times with distilled water. The product was dried in a vacuum oven (ca. 0.1 MPa) at 60 C for about 6 h before characterization and photocatalytic activity measurement. 2.3. Characterization X-ray powder diffraction was performed on a XPERT SW X-ray diffractometer operated at 30 kV and 100 mA with CuK radiation. The morphology and microstructures of the as-prepared composites were determined by means of SEM (JEOL, JSM-6700F) equipped with an energy dispersive X-ray spectrometer (EDS) and TEM (JEOL, JEM-2010) at an accelerating voltage of 200 kV, respectively. The nitrogen adsorption/desorption isotherms at 77 K were measured using a Micrometrics ASAP 2010 system after the sample was degassed in vacuum at 130 C overnight. A Shimadzu UV-1601PC spectrophotometer was used to record the UVvis spectra of the aqueous solutions of various samples. 2.4. Photocatalytic activity measurement A 200-W high-pressure Hg lamp (340 nm, Wacom, BMO500DY) was used as the light source. The experiments to degrade eosin B with ZnS-MMT composites as catalyst were carried out in a 100 ml Pyrex conical ask equipped with a magnetic stirrer. 50 mg of ZnS-MMT powders and 75 ml of eosin B aqueous solution (3.2 105 mol L1 ) were loaded into the ask to form a suspension under stirring. The suspension was irradiated with UV lamp for different time. The concentration of the residual eosin B in aqueous solution was analyzed with UVvis spectrophotometer at the wavelength of 517 nm after removal of solid catalysts by centrifugation at 6000 rpm for 6 min. Similarly, the experiments to remove eosin B from its aqueous solution with the as-prepared ZnS-MMT composite as adsorbent were performed in dark. 3. Results and discussion 3.1. XRD analysis The XRD patterns of the pristine MMT, HTAB-MMT, HTAB-MMT treated in aqueous solution at 170 C, and the ZnS-MMT composites are shown in Fig. 2. Fig. 2a displays

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3.2. Morphology The morphology and microstructures of the pristine MMT, HTAB-MMT, hydrothermal treated HTAB-MMT at 170 C, and ZnS-MMT composites were examined by SEM and TEM observation. Fig. 3a shows the SEM image of the pristine MMT and the inset is a low magnied image, which exhibited granular morphology of ocs. After ion-exchange with HTAB, there was no obvious variation of MMT morphology except that the size of the granules decreased, as shown in Fig. 3b. After the HTAB-MMT was treated in 170 C water for a period of time, its morphology changed remarkably, as displayed in Fig. 3c. From Fig. 3c and the inset, it can be observed that many leaf-like layers with curled edge were produced in this process. This morphology change may result from coagulation process, in which the surface charges of MMT was compensated by HTAB+ cations and the hydrophilic surface of MMT partly became hydrophobic due to the presence of the surfactant molecules. After loading ZnS on MMT via subsequently hydrothermal process, the amount of disorder leaf-like layers increased, i.e., the ordered structure of MMT had been delaminated into isolated layers with the thickness of 20200 nm, as demonstrated in Fig. 3d. It can also be seen that many nanoparticles with size of about 25 nm were homogeneously dispersed on the disordered or exfoliated sheets of MMT (Fig. 3e). These nanoparticles are deposited on the MMT layers. This demonstrates that the MMT can act as support for these nanoparticles. Fig. 3f shows the EDS spectrum of the composites, which indicates that elements Zn and S were present in the composites, and the Zn:S molar ratio was 0.972, further conrming that ZnS was formed. Fig. 3g is a TEM image of the ZnS-MMT composites. It shows that the ZnS nanoparticles were homogeneously planted on the layers of MMT. 3.3. Nitrogen sorption analysis Fig. 4 illustrates the N2 sorption isotherms of the pristine MMT, the HTAB-MMT, and the ZnS-MMT composites, respectively. All these samples exhibited IV type sorption isotherms according to the IUPAC classication [35], and the specic surface areas were determined by the BET method in the relative pressure range 0.050.20 from nitrogen adsorption isotherms [36]. It was demonstrated that the specic surface areas decreased from 39.2 m2 /g of the pristine MMT to 5.3 m2 /g of the HTAB-MMT due to the modication by THAB, and to 5.9 m2 /g after the deposition of ZnS nanoparticles. The specic surface area of MMT decreases after hydration and the sorption of interlayer water [31,37], which causes a denser packing of the particles in the interlayer spaces. The slight hysteresis of the composite indicates less mesoporosity, suggesting that the ZnS nanoparticles occupy the mesopores, leaving relatively little free volume in the clay [38]. From the N2 sorption isotherms, it was known that the total pore volume is reduced from 0.137 ml/g of the pristine MMT to 0.05 ml/g of the ZnSMMT composites. Furthermore, the pore size distribution is much broader because of the deposition of ZnS nanoparticles in the composite.

(a)

(b) Fig. 2. (a) Wide-angle XRD patterns of the ZnS-MMT composites (z: ZnS; m: MMT), (b) low-angle XRD patterns of the pristine MMT (pattern a), HTABMMT (pattern b), HTAB-MMT treated in aqueous solution at 170 C (pattern c), and ZnS-MMT composites (pattern d).

the wide-angle XRD patterns of the ZnS-MMT composites. It can be seen that several small peaks appear at 27.2 , 28.9 , 30.9 , 48.2 , 57.1 , which are well indexed to the (100), (002), (101), (110), (112) plane diffractions of hexagonal ZnS (JCPDS number is 80-00070), indicating that ZnS is present in the nal product. Fig. 2b shows the low-angle XRD patterns of the resulting samples, which indicated that the basal diffraction peak of the pristine MMT at 9.03 (corresponding to d001 = 0.98 nm) shifted to 2.34 of the HTAB-MMT (pattern b, d001 = 3.77 nm), suggesting that the HTAB molecules were impregnated into the interlayer space of the MMT. Pattern c in Fig. 2b is for the HTAB-MMT treated in water at 170 C. Compared to pattern b, the rst peak in pattern c was much wider and the intensity was weaker, which indicates the crystalline density of MMT layers decreased and the surfactant molecules were still present in the interlayers of MMT [34]. For ZnSMMT sample, the basal diffraction peak only slightly shifted to 2 = 2.28 (d001 = 3.89 nm), suggesting that the structures of MMT in HTAB-MMT and ZnS-MMT were similar. However, the basal diffraction intensity of ZnS-MMT was slightly higher than that of HTAB-MMT, which may result from the incorporation of ZnS nanoparticles into the interlays and lling up the voids to reconstruct the order of the layered structure of the organic clay. This result is similar to that of Han et al., who intercalated CdS into the interlayers of MMT, conrmed by the XRD analysis [31].

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Fig. 3. SEM images of (a) pristine MMT, (b) HTAB-MMT, (c) hydrothermally treated HTAB-MMT at 170 C for 4 h, ZnS-MMT composite (d: parallel to the layer; e: vertical to the exfoliated layer), (f) EDS of ZnS-MMT, (g) TEM image of ZnS-MMT composite, and (h) SEM images of ZnS-MMT composite after 5 reaction runs.

3.4. Possible formation mechanism of ZnS-MMT composites In this work, MMT was rst treated with the surfactant, HTAB, generating exchanged MMT with cation of HTAB, as

conrmed by XRD analysis. The interlayer space in HTABMMT was enlarged due to the impregnation of cation of HTAB, which is, to some extent, favorable to accommodating guest molecules [39,40]. It was reported that CdCl2 and thiourea

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Fig. 5. Sketch map of the process to prepare ZnS-MMT composites. (a) Pristine MMT, (b) HTAB pillared MMT, (c) HTAB-MMT loaded with ZnS in the nal ZnS-MMT composite.

(a)

Fig. 6. UVvis absorption spectra of the eosin B solution (3.2 105 mol L1 , 75 ml) treated with ZnS-MMT nanocomposite (50 mg) under UV irradiation for different time.

3.5. Catalytic activity for degrading eosin B


(b) Fig. 4. N2 adsorption/desorption isotherms of the (P) pristine MMT, (1) HTAB-MMT, and (2) ZnS-MMT.

could form complex, Cd[NH2 CSNH2 ]2 Cl2 , in aqueous solution, and the complex was used as precursor for CdS [31]. Similarly, Zn(OOCHCH3 )2 and NH2 CSNH2 used in this work could form complex, Zn[NH2 CSNH2 ]2 (OOCHCH3 )2 , in aqueous solution. When HTAB-MMT was added into the above solution, the surface charges compensated by HTAB+ cations and the partly hydrophobic surface of MMT was much more accessible to the precursor complex, and some complex would enter the interlayer space of MMT due to the interaction between the complex and the chain of HTAB. The hydrothermal treatment could destroy the original layered structures of organic MMT to some degree, leading to some exfoliated sheets, as illustrated by SEM observation. Thus the subsequent hydrothermal decomposition of the complex in the intergallery of the MMT produced ZnS nanoparticles or pillars, resulting in the occupation of the voids by the newly formed ZnS nanoparticles, as conrmed by XRD analysis. MMT modied with surfactant has low surface charge. This is favorable for penetration of the inorganic cations into the expanded interlayer of MMT [41], and the hydrophobic intergallery originated from the long alkyl chains of HTAB can provide adsorption sites for Zn[NH2 CSNH2 ]2 (OOCHCH3 )2 complex species [42]. Moreover, the hydrothermal decomposition of the complex outside the intergallery of the MMT produced ZnS nanoparticles, which deposit on the surface of the MMT layers. The process to prepare ZnS-MMT composites can be schematically illustrated in Fig. 5 [31,32,34].

It was reported that MMT had strong ability to adsorb organic compounds from aqueous solutions [43,44], and ZnS could be used as a semiconductor-type photocatalyst for the photoreductive degradation of water pollutants. To demonstrate the potential applicability of the present ZnS-MMT composite in photoreductive area, the catalytic activity of the prepared ZnS-MMT composites was determined via degrading eosin B in aqueous solution as a test reaction under UV irradiation. Based on the assumption that all the zinc salt were converted into ZnS and deposited on MMT, the ZnS content of the ZnS-MMT composites prepared in this work was 9.8 wt%. Fig. 6 shows the time proles of the degradation of 75 ml eosin B aqueous solution with the initial concentration of 3.2 105 mol L1 in the presence of 50 mg of the ZnS-MMT composites, i.e., 4.9 mg of ZnS on the catalyst, under exposure to UV light for various durations. The absorption peak of the eosin B at 517 nm diminished gradually as the exposure time increased, and completely disappeared after about 20 min. No new absorption band appeared in either the visible or ultraviolet regions, indicating complete photodegradation of the eosin B. Several experiments were carried out to investigate the catalytic activity of the ZnS-MMT composites. The aqueous solution of eosin B was treated with pristine MMT or ZnS-MMT composites under UV irradiation or in dark, and the results are illustrated in Fig. 7. It can be seen that about 10% eosin B was removed with the pristine MMT in dark (curve a) due to the adsorption of MMT, while about 20% eosin B was removed by the ZnS-MMT composites under the same conditions (curve b). This indicates that both the pristine MMT and the ZnS-MMT composites have adsorptive ability to remove eosin B without

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reduction potentials, which might render the nanocrystallites to be electron donors for the photoreduction of the electrondecient dyes under UV irradiation. 4. Conclusions The ZnS-MMT composites were fabricated via hydrothermal treatment of the aqueous solution of thiourea and zinc acetate in the presence of the MMT exchanged with HTAB. The interlamellar space of the pristine MMT was greatly pillared by the HTAB molecules and the layered structure of MMT in the ZnS-MMT composites was destroyed to some extent. The ZnS particles with size of about 25 nm were planted onto the MMT layers. The prepared ZnS-MMT composites combined the adsorptive ability of MMT and the catalytic degradation ability of ZnS to remove eosin B from its aqueous solution efciently. The ZnS-MMT composites prepared in this work may nd some applications in catalysis eld. Acknowledgment This work is nancially supported by National Natural Science Foundation of China (Nos. 50472096, 20374057). References
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Fig. 7. Residual concentration of the eosin B aqueous solution (3.2 105 mol L1 , 75 ml) under different conditions: (a) with MMT in the dark, (b) with ZnS-MMT composite in dark, (c) with pristine MMT under UV irradiation, (d) with ZnS-MMT composites under UV irradiation.

UV irradiation. The difference between their adsorption capacities results from the different surface nature. As described above, the surface of ZnS-MMT composites is more hydrophobic compared to that of the pristine MMT. Because eosin B possesses large organic anion, it should be easily adsorbed by the hydrophobic surfaces. Therefore, it can be easily adsorbed by the ZnS-MMT composites. Under UV irradiation the ZnS-MMT composites exhibit much higher activity to remove eosin B from its aqueous solution than the pristine MMT. From curve d in Fig. 7, it can be seen that eosin B was almost removed completely by the ZnS-MMT composites within 20 min under UV irradiation. The highly catalytic activity of the composites probably results from their microstructures. As described above, ZnS nanoparticles were deposited on MMT. As supports, MMT stabilizes the ZnS nanoparticles to prevent them from aggregating, meanwhile, the modied MMT can also adsorb eosin B molecules, which is favorable to providing more opportunity for eosin B molecules to meet the ZnS nanoparticles deposited on MMT. Therefore, the as-prepared ZnS-MMT composites exhibited higher efcient photocatalytic activity to degrade eosin B. The reuse ability of the ZnS-MMT catalyst was tested by repeating the photoreduction degradation experiments under the same conditions using the recycled catalyst. The activity loss after ve runs was not considerable. The catalyst was examined by SEM after used ve times, and a typical SEM image is shown in Fig. 3h. It can be observed that the morphology of the sample almost kept unchanged, and ZnS nanoparticles (<50 nm) were still adhered perfectly to the surface of MMT and no large ZnS agglomerates formed. The enhancement of the photocatalytic activity is probably due to the size effect and the inhibition of hole and electron recombination by the electron transfer from the guest semiconductor to the host layer of MMT. It was reported that for doped ZnS nanospheres, guest metal ions could occupy the Zn2+ sites in the lattice, leading to the formation of Zn-metal-S multiple system [6,39]. For the ZnS-MMT composites prepared in this work, some transition metal ions present in MMT may enter the lattice of ZnS, leading to plenty of defects on ZnS nanoparticles. Therefore, the excited electrons on ZnS nanoparticles probably exhibit highly negative

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