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ชื่อบทความที่เผยแพร่ Intercalation of Zinc Sulfide-Manganese Sulfide in Montmorillonite by Solid-Solid Reaction 
วัน/เดือน/ปี ที่เผยแพร่ 11 พฤษภาคม 2556 
การประชุม
     ชื่อการประชุม International Symposium on Materials Chemistry of Intercalation Compounds (MCIC2013) 
     หน่วยงาน/องค์กรที่จัดประชุม committee of MCIC2013  
     สถานที่จัดประชุม Waseda Campus, Waseda University 
     จังหวัด/รัฐ Nishiwaseda, Shinjuku-ku, Tokyo 
     ช่วงวันที่จัดประชุม 11 พฤษภาคม 2556 
     ถึง 11 พฤษภาคม 2556 
Proceeding Paper
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     บทคัดย่อ Intercalation of organic and/or inorganic species in the interlayer spaces of layered inorganic solids is an interesting topic for constructing ordered organic-inorganic or inorganic-inorganic materials with unique nanostructures controlled by host-guest and guest-guest interactions [1]. Montmorillonite is a 2:1 layered clay mineral, which exhibits useful characteristics including large surface area, swelling ability, adsorptive and cation exchange properties for creating functional intercalation compounds. On the other hand, mixed metal sulfides have attracted considerable attention due to its tunable surface and optical properties. Several complicated methods such as reverse micelle, microemulsion-mediation and core-shell processes have been carried out to synthesize mixed metal sulfides including zinc sulfide-manganese sulfide and so on [2]. Here, a facile method, solid-solid reaction, was used to prepare mixed zinc sulfide-manganese sulfide in the interlayer space of montmorillonite. The in-situ formation of zinc sulfide and manganese sulfide in montmorillonite may lead to a highly luminescent hybrid. Zinc(II)-manganese(II) exchanged montmorillonite was prepared by adding the aqueous solutions of zinc(II) chloride (ZnCl 2 ) and manganese(II) chloride tetrahydrate (MnCl 2 ∙4H 2 O) into a dispersion of montmorillonite. The mixture was stirred overnight. The amount of the added zinc(II) or manganese(II) cation was 60 meq/ 100 g clay. The resulting solid was separated by centrifugation and washed repeatedly with deionized water until a negative chloride test was obtained and dried at 60°C in air atmosphere for 24 h. The solid was called zinc(II)-manganese(II)-montmorillonite. The mixed metal exchanged montmorillonite and sodium sulfide (Na 2S∙xH2 O) were manually ground in an agate mortar for 10-15 minutes and subsequently heated at 200°C for 1 h in air. The product was named zinc sulfide-manganese sulfide@montmorillonite. After the solidsolid reaction, the XRD pattern of the product showed the basal spacing of 1.46 nm. No reflection due to zinc sulfide, manganese sulfide, sodium sulfide and/or their compounds was seen in the XRD pattern of the product. This result indicated to the intercalation of sulfide ions in montmorillonite. Raman spectrum of the hybrid showed two broad and weak peaks at 261 and 344 cm -1 due to first-order LO and TO phonons of zinc sulfide, a intense peak due to manganese sulfide was observed at 511 cm -1 , supporting the formation of zinc sulfide and manganese sulfide in the hybrids. The absorption onset (Fig. 1b) observed at 338 nm was blue-shifted compared with those of pure zinc sulfide (348 nm, Fig. 1d) and manganese sulfide (350 nm, Fig. 1c), suggesting that the particle size of the incorporated mixed metal sulfides was smaller than that of the pure metal sulfides. The hybrid exhibited three emission bands (Fig. 1b) at 416, 438, 469 nm. The emissions peaks of zinc sulfide and manganese sulfide were seen at 451 and 469, as well as at 480 nm. The blue shift of three emission maxima (416, 438 and 469 nm) of the hybrid was due to the de-aggregation of zinc sulfide and manganese sulfide in the hybrid. In addition, the photoluminescence intensity of the hybrid was higher than those of zinc sulfide and manganese sulfide, indicating that the photoluminescence efficiencies of both zinc sulfide and manganese sulfide could be improved by the confinements into the interlayer space of montmorillonite. These results supported that zinc sulfide and manganese sulfide was successfully intercalated in montmorillonite by solid-solid reaction. 
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