1. Studies on the Syntheses and Applications of 3D Arrayed Quantum-Dot Nano-Clusters with the Orders of Teras in Zeolite Hosts 경북대학교 응용화학과 구조화학연구실 E1-301~303, Tel. 82-(0)53-950-5589, Fax. 82-(0)53-950-6594 Nam Ho Heo, Professor, Ph.D. (nhheo@mail.knu.ac.kr) Ph.D. Candidates Seok Han Kim, Gee Jin Jung, Ghyung Hwa Kim Master Candidates Hyun Jung Kim, Thanh Nga Nguyen Thi, Cheol Woong Kim Subjects & Objectives Studies on A. The Nature of Various Zeolitic Species a.New Chemical Species b.New Sorption Complexes c.Advanced Materials (3D Nanoclusters etc) d.Knowledge on Various Known Species B. The Applications of Zeolites a.Sorption Properties b.Encapsulation & Occlusion c.Physical Properties of New Materials d.Others Methodology A. Syntheses & Modifications a.Syntheses b.Static & Dynamic Ion-Exchanges c.Chemical & Physical Modifications d.Sorption & Reactions B. Characterizations a.Crystallographic Studies b.Spectroscopic Properties c.Sorption Properties d.Others Prepare Single Crystals X-ray Experiment Structure Determination Chracterization of New Nano Materials Advanced Nano Materials A. Quantum Dots (Nanoclusters) a. Nanoclusters of Indium Speices 1. In 5 Clusters in In-A a-c 2. In 5 Clusters in In-X d b. Nanoclusters of Silver Halides 1. Ag 4 I 4 Clusters in K-A e 2. Ag 4 Br 4 Clusters in K-A f B. 3D Array of Quantum Dots a. 3D In 5 Clusters in In-X g a N. H. Heo et al, J. Phys. Chem. B 1997, 101, 5531-5539. b N. H. Heo et al, J. Phys. Chem. B 1998, 102, 17-23. c N. H. Heo et al, J. Phys. Chem. B 2002, 106, 4578-4587. d N. H. Heo et al, J. Phys. Chem. B 2000, 104, 8372-8381. e N. H. Heo et al, J. Phys. Chem. B 2004, 108, 3168-3173. f N. H. Heo et al, manuscript in preparation. g N. H. Heo et al, J. Phys. Chem. B 2003, 107, 1120-1128. SynthesisSynthesis * Y. Kim, K. Seff, J. Phys. Chem., 82, 1978, 1071 Characterization Na-A By flow method for 2 days Ag-A * 0.05M aqueous AgNO 3 solution Washing with MeOH CAD4/Turbo Diffractometer PAL X-ray Diffractometer RIST XPS, etc In 5 Nanoclusters in In-A & X All sodalite units of In66-X are filled with the In 5 clusters All sodalite units of In66-X are filled with the In 5 clusters XPS(ESCA) Experiment Electron-Probe X-ray Analysis Ag 4 I 4 Nanoclusters in K-A(Ag 4 I 4 ) 0.5 (KI) Diameter of AgI nanocluster = 4.80 + 1.13 + 1.96= 7.89 Å One of the smallest nanoclusters in the world Blue shift Evidence for Quantum Size Effect of Ag 4 I 4 Nanoclusters (UV-Vis Spectrum) Applications of Ag 4 X 4 & In x Nanoclusters - Photocatalysts for solar energy conversion. e - Image plates for x-ray computerized radiography. f - Medium for optical information or image storage. G - Semiconductor materials for new device. e R. Beer, G. Calzaferri, J. lin, and B. Waldeck, Coord. Chem. Rev 111, 1991, 193 f Sonada, M.; Takano, M.; Miyahara, J.; Kato, H. Radiology 148, 1983, 833 g Hirono, T.; Yamada, T. Japanese Patent 61-061894, 1986 K-A(AgI or AgBr ) Reaction with KI (or KBr) solution in MeOH for 2 days X-ray Photoelectron Spectroscopy (XPS) XPS Image of In-X VG XPSLAB 250 012 3 45 L  's L  L  In Tl M a 's & M  's Si K a 's Al K  's In 87 -X In 88 -X Tl 92 -X Relative Intensity KeV 012345 O K  's S K  's In L  's In L  1 Al K  's Si K  's In L  's (A) (B) Relative Intensity KeV In 66 -X Fisons KEVEX/SIGMA system, an EDS system attached to a Hitachi S-4100 SEM