1. Department of Chemistry-BK21, SungKyunKwan University, Suwon 440-746, Korea Chang, Juyeon and Jung, Duk-Young* Synthesis of Mesostructured Vanadium Oxide

2. SKKU Inorganic Materials Lab. Introduction Microporous Mesoporous Macroporous Pore size / Å 510501005001000 1. Liquid Crystal Templating(LCT) Machanism2. Folding Sheet(FS) Machanism hydrophilic head group hydrophobic tail group Surfactant as Template Synthetic Mechanism

3. SKKU Inorganic Materials Lab. (B) Distribution diagram for V(V)-OH- species (A) 51 V NMR spectra of vanadate solutions Structure of Vanadate in water Soln.

4. SKKU Inorganic Materials Lab. 1.VO x n- (pH, conc. control) : 0.15M NaVO 3 solution(pH8.4, 6.5, 4.8) with addition of 2M HCl soln. 2.VO x n- + CTA-bromide : Addition of excess CH 3 (CH 2 ) 15 N(CH 3 ) 3 Br soln.(wt 2.7%) to vanadate soln. 2.The colored precipitates are obtained. : CTAV1(white, pH8.4), CTAV3(pale- yellow, pH6.5) and CTAV5(orange, pH4.8) filtered, washing with double distilled water. 4.Hydrothermal treatment with pH control. : Starting material-CTAV1, CTAV3 and CTAV5, Solvent-double distilled water, pH control with 0.2M HCl soln. 5.UV/O 3 treatment. : Using UV/O 3 lamp (electrical power 20W, UV power 5W at 254 and 180nm) Procedure

5. SKKU Inorganic Materials Lab. Small angle X-ray diffraction of CTAV1, CTAV3 and CTAV5 25.3 27.0 26.4 2  (degree) 13.4 13.2 8.90 12.6 11.4 10.4 9.5 CTAV1 CTAV3 CTAV5

6. SKKU Inorganic Materials Lab. Small angle X-ray diffraction of CTAV1 with different conditions 24.9 12.5 27.0 13.4 30.7 25.1 34.8  degree) a b c d a.CTAV1 b.Sample a. dissolved in EtOH & titrated to pH 2.2 with HCl, c.Sample from b. synthesized hydrothermally at 120 o C d.Sample from b. synthesized hydrothermally at 160 o C

7. SKKU Inorganic Materials Lab. Small angle X-ray diffraction of CTAV3 with different conditions a b c d 23.5 26.4 13.2 24.9 26.4 33.3 13.9 26.9 13.5 26.4 23.5 13.3 12.8  degree) a. CTAV3 b. sample from a. synthesized hydrothermally at 100 o C c. sample from a. synthesized hydrothermally at 140 o C d. sample from a. synthesized hydrothermally at 180 o C

8. SKKU Inorganic Materials Lab. Small angle X-ray diffraction of CTAV5 with different conditions a b c d  degree) 24.0 23.4 22.7 11.9 26.6 23.4 29.1 12.0 11.9 9.87 10.5 11.2 a. CTAV5 b. sample from a. synthesized hydrothermally at 100 o C c. sample from a. synthesized hydrothermally at 140 o C d. sample from a. synthesized hydrothermally at 180 o C

9. SKKU Inorganic Materials Lab. d = 34.3 (211) (220) 2 Theta (degree) a.Hydrothermal treatment(at 180 o C) of isolated product by adding HCl from CTAV3 dissolved in EtOH Small angle X-ray diffraction of Vanadate with different conditions 38.6 31.211.1 2 Theta (degree) 44.4 (211) (220) (321) a. b. b. Hydrothermal treatment(at 170 o C) of CTAV3 in water Solution(pH6.7~7.4 with 0.2 NH 3 soln.)

10. SKKU Inorganic Materials Lab. 55.5 26.9A 29.8 27.6 (100) 24.5 (110) 21.1(200) d = 42.4A a b Aging for 24hrs As-synthesized Calcination at 330 o C UV/O 3 treatment for 60hrs UV/O 3 treatment for 90hrs Small angle X-ray diffraction of Vanadate with different conditions 27.6 a. Hydrothermal treatment(at 190 o C) of CTAV3 in water Solution b. UV/O 3 treatment from sample b. UV/O 3

11. SKKU Inorganic Materials Lab. C-H stretch CH 3 bend CH 2 bend V-O FT-IR As-synthesized UV/O 3 treatment for more than 6ohrs

12. SKKU Inorganic Materials Lab. Conclusion I. Various mesostructured materials using CTAB as template with hydrothermal treatment were synthesized. II. The products have poor thermal stability because of condensation of vanadates or strong interaction between surfactant and vanadates. III.According to XRPD and FTIR data, UV/ozone treatment provides an efficient means for the condensation of vanadate clusters, but not efficient for removing of organic surfactant.