Krean Chem. Eng. Res., Vl. 44, N. 4, August, 2006, pp. 399-403 재현성있는메조포러스 박막의제조에대한연구 miçm m*çi**çqj***ç***çs*, ne, ** 130-743 ne r 90 * 440-746 e qk }} 300 *** l rl 136-791 ne 39-1 (2006 7 4p r, 2006 7 13p }ˆ) Reprducible Synthesis f Peridic Mesprus Thin Film Jae Yung Hur, Hyung Ik Lee*, Yung-Kwn Park**, Oh-Shim J***, Gwi-Nam Bae*** and Ji Man Kim*, Department f Envirnmental Engineering, **Faculty f Envirnmental Engineering, University f Seul, 90, Chennng-dng, Dngdaemun-gu, Seul 130-743, Krea *Department f Chemistry, Sungkyunkwan University, 300, Chenchen-dng, Jangan-gu, Suwn 440-749, Krea ***Envirnment & Prcess Technlgy Divisin, Krea Institute f Science and Technlgy, 39-1, Hawlgk-dng, Sungbuk-gu, Seul 136-791, Krea (Received 4 July 2006; accepted 13 July 2006) k q p r s k p p band gap p p l p sd p l v p re pp, p d m p l sl m p k q p lv rp rrp rl m. p nk l r~ pp s~mp qsl p s rl p r ~ m d tp m p p p. ll 2 sp sp v p q p lp p e sp }q m. p p HCl r~p r~m P-123p p s k Žr tp p p dm m m l e p m p XRDm TEM p m. h Abstract There has been numerus reprts fr the synthesis f mesprus thin films due t nt nly the high surface area and regular messcale pres but als wide band gap and pht activity. Hwever, the synthesis has been restricted by the limited reprducibility mainly due t the extrardinarily fast hydrlysis and cndensatin rate f titania precursrs. In this reprt, mlar cmpsitin f reactin batch (HCl/Ti and Ti/P123) and exterir cnditin (humidity and temperature) during cating and anealing prcess. Thereafter, the mesprus thin films were characterized by XRD and TEM. Key wrds: Mesprus, Thin Film,, Sl-gel 1. 1992 l p p r s p n p rp v s d e vp p p l[1], p s d e v pnl p k p s d rp l ep t v p[2]. vp p p v pp T whm crrespndence shuld be addressed. E-mail: jimankim@skku.edu, qn }l p p p v p l ~q,,, q, lv r [2-12] p n ql k rn p qqp p l q p ep ppˆ p vp. p p, l lel sp v Žn ˆp p l l p p v p. 1995l Antnellim Yingp s~ phsphate qn r n l sp v mp [3], Sanchezm lvp CTABrp s~ l EISA 399
400 qmëp pëmëtmeëëv (evapratin-induced self-assembly) p p l Tim HClp l sp, Žp petri dishl k m, k ml l} l 2D hexagnal(p6 m) s v Žn ˆp mp[13], Yuem Ga s ~ P123 pn l Tim H 2 Op hydrlysism cndensatin pp sr CeCl 3 ~ l n lrkr p s d m[14]., Jimmy p s~ n v k, pž pn l 3 s (wrmhle-like framewrk)p p p v lr krp sp m[15]. p ˆp n pq r p l rqm kqp p plv l pn l pl r l l l, s d p p er pnl tn pq. prp s p v vp s~p q rp q s p l p s- p pn l p. l pl p p SiO 2 m p r v p sp v s l rp nl mp, sp v p l lnp k. r~ rp s~mp qnp e p k n p p pp l srp l, p sp p s(s,, s~p s, r s, ph, l} m )l l q p lv n p[2, 4]. sp p rp r~ nkl q sl pp l rp l p p p pp rr srp tn l, p srp }p p p q p sr qnr n n n l p p p lr pf ssp sr k., sp rr sr pf ˆp sp p q p p p. ll rp sp l pf r l sp v p rs prp q p p re q. p ph srp r~p p sr s~ n ky triblck cplymerp sr l sp v sp l l m., pnkp Ž rl dm np v p p s l m v p (aging) rl mm d l p p s rp ˆ m. 2. prpanl : 0.011~0.034 P123pl. nkp ml 10 e. llv Ž nkp v lˆm Žmp ve eˆ l Ž l d Ž l p eˆ, m 8 C, 25 C, 40 Cl 5p e. srp 1 C/minp dm 120 Cv m 120 Cl 1e veˆ, e dm e 350 Cv l, 350 Cl 3e ve s~ n P123 r. 3. s d p pl prp s d p m v sp r~ p s rp ssp p sp p r tn np. nl l m p m p pl p p r~p s, r n P123 pm ky qm r ~p p n HClp kl ph s d p l m l l l m. n sp k p v r~ n l s d rs m. lšp(ethxide), kp p(i-prpxide), Šp(n-butxide) r~p n mp, v r~p pp l lˆm, kp Žm, ˆmp eˆ p pp p. pp p lšp>kp p>špp p, s d p p kp p Ti r~ rr p pl l rr p k pl(fig. 1). sp rp kp s d p l m l e p m. n P123 s~ ky triblck cplymerp P123(PEO 20 PPO 70 PEO 20 ) n m. k Ti-k e p r~ n m, p rp p p e m. 4.3 gp Ti(IV) isprpxide (TTIP) 3.12 gp HCl(35 wtí)l l ml 5 t, 12 gp 1-prpanll 1~3 gp P123 n nk m. n ekp 1 TTIP : 1.6~2.2 HCl : 6~8 H 2 O : 13 44 4 2006 8k Fig. 1. XRD patterns f mesprus different precursrs, after calcinatin at 350 C (1.0 Ti(OR) 4 : 0.0085 P123 : 2.0 HCl : 13 prpanl).
q p sd p rsl l 401 Fig. 2. XRD patterns f mesprus different amunt f P123, after calcinatin at 350 C (1 TTIP: x P123 : 2.0 HCl : 7.5 H 2 O : 13.2 prpanl). pmp v kp nkl k pmp qnl p r~m qs p, p q r kpm rl rp v p (k 7~10 nm)p }. v, r sp sp vp l p srp rp l p ˆ ls p p l lvl p p[16, 17]. Fig. 2 r, P123p l s d p p r r p X- r(xrd) lt. r~ l P123p kp 0.0057, 0.0114, 0.0171, 0.0228p p XRD Ž p P123p kp 0.0114 p, 0.0171 p p l r sp ppp k p. 0.0057p P123 n sl r pp l rl rp r s eˆ ll, p P123, 0.0228p nl p ss l pp r l p r l s mr p r. P123=0.0171p s d p TEM 2D-hexagnal s ppp pl, p 2D-hexagnal sp p nl. p rp np pnkp ph p, p r~p p pp k rm r~p qnl m p ~ s s l tn n r rp. Fig. 3p r~ HClp eˆ s d p XRD lt. m p p n Fig. 3. XRD patterns f mesprus different amunt f HCl, after calcinatin at 350 C (1.0 TTIP: 0.0085 P123 : x HCl : 3.7x H 2 O : 13 prpanl). r~p l r~ 2 p p HClp n l p p pp lr mp l r sp s d p p p k pl. p sp r l sp s d lp p lv p ˆ rs Ž r l} rlp d m p sl r s s d p vp p ep e p l k l, p dm m m l l l. Fig. 4l re m p, Žrl d p t ˆ s d l m j. t(d 45Í)l d Žp l p l nm l v, lˆm Žm eˆ l p lp np ep sp tp p } p l q r sp sp XRD p ltl. v l d Ž rl dl p p p pp }rp k t pp, lˆmp Žm eˆ tl p d Ž nl p pp lr pnl Ž nk l np vv sr pl n q r sp s d p lp p. p p pnkp nm p Žmp eˆ l Ž mp nl q r sp p lp pl. Krean Chem. Eng. Res., Vl. 44, N. 4, August, 2006
402 qmëp pëmëtmeëëv Fig. 4. XRD patterns f mesprus thin films, prepared under different spin cating cnditin, after calcinatin at 350 C (1.0 TTIP: 0.0085 P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl). Fig. 6. XRD patterns f mesprus thin films, prepared under different aging temperature, after calcinatin at 350 C (1.0 TTIP: 0.0085 P123 : 2.0 HCl : 7.5 H 2 O : 13 Prpanl). Fig. 5. TEM images f mesprus thin films prepared under different spin cating envirnments (1.0 TTIP : 0.0085 P123 : 2.0 HCl : 7.5 H 2 O : 13 prpanl). tlm Žm l Ž p v e Œrq (HRTEM)p n l p s s m(fig. 5). XRD m m p t(d 45Í)l Ž l lp e v s l p, Žm l Ž ep n 2D hexagnal s q r sp 44 4 2006 8k l., Žm l rs ep n TEM lp q (5.7 nm) XRD (5.5 nm) p p p k p. s d p rs rl Ž r k Ž eˆ r n tn p r p, m ssl m p p k pl. Fig. 6p XRD l pp m p p p p m, 8 Cl l} e sp s vp k pl. 4. s d v tl p s d l pn p ppl p q r p l rkp plm. ll s d p q p p re q s k Ž r Ž p r~p p p pl t n d np v s d p l m p s rp l pf q p l s d p rs pl. l lp vp k ld. y 1. Kresge, C. T., Lenwicz, M. E., Rth, W. J., Vartuli, J. C. and Beck, J. S., Ordered Mesprus Mlecular Sieves Synthesized by a Liquid-crystal Template Mechanism, Nature, 359, 1710-1712(1992).
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