TP CH KHOA HC V CNG NGH, I HC NNG - S 3(26).

2008

XC TC QUANG HA TIO2 MICRO NANO COMPOSIT MANG TRN VT LIU NANO CARBON C CU TRC
TIO2 MICRO NANO COMPOSITES PHOTOCATALYST CARRIED ON NANO CARBON MATERIAL WITH MACROSCOPIC STRUCTURE NG TUN ANH - NGUYN NH LM
Trng i hc Bch Khoa, i hc Nng
TM TT Xc tc quang ha trn c s composit TiO2/Cacbon nano hin ang c u t nghin cu rt nhiu trn th gii bi hot tnh quang ha cao v c kh nng hp th hu ht cc bc x t mt tri. Khi hp th cc photon, xc tc ny c th -xy ha hon ton cc hp cht hu c, to sn phm cui cng l CO 2 v H2O. Nghin cu ca chng ti hng n mt loi xc tc quang ha hon ton mi trn c s composit TiO2 thng mi, TiO2 sol-gel v Carbon nano, c mang trn vt liu c cu trc. Loi xc tc mi ny cho php tng cng hot tnh quang ha v gim gi thnh xc tc. Xc tc ny c ng dng ti phng th nghim trong h thng thit b phn ng quang ha lin tc phn hy cc hp cht hu c nhim trong nc thi. ABSTRACT Composite TiO2/Carbon nano based photocatalysts are being investigated widely in the world because of their high photoactivity and their capacity of absorbing almost of suns irradiation. By absorbing a photon, these catalysts can promote the total oxidation of organic compounds to CO2, H2O products. Our researches are now focused on the new photocatalysts based on composite TiO 2 commercial, sol-gel / Carbon nano with macroscopic structure. This new type of catalyst allows amplifying the photoactivity and reducing the cost. These catalysts were successfully applied in our laboratory for continuous systems to degradate organic compounds in waste water.

1. t vn Trong nhng nm gn y, titan dioxit (TiO2) c s dng nh mt xc tc quang ha x l nhng vn nhim mi trng, c bit l loi cc hp cht c hi trong nc thi [1-3]. Tuy nhin, ch c nhng bc x t ngoi, chim khong 4% bc x mt tri [4], ng vi cc photon c nng lng ln hn 3,2eV mi c hp th v to ra hiu qu quang ha. Do , cc hng nghin cu v tng kh nng quang ha ca TiO2 trong vng nh sng kh kin c pht trin mnh s dng c hiu qu hn c tnh quang ha loi vt liu ny. Trong nhng nghin cu gn y, ngi ta c bit ch trng n vic p dng cc dng Cacbon nano ng (CNT) v Cacbon nano si (CNF) nh vo cc c tnh u vit ca n: kh nng dn in rt tt, ng knh c kch thc nano, hp ph cao v en tuyt i [5] v khi kt hp vi TiO2 to ra hot tnh

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quang ha rt mnh [6]. Cc loi xc tc quang ha trn c s composit TiO2/CNT v ang c nghin cu nhiu nhng ch dng li vic kho st trn h thng phn ng gin on. Xc tc c tng hp di dng bt gy kh khn cho vic ng dng vo thc t v chi ph cao cho h thng lc xc tc [7]. Hn na, phng php ph bin hin nay a TiO2 ln CNT l phng php sol-gel i t cc tin cht ca alkoxide titan. Gi thnh ca alkoxide titan rt cao, cng thm cc iu kin khc nghit khi nung thiu kt nhit cao khin cho gi thnh xc tc tng ln rt nhiu. Vi nhng l do nh trn, nghin cu ca chng ti hng n vic tng hp ra loi xc tc quang ha mi dng composit ca TiO2 v nano cacbon: cacbon nano ng a lp MWNT v cacbon nano si CNF mang trn vt liu c cu trc. Loi xc tc mi ca chng ti c hot tnh tng cng nhiu ln so vi cc loi tng c cng b, ng thi gi thnh gim ng k nh vic tn dng hot tnh cao ca pha anatase TiO2 thng mi c trong thnh phn xc tc. Vic kim tra hot tnh quang ha ca xc tc c thc hin bng phn ng phn hy methylen xanh di bc x nh sng mt tri trong h thng thit b phn ng gin on v lin tc. 2. Tng hp xc tc Xc tc c tng hp vi 3 hp phn: TiO2 thng mi, TiO2 sol-gel v Cacbon nano ng a lp (MWNT) hoc Cacbon nano si (CNF). TiO2 thng mi (99% dng anatase, kch thc ht trung bnh l 1,7 micromet) t tp on SENSIENT c s dng trc tip. TiO2 sol-gel c tng hp bng phng php sol-gel t tin cht Ti(OC3H7)3. MWNT v CNF c tng hp theo phng php kt t ha hc trong pha hi (CVD). y l cc sn phm ca cng trnh nghin cu v cacbon nano ca TS Nguyn nh Lm, trng i hc Bch Khoa, i hc Nng. Hnh 1 m t hnh nh bn ngoi v cu trc ca CNF sau khi c pht trin v nh hnh trn m carbon thu c t knh hin vi in t qut (SEM).

Hnh 1: nh bn ngoi v cu trc ca CNF mang trn m carbon (nh SEM). Chng ti tin hnh tng hp xc tc quang ha trn c s TiO2, vi tn gi micro nano composit, bng cch dn TiO2 thng mi c kch thc trung

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bnh 1,7 micromet (TiO2 TM) ln MWNT v CNF vi qua lp TiO2 sol-gel cng c chiu dy c nano. Tn gi cho cc loi xc tc khi dng MWNT v CNF trn vt liu c cu trc ln lt l micro nano composit 1 v micro nano composit 2 vi cc t l thnh phn theo khi lng nh sau:. - Xc tc Micro nano composit 1: TiO2(TM)/TiO2 sol-gel/MWNT = 1/0,25/0,05. - Xc tc Micro nano composit 2: TiO2(TM)/TiO2 sol-gel/MWNT = 0,8/0,2/0,7 Pha anatase ca TiO2 thng mi c s dng vi vai tr l pha quang hot chnh trong xc tc ca chng ti. iu ny lm gim ng k gi thnh xc tc composit v s dng c hot tnh cao ca TiO2 thng mi. 3. nh gi hot tnh xc tc Hot tnh quang ha ca xc tc c nh gi da trn kh nng phn hy cc hp cht hu c di tc dng ca bc x nh sng. 3.1. Cht phn ng Trong nghin cu ny, chng ti nh gi hot tnh qua kh nng phn hy Methylen xanh. Cc thng tin ca Methylen xanh (MB) c trnh by trong bng 1. Methylen xanh dng bt ban u c pha vo nc ct theo cc nng cho trc (50, 100 v 200mg/l). Bng 1: Mt s thng s ca Methylen xanh Cng thc C16H18ClN3S 3.2. Ngun sng Chng ti s dng 2 ngun bc x nh sng khc nhau: n cao p hi thy ngn (Osram 250 W) - cng sng ti v tr trn b mt ng phn ng l 57 klux tng ng vi 83,4 W/m2 v nh sng mt tri c dng t 10h n 15h hng ngy, cng sng trung bnh ti b mt ng phn ng l 78 klux tng ng vi 114,2 W/m2. 3.3. Thit b phn ng (TBP) Trong h thng phn ng gin on, chng ti s dng TBP hnh tr bng thy tinh, ng knh 100mm, dung tch 300ml. H thng TBP lin tc c thit k v ch to ti phng th nghim Lc ha du, trng i hc Bch khoa, i hc Nng, gm cc ng thy tinh c ng knh 6mm, b dy thnh ng 0,4mm; c b tr gia h thng cc tm knh phn quang (hnh 2). Lu lng x l qua TBP c iu khin bng valve. Cu trc ha tan trong nc 50 g/l Mu Xanh da tri Bc sng hp ph 650nm

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Hnh 2: H thng TNP lin tc c ch to ti trng i hc Bch khoa, H Nng 3.4. Qui trnh phn ng v phn tch mu 3.4.1. H thng phn ng gin on: Mt lng xc tc tng ng 0,2g TiO2 c cho vo TBP (TiO2 TM, TiO2 sol-gel, TiO2 sol-gel/CNT v micro nano composit 1), sau thm 100ml dung dch MB 200 mg/l iu chnh pH = 3. Hn hp c khuy t trong bng ti trong 1h qu trnh hp ph t cn bng. Mu u tin c ly ra xc nh nng MB ban u trc khi phn ng. Sau hn hp huyn ph c chiu sng bng n cao p thy ngn v khuy t lin tc vi tc khng i. Mu c ly ra theo chu k trong sut thi gian phn ng. Sau khi ly tm tch xc tc, nng MB trong mu c xc nh bng hp th quang trn my UVVis (JENWAY 6305) bc sng 650nm v xc nh ch s COD theo ASTM D1252 ti Trung tm ng dng Tin b Khoa hc v Cng ngh, S Khoa hc v Cng ngh Nng. 3.4.2. H thng phn ng lin tc: Mt lng xc tc tng ng 0,7g TiO2 (micro nano composit 2 v TiO2 TM-TiO2 sol-gelcacbon hot tnh) c cho vo TBP dng ng v lp vo h thng. Dung dch MB nng 50 mg/l c iu chnh pH = 3 c cho chy qua h thng thit b phn ng vi lu lng c khng ch. Ton b cc ng phn ng c chiu sng bng n hoc nh sng mt tri. Qu trnh phn tch mu c thc hin tng t i vi h thng phn ng gin on. 4. Kt qu v tho lun 4.1. Cu trc micro nano composit 1 thu c t knh hin vi in t truyn qua. Cc nh TEM ca xc tc micro nano composit 1 thu c trn hnh 3 chng minh bn c hc cao h xc tc phc hp ny sau khi b phn tn trong

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dung mi di tc dng ca vi sng cng cao. Hon ton khng c ng nano carbon no nm ring l cho thy ton b cc ng nano carbon c dn rt tt trn b mt ht TiO2 thng mi bng lp TiO2 sol-gel. Ti mi v tr c nano carbon u c TiO2 sol-gel (v tr c mu en m trn nh), v b dy lp sol-gel c kch thc rt nh, cha n 50 nm.

Hnh 3: nh knh hin vi in t truyn qua (TEM) ca xc tc "Micro Nano Composite 1" iu ny cho thy phng php tng hp xc tc ca chng ti l hon ton ng n v nh hot tnh xc tc rt cao c thc nghim chng minh khi kho st phn ng phn hy MB di tc dng ca nh sng. 4.2. Phn hy Methylen xanh di tc dng ca xc tc quang ha trn h thng phn ng gin on Quan h gia chuyn ha v thi gian phn ng trn cc cht xc tc khc nhau c th hin trn hnh 4. Kt qu cho thy rng chuyn ha ca TiO2 sol-gel thp hn TiO2 thng mi (TiO2 TM) do kh nng hp ph km ca n [17]. Vi mu TiO2/CNT, giai on u CNT hp ph mnh MB nn lm gim mnh nng MB trong dung dch, tuy nhin khi chiu sng th nng MB gim chm. chuyn ha ca xc tc micro nano composit 1 ln hn TiO2 TM khong 10%, v t 98% sau 3h chiu sng. iu ny chng minh s tn ti ca hiu ng synergic gia cacbon nano v TiO2. Ngoi ra chng ti cng kho st s phn hy MB trong mi trng CO2. Mt lng xc tc khc tng ng 0,2g TiO2 v 100ml dung dch MB 50 mg/l. Sau 1 gi phn ng, mu dung dch sau c ly tm tch xc tc v phn tch COD. Kt qu c th hin trn hnh 5. Kt qu cho thy mu micro nano composit 1 c kh nng phn hy trit hn TiO2 thng mi. Sau 1h chiu sng th hu nh tt c cc hp cht hu c b oxi ha hon ton to CO2 v H2O. Cn phi ch rng: iu kin thng (25oC 1 atm), lng oxi ha tan trong nc bo ha 9 mg/l [10]. Nh vy c th c th khng nh rng cc nguyn t Hydro v Oxi hot tnh sinh ra trn b mt xc tc t qu trnh quang in phn nc ng vai tr chnh trong vic kh v oxi ha cc hp cht hu c.

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chuyn ha, %

COD, mgO2/l

1 - TiO2 thng mi 2- Micro composite

Hp ph Chiu sng

Thi pht

gian,

Hnh 4: Chuyn ha ca MB theo thi gian Hnh 5: COD trcv sau 1 gi phn ng Phn tch kt qu thu c trn xc tc micro nano composit 2 cng cho kt qu tng t, tuy nhin trn CNF hiu qu quang in phn cao hn do cc tm kim loi tn ti nh ca si nano carbon nh c chng minh trn cc nh thu c t knh hin vi in t truyn qua (TEM, hnh 6) v qut (SEM, hnh 7).

Hnh 7: nh SEM thu c ch composit vt liu CNF/m Carbon, Hnh 6: nh (TEM) m t s chng minh cc tm xc tc Ni b y ra pht trin ca CNF trn cc tm khi b mt cht mang trong qu trnh xc tc Ni [12] pht trin CNF. [12] T cc kt qu thc nghim trn, chng ti xut c ch hot ng ca xc tc micro nano composit theo 4 phn ng nh sau: Ni/MWNT/TiO2 + h Ni-/MWNT+/TiO2 (1) + + Ni /MWNT /TiO2 Ni /MWNT/TiO2 (2) + + o 2Ni /MWNT/TiO2 + H2O(hp ph) 2Ni/MWNT/TiO2 + 2H +2OH (3) 2Ni-/MWNT/TiO2+ + H2O(hp ph)2Ni-/MWNT/TiO2+Oo+ 2H+ (4)

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Oxi nguyn t v Hydro mi sinh ny vi hot tnh rt mnh v s thc hin cc qu trnh oxi ha v kh cc cht hu c b hp ph trn b mt xc tc. Cc qu trnh ny c th c m t trn hnh 8. Theo c ch ny, b dy lp TiO2 sol-gel nh hng rt ln n kh nng chuyn electron, b dy cng nh th hiu qu chuyn cng cao. iu ny c khng nh r rng khi chng ti tin hnh so snh hot tnh ca 2 loi composit trn c s CNF v cacbon hot tnh trn h thng lin tc, c trnh by phn tip theo.

Hnh 8: C ch hot ng ca micro composit 4.3. Phn hy Methylen xanh di tc dng ca xc tc quang ha trn h thng phn ng lin tc Trn h thng ny, thi gian lu t chuyn ha MB 100% l 21 pht v 24 pht tng ng vi trng hp chiu bng nh sng mt tri v chiu n cao p thy ngn. Quan h gia thi gian lu v chuyn ha c th hin trn hnh 9.
chuyn ha, % chuyn ha, % 2

Thi gian lu, pht

Thi gian chiu sng, h

Hnh 9: chuyn ha di n v Hnh 10: chuyn ha theo thi gian hot nh sng mt tri theo thi gian lu ng ca xc tc composit TiO2 TM-SG / CA Mt lng xc tc composit TiO2 TM SG cacbon hot tnh (CA) vi phng php tng hp tng t c th hot tnh ng thi so snh. Kt qu cho thy mu xc tc trn CA cho hiu qu quang ha rt thp, bn c hc km v gim hot tnh nhanh chng (hnh 10). nh gi bn ca xc tc, chng ti cho h thng hot ng thi gian lu c nh 24 pht v ly mu phn tch nh k. Khi chuyn ha gim xung cn 95%, chng ti s tin hnh ti sinh xc tc v ti s dng xc tc. Xc tc c ti sinh ch bng cch cho chiu sng di dng nc ct chy lin tc

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trong 20h. S thay i chuyn ha theo thi gian s dng v s ln ti sinh c th hin trn hnh 11.
Chiu sng
chuyn ha, %

Ti sinh ln 1

Chiu sng 20h

Ti sinh ln 2

Chiu sng 18h

Ti sinh ln 3

80h

Thi gian, h

Hnh 11: chuyn ha theo thi gian ca xc tc Micro Nano Composit 2 Nguyn nhn ca s gim hot tnh xc tc c th c gii thch do cc sn phm trung gian sinh ra trong qu trnh phn ng b hp ph ln tm xc tc, c th l cc hp cht cha N, S v cc cht khong (Na+, Cl-, SO42-) [13,14,15,16]. Hot tnh ca xc tc c phc hi sau mi ln ti sinh c th c gii thch nh vo vic phn hy hon ton cc hp cht hu c trung gian bng oxi v hydro nguyn t trong qu trnh quang in phn nc. 5. Kt lun v xut Vi nghin cu ny, chng ti to ra c mt loi xc tc quang ha hon ton mi, trn c s t hp cc vt liu kch thc micro v nanomet, c mang ln vt liu c cu trc. Hot tnh quang ha ca xc tc mnh v c th hot ng n nh trong thi gian di. c bit, h xc tc ny c th c ng dng trong h thng x l nc thi lin tc x l cc cht nhim hu c di tc dng ca nh sng mt tri. Chi ph sn xut xc tc tnh cho 1 gam TiO2 c gim i ng k do s dng c cc loi TiO2 thng mi vi pha anatase trong thnh phn v gim c lng TiO2 sol-gel. Cn phi ch rng: Chi ph sn xut TiO2 sol-gel rt ln bi gi ca alkoxide titan cao v chi ph vn hnh l nung to dng anatase rt ln, do cn nhit nung cao (400-500oC) v mi trng kh tr hoc chn khng trnh t chy carbon nano. Khi vn hnh trn h thng nghin cu trong phng th nghim ca chng ti, kt qu x l rt tt v chi ph vn hnh rt nh khi s dng nng lng mt tri, hu nh bng 0. Kt qu y tim nng ca nghin cu ny c th c ng dng rng ri cho h thng cng nghip trong vic phn hy cc hp cht hu c c trong nc thi m cc phng php truyn thng khng th thc hin c. TI LIU THAM KHO [1] A. Mills, S.L. Hunte, J. Photochem. Photobiol. A 108 (1997) 1. [2] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1 (2000) 1.

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[3] O. Legrini, E. Oliveros, A.M. Braun, Chem. Rev. 93 (1993) 671 [4] Amy L. Linsebigler, Guangquan Lu, and John T. Yates, Surface Science Center, Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 [5] P. Serp, M. Corrias, P. Kalck, Appl. Catal. A 253 (2003) 337 [6] Wendong Wang, Philippe Serp, Philippe Kalck, Joaquim Lus Faria, Journal of Molecular Catalysis A: Chemical, 235 (2005) 194199 [7] Arie Dipareza Syafei, Cheng-Fang Lin, Chung-Hsin Wu, Journal of Colloid and Interface Science, 2008 (article in press) [8] Cheewita Suwanchawalit, Sumpun Wongnawa, Applied Catalysis A: General ,338 (2008) 8799 [9] Yongjun Chen, Dionysios D. Dionysiou, Journal of Molecular Catalysis A: Chemical, 244 (2006) 7382 [10] Peter Askin, Physical chemistry, 2006 [11] M. Radecka, M. Rekas, A. Trenczek-Zajac, K. Zakrzewska, Journal of Power Sources, 181 (2008) 4655 [12] Nguyn nh Lm, Bo co nghim thu ti cp b, Nghin cu tng hp vt liu Nano cacbon (nanotube v nanofiber) bng phng php phn hy xc tc cc hp cht cha cacbon trong iu kin Vit Nam, 2008 [13] Jing Shang, Yongfa Zhu, Yaoguo Duw and Zili Xuw, Journal of Solid State Chemistry, 166, 395399 (2002) [14] V. Vorontsov,1 E. N. Kurkin, and E. N. Savinov, Journal of Catalysis, 186, 318324 (1999) [15] Nuria Gonzlez-Garca, Jos A. Aylln, Xavier Domnech, Jos Peral, Applied Catalysis B: Environmental, 52 (2004) 6977 [16] Eva Piera, Jos A. Aylln, Xavier Domnech, Jos Peral, Catalysis Today, 76 (2002) 259270 [17] A. Piscopo, D. Robert_, J.V. Weber, Journal of Photochemistry and Photobiology A: Chemistry, 139 (2001) 253256

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