Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

XC TC QUANG HA MICRO NANO COMPOSIT TRN C S TIO2 - NANO CARBON MANG TRN VT LIU C CU TRC
MICRO NANO COMPOSITES BASED ON TIO2 NANO CARBON PHOTOCATALYST WITH MACROSCOPIC SHAPING SVTH: Ng Tun Anh,
Lp 03H5 Trng i hc Bch Khoa

GVHD: Nguyn nh Lm
Trng H Bch khoa, H 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 CO2 v H2O. Tuy nhin, nhng nghin cu v loi composit ny ch dng vic tng hp xc tc dng bt cho h thng phn ng gin on v hon ton khng c kh nng p dng trong cc h thng x l lin tc. Vit Nam, loi xc tc ny hu nh vn cn rt mi m. Nghin cu ca chng ti hng n mt loi xc tc quang ha hon ton mi trn c s composit TiO 2 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 abundantly in the world because of their high photoactivity and their capacity in absorbing almost of suns irradiation. By absorbing a photon, these catalysts can promote the total oxidation of organic compounds to CO2, H2O products. However, researches about this composite are just for a the powder catalysts applications in a batch reactor. Theirs uses in the continuous system seem impossible. In Vietnam, these catalysts are completely untouched. Therefore, our researches are now foccused onto the new photocatalysts based on composite TiO 2 commercial, sol-gel / Carbon nano with macroscopic shaping. 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. T kha: TiO2, xc tc quang ha, carbon nanotube, carbon nanofiber, sol-gel

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, ng vi cc photon c nng lng ln hn 3,2eV mi c hp th v to ra hiu qu quang ha [4]. Trong cc 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]. Vt liu CNT-CNF to c hiu ng synergic rt tch cc vi TiO2, dn n vic hnh thnh mt h thng xc tc c hot tnh quang ha rt mnh ngay trn b mt [6]. iu ny cho php tng kh nng quang ha ca TiO2 trong vng nh sng kh kin. Tuy nhin, hin nay cc loi xc tc quang ha trn c s composit TiO2/CNT c tng hp di dng bt gy kh khn cho vic ng dng vo thc t v tn chi ph cao cho h thng lc xc tc

208

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

[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 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 mt loi xc tc quang ha hon ton mi dng composit ca TiO2 v nano cacbon: cacbon nano ng nhiu 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. 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 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 lng ng pha hi ha hc xc tc (CVD) vi xc tc Fe v Ni tng ng. CNF c pht trin v nh hnh trn cc tm m (felt) cacbon. y l cc sn phm thu c t cc cng trnh nghin cu v cacbon nano ca Tin s Nguyn nh Lm, i hc Bch Khoa, i hc Nng. TiO2 thng mi (99% dng anatase, kch thc ht trung bnh l 1,7 micromet) t tp on SENSIENT c s dng trc tip, khng chu bt k mt qu trnh x l tip Hnh 1: nh bn ngoi v cu trc ca CNF sau khi pht trin theo no. trn m carbon thu c t knh hin vi in t qut (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 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 tng ng l micro nano composit 1 v micro nano composit 2 vi cc t l 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. Trong c hai loi xc tc ny, 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 hot tnh tng mnh sau khi nung 350oC. 3. Phn tch 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 (MB) (bng 1). MB dng bt ban u c pha vo nc ct theo cc nng cho trc (50, 100 v 200mg/l). Dung dch H2SO4 v NaOH long c s dng iu chnh pH ca nguyn liu phn ng ban u. 3.2. Ngun sng

209

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

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 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. 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, gm cc ng thy tinh c ng knh 6 mm, b dy thnh ng 0,4 mm; c b tr gia h thng cc tm knh phn quang (hnh 2). 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 solgel/MWNT v micro nano composit 1, sau thm 100 ml 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 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 Hnh 2: H thng thit b phn ng di n phn ng. Nng MB trong mu c xc nh bng hp th quang trn my UV-Vis cao p hi thy ngn v di nh sng mt tri (JENWAY 6305) bc sng 650 nm v xc nh ch s COD theo ASTM D1252. 3.4.2. H thng phn ng lin tc: Mt lng xc tc tng ng 0,7g TiO2 (micro nano composit 2 v TiO2TM-TiO2sol-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 TBP vi lu lng c khng ch. Qu trnh phn tch mu c thc hin tng t i vi h thng phn ng gin on.

Bng 1: Mt s thng s ca Methylen xanh

Cng thc Cu trc Mu Bc sng hp th cc i Xanh da tri 650 nm C16H18ClN3S

4. Kt qu v tho lun 4.1. nh cu trc micro nano composit 1 t knh hin vi in t truyn qua (TEM)

TiO2 TM

TiO2 sol-gel MWNT

TiO2 sol-gel

Hnh 3: nh thu c t knh hin vi in t truyn qua (TEM)

210

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

m t cu trc ca micro nano composit 1 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 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. iu ny cho thy phng php tng hp xc tc ca chng ti rt kh thi 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 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. Dung dch MB 50 mg/l cng c kho st trong mi trng kh CO2 vi 0,2g xc tc micro nano composit 1 c chiu sng bng n cao p thy ngn trong 1h. 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. 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 qu trnh quang in phn nc ng vai tr chnh trong vic kh v oxi ha cc hp cht hu c. Vi cu trc ca loi micro nano composit 1, qu trnh quang in phn H2O c th c kch thch bi hu ht cc loi bc x trong vng t ngoi v kh kin, band-gap ln hn hiu in th in phn H2O, 1,23 eV v ph hp vi th ca qu trnh in phn to H2 v O2: EC > EH2O/H2; EV < EO2/H2O [11]. ng thi tc ti hp ca eHp ph v h+ gim i ng k v qu trnh oxi haChiu sng kh xy ra ti nguyn t kim loi trn Thi gian, pht Cacbon nano (Fe, trong trng hp MWNT, Ni trong trng hp MWNF) v ti b mt TiO2, c bit l trong nhng dung dch c Hnh 4: chuyn ha ca Methylene xanh theo thi gian nng thp ( chuyn ha cao). Phn tch kt qu thu c trn xc tc micro nano composit 2 cng cho kt qu tng 1 - TiO thng mi t, tuy nhin trn CNF hiu qu quang in 2- Micro composite 1 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).
chuyn ha, %
2

211

COD, mgO2/l

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

T cc kt qu thc nghim trn, chng ti xut c ch hot ng ca xc tc micro nano composit nh c trnh by trn cc Hnh 5: Gi tr COD ca dung dch trc phn ng (1) n (4). v sau 1h chiu sng Ni/MWNT/TiO2 + h Ni-/MWNT+/TiO2 (1) + + Ni /MWNT /TiO2 Ni /MWNT/TiO2 (2) 2Ni-/MWNT/TiO2+ + H2O(hp ph) 2Ni/MWNT/TiO2+ + 2Ho + 2OH- (3) 2Ni-/MWNT/TiO2+ + H2O(hp ph) 2Ni-/MWNT/TiO2 + Oo + 2H+ (4) 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 Hnh 6: nh thu c t knh hin vi in ca 2 loi composit trn c s CNF v t truyn qua (TEM) m t s pht trin cacbon hot tnh trn h thng lin tc.
ca CNF trn cc tm xc tc nano Ni [12]

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 n. 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 94%, chng ti tin hnh ti sinh xc tc. Xc tc c ti sinh ch bng cch cho chiu sng di dng nc ct chy lin tc trong 20h. S thay i chuyn ha theo thi gian s dng v s ln ti sinh c th hin trn hnh 9.
Chuyn ha 100%
chuyn ha, %

Ti sinh ln 1

Chuyn ha 100% 20h

Ti sinh ln 2 Chuyn ha 100% 18h

Ti sinh ln 3

80h

Thi gian, h

212

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 6

i hc Nng - 2008

Hnh 9: chuyn ha theo thi gian hot ng ca xc tc Composit N21 TiO2 TM-SG / MWNF Nguyn nhn ca s gim hot tnh xc tc c th c gii thch do cc snphm trung gian sinh ra trong qu trnh phn ng b hp ph ln tm xc tc, c th l cc hp cht cha N, Sv 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. Kt qu cho thy: trong ln s dng u tin, hot tnh xc tc rt n nh, chuyn ha t 100% trong vng 80 h s dng, sau mi ln ti sinh, n nh ca xc tc c gim nhng vn bo m s lm vic vi chuyn ha 100% trong mt thi gian di. 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] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] A. Mills, S.L. Hunte, J. Photochem. Photobiol. A 108 (1997) 1. A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1 (2000) 1. O. Legrini, E. Oliveros, A.M. Braun, Chem. Rev. 93 (1993) 671 Amy L. Linsebigler, Guangquan Lu, and John T. Yates; Surface Science Center, Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260 P. Serp, M. Corrias, P. Kalck, Appl. Catal. A 253 (2003) 337 Wendong Wang, Philippe Serp, Philippe Kalck, Joaquim Lus Faria; Journal of Molecular Catalysis A: Chemical 235 (2005) 194199 Arie Dipareza Syafei, Cheng-Fang Lin, Chung-Hsin Wu; Journal of Colloid and Interface Science, 2008 (article in press) Cheewita Suwanchawalit, Sumpun Wongnawa; Applied Catalysis A: General 338 (2008) 8799 Yongjun Chen, Dionysios, Journal of Molecular Catalysis A: Chemical; 244 (2006) 7382 Peter Askin, Physical chemistry, 2006 M. Radecka, M.Rekas; Journal of Power Sources 181 (2008) 4655 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 Jing Shang, Yongfa Zhu, Journal of Solid State Chemistry 166, 395399 (2002) V. Vorontsov,1 E. N. Kurkin, and E. N. Savinov; Journal of Catalysis 186, 318324 (1999) Nuria Gonzlez-Garca, Jos A.Aylln; Applied Catalysis B: Environmental 52 (2004) 6977 Eva Piera, Jos A. Aylln, Xavier Domnech, Jos Peral; Catalysis Today 76 (2002) 259270

[13] [14] [15] [16]

213