Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010

TNG HP V NG DNG XC TC QUANG HA TRN C S TITAN DIOXIT (TIO2) V CACBON NANO DNG NG (CARBON NANOTUBE-CNT) KH LU HUNH SU TRONG DIESEL
SYNTHESIS AND APPLICATIONS OF THE PHOTOCATALYST BASED ON TIO2 AND CARBON NANOTUBE (CNT) BY DEEP DESULFURIZATION OF DIESEL SVTH: L Vn Long, Phan Thanh Sn
Lp 05H5, Khoa Ha, Trng i hc Bch Khoa

KS. Trn Th Ne
Hc vin Cao hc Vt liu Hu C cu trc Nano v Bn vng, i hc Nam Toulon Var Php i hc Quc gia H ni

TS. V Th Thu H
Vin Ha hc Cng nghip

GVHD: TS. Nguyn nh Lm

Khoa Ha, Trng i hc Bch Khoa
TM TT Xc tc quang ha trn c s composite ca TiO2 anatase-CNT c to ht bng phng php gel ha d th t CNT tng hp ti Vit Nam v TiO2 thng mi (TiO2 TM). Cc php phn tch hin i nh php o hp ph ng nhit nit, nhiu x tia X, hin vi in t qut (SEM), hin vi in t truyn qua (TEM) c thc hin lm ni bt nhng c trng ca xc tc t hp. Nhng kt qu thu c t cc php o ch ra rng s c mt ca CNT trong thnh phn ca xc tc ngn khng cho cc ht TiO2 kt t li vi nhau, khng nhng th n cn gp phn lm tng kh nng quang ha ca TiO2 trong vng nh sng kh kin. Hot tnh quang ha ca xc tc c nh gi thng qua hiu qu kh lu hunh trong du diesel thng mi. S chuyn in t (e) gia TiO2 v CNT l nhn t quyt nh to nn hiu ng synergic ca hai thnh phn chnh trong composite. ABSTRACT Composite TiO2-Carbon nano based photocatalysts was synthetized in form of the bead by heterogenous gelation methods from the CNT that was synthetized in Vietnam and commercial TiO2. N2 adsorptiondesorption isotherm measurements, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy were carried out to characterize the composite catalysts. The results suggest that the presence of CNT embedding in the composite catalysts matrix prevents TiO2 particle agglomeration. Furthermore, its presence contribute to enhance the photocatalytic activities of the composite catalysts. The photocatalytic activities were evaluated throughout the effect of the desulfurization of diesel. The transfer of electron (e-) between TiO2 and CNT is the determining factor which forms the synergic effect of two main components of the composite.

Key words: Photocatalytic, desulfurization, TiO2-CNT 1. t vn Trong qu trnh chy ca nhin liu, cc hp cht cha lu hunh trong du c gii phng vo khng kh di dng SOx, gy nn s nhim khng kh v ma axit. Vi mc ch gim thiu nhng tc ng xu n sc khe v mi trng t kh thi ng c,
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nhiu nghin cu c u t tm ra phng php h hm lng lu hunh trong nhin liu xung thp. Kh lu hunh bng Hydro vi s c mt ca xc tc (HDS) thng c s dng gim hm lng lu hunh trong du. Tuy nhin, phng php ny kh c th p ng c yu cu kh lu hunh su (< 50 ppm). Bi v dibenzothiophene (DBT) v cc dn xut ca n rt bn vi qu trnh hydro ha do i hi s dng nhng xc tc ci tin vi cc iu kin phn ng nghim ngt hn. Gn y, Vic s dng TiO2 nh l mt cht xc tc quang ha loi b DBT v cc hp cht d vng ca lu hunh trong du diesel c u t nghin cu rt nhiu trn th gii[13]. Ngoi TiO2 th mt s cht bn dn khc cng c th c s dng lm cht xc tc quang ha nh ZnO[4], CdS v GaP [5]. Cc cht ny hp ph nhiu ph mt tri hn so vi TiO2 song chng b phn hy trong qu trnh quang ha xc tc. Chnh v vy m TiO2 dng anatase vi hot tnh quang ha cao, bn ha hc, khng c hi v gi thnh thp c s dng nhiu nht cho ng dng quang ha. Tuy nhin, ch c nhng bc x t ngoi, chim khong 4% bc x t mt tri [4], ng vi cc photon c nng lng ln hn 3,2 eV (nng lng band gap ca TiO2 anatase) mi c hp th v to ra hiu qu quang ha. V vy, vic tng kh nng quang ha ca TiO2 trong vng nh sng kh kin thu ht c rt nhiu s u t nghin cu ca cc nh khoa hc trn th gii. Mt trong nhng phng php thng c s dng gn y l kt hp CNT v TiO2 [7-9]. Nh vo cc c tnh u vit ca CNT nh dn in tt, hp ph cao, ng knh vi kch thc nano v en tuyt i [10] m n lm tng cng kh nng quang ha ca TiO2 trong vng nh sng kh kin. Composit trn c s TiO2-CNT c th c tng hp t nhiu phng php khc nhau nh: phng php Sol gel [7],[8], phng php electro spinning [11],[12], phng php lng ng in di [13] hay phng php kt t ha hc trong pha hi (Chemical Vapor Deposition CVD). Song cc phng php ny kh phc tp, i hi cc thit b c bit ng thi gi nguyn liu tng i cao. Do , trong nghin cu ny chng ti s dng phng php to ht ng nht bng phng php gel ha d th h phn tn cha CNT v TiO2. Nh cu trc dn in ca CNT lm gim tc ti kt hp ca electron v l trng b mt tip xc ca CNT-TiO2 m vt liu composit trn c s CNT-TiO2 lm tng tc oxi ha quang ha DBT v cc dn xut ca n trong diesel. 2. Thc nghim 2.1. Tng hp xc tc CNT nh m t hnh 1 c tng hp bng phng php CVD trn xc tc Fe/ Al2O3 [14] ti phng th nghim lc ha du, trng i hc Bch Khoa, i hc Nng vi nguyn liu l LPG nhit 690oC 710oC . ng knh ng cacbon nano khong 11 - 16 nm, din tch b mt ring 180 200 m2.g-1 [15]. TiO2 thng mi ( tinh khit 99,4%), kch thc ht trung bnh khong 130 nm sn xut bi cng ty TNHH ROHA Dyechem Vit Nam c s dng trc tip khng qua bt k qu trnh x l no. Xc tc quang ha trn c s composite ca TiO2-CNT c tng hp t mt h cha TiO2 v CNT c phn tn bng sng siu m v c to ht theo phng php gel
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ha d th trong dung dch CaCl2 theo quy trnh sau: 0,4g sodium alginate c cho t t vo 60 ml nc ct, ng thi khuy c hc cho n khi t hn hp ng nht, CNT v TiO2 TM c phn tn u trong h keo nh sng siu m trn my VC 505 VC 750 theo t l khi lng TiO2:CNT l 1:0,05. Xc tc c to ht trong dung dch CaCl2 nng 0,5 M [16], cc ht ny c ra sch, kh ngoi khng kh ri sy nhit 80oC trong 5h, ht xc tc sau c nung nhit 400oC di khng kh trong vng 5h. (a) (b)

Hnh 1. nh cu trc CNT c chp theo phng php hin vi in t truyn qua TEM (a) v phng php hin vi in t qut SEM (b)

2.2. Cc phng php nh gi c trng Gin nhiu x tia X (X-Ray Diffraction - XRD) c ghi li trong di 2 = 10 80 nh my D8 advance ca hng Bruker, s dng s pht x Cu K1 ( = 0,16 ) l ngun pht x tia X, thit b c trang b mt u d phn tn nng lng SOL-XE. nh hin vi in t qut (SEM) c thc hin nh thit b SEM S-4800 ca hng Hitachi. nh hin vi in t truyn qua c quan st nh thit b JEOL JEM-1010 (80 kV). Mu c phn tn trong ethanol, c nh siu m v chuyn ln mt li bng ng c ph cacbon.
o

2.3. Kh lu hunh trong du diesel thng mi

Hnh 2. Thit b phn ng quang ha v hp ph lu hunh trong du diesel thng mi

Diesel thng mi (hm lng lu hunh tng 2500 ppm) sau khi mua v c x l bng hp ph qua ct silicagel loi b cc hp cht gy mu v cc hp cht cha lu hunh c hm lng nh (Sulfoxide v sulfone). Diesel ny sau c x l bng xc tc quang ho (1 g xc tc cho 100 ml du diesel) di tc dng ca bc x t n hi cao p thy ngn OSRAM 250W nh ngun pht quang ph mt tri (nh sng trng). S th nghim c trnh by trn hnh 2. Mu c ly ra tun t t thit b phn ng theo
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thi gian 20, 40, 60, 80, 100 v 120 pht, c ly tm tch xc tc v em i hp ph Sulfone trn silicagel (hnh 2) trc khi em xc nh hm lng lu hunh bng phng php hunh quang tia X (XRF) trn my TS-100V ca hng MITSHUBISHI. 3. Kt qu v tho lun 3.1. Nhng c trng ca xc tc quang ha trn c s composite TiO2-CNT Hnh thi hc v cu trc vi m ca composit TiO2-CNT c kim tra bi nh SEM v TEM trong hnh 3. T cc nh thu c trn ta c th thy rng CNT v TiO2 c phn tn rt tt vo nhau, to nn mt loi vt liu ng nht v bn vng. Kt qu thu c t cc nh TEM v SEM trn hnh 3 cho thy rng tt c cc ht TiO2 c gn kt vi cc ng cacbon nano, hu nh khng tm thy cc cu trc TiO2 nm ring r. Gin nhiu x tia X ca composite TiO2-CNT sau khi nung 400oC trong 5h c th hin trong hnh 4. Theo cc ti liu nghin cu, pha anatase ca TiO2 c to thnh nhit di 500oC, bt u chuyn sang dng cu trc dng rutile nhit trn 600oC v chuyn hon ton thnh dng rutile nhit 700 900 oC [9]. (a) (b)

Hnh 3. nh m t cu trc ca xc tc Micro nanocomposite thu c t phng php hin vi hc in t qut (a) v phng php hin vi hc in t truyn qua (b)

Qu vy, trong gin trn ta thy cu trc ca TiO2 trong xc tc hu nh khng thay i so vi cu trc ban u ca TiO2.

Hnh 4. Ph nhiu x tia X ca TiO2TM (a), xc tc quang ha t hp TiO2-CNT (b) 346

Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010

3.2. Hot tnh quang ha qu trnh kh lu hunh trong du diesel Quan h gia hm lng lu hunh trong du diesel v thi gian phn ng c th hin trn hnh 5 kt qu cho thy rng tc quang ha ca TiO2 TM thp hn rt nhiu so vi tc quang ha ca xc tc t hp TiO2-CNT iu ny mt ln na chng minh hiu ng synergic gia TiO2-CNT trong vic loi b cc hp cht ca lu hunh trong du diesel. S chuyn ha ca DBT v cc dn xut ca n thnh Sulfone bi xc tc quang ha c chng minh da vo kt qu phn tch theo phng php ph hng ngoi bin i Fourrier (FT-IR) vi cc peak c trng cho dao ng ca cc hp cht sulfone xut hin hai v tr tng ng vi s sng l 1160 cm-1 v 1280 cm-1[17]

Hnh 5. th biu din quan h gia hm lng lu hunh (ppm) v thi gian phn ng (pht)

Quan st kt qu ph hng ngoi thu c trn ta thy rng diesel sau khi x l bng silicagel loi b c hu ht tt c cc hp cht ca sulfone v cc hp cht ny xut hin tr li sau qu trnh quang ha xc tc nh c chng minh nh k thut FT-IR c trnh by trn hnh 6.

Hnh 6. Ph hng ngoi ca diesel sau khi hp th bng silicagel v sau khi x l bng xc tc hai v tr xut hin peak cc hp cht sulfone 1280(a) v 1160 (b)

C ch ca qu trnh -xy ha quang ha trn xc tc TiO2 cc hp cht cha S trong sn phm diesel to ra Sulfone v cc dn xut ca n c th c minh ha trong hnh 7.
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3.3. C ch tng cng tnh cht quang ha composite TiO2-CNT C hai c ch c nu ra gii thch s tng cng hot tnh quang ha ca composite TiO2- CNT [18]. C ch 1: Theo Hoffmann v cc cng s th khi mt photon nh sng c nng lng cao kch thch mt electron chuyn t vng ha tr sang vng dn ca TiO 2 anatase. Cc e- ny c hp th bi CNT, v l trng cn li trn TiO2 tham gia vo cc phn ng oxi ha kh. S ca c ch c minh ha trong hnh 8 (a).

Hnh 7. S c ch oxi ha DBT v cc dn xut thnh cc hp cht sulfone (a), cc sn phm ca qu trnh quang oxi ha DBT v dn xut ca n (b)

C ch 2: Theo Wang v cng s th CNT c xem nh mt cht lm nhy, n sinh ra cc e- khi hp th cc photon nh sng, cc electron ny sau c chuyn vo vng dn ca TiO2 ri c hp ph bi cc phn t oxy to thnh cc gc oxi ha mnh (superoxide). Mt khi qu trnh trn xy ra, in tch dng trn CNT (to thnh khi echuyn vo vng dn ca TiO2) ly i mt electron vng ha tr ca TiO2 v li mt l trng, lc ny TiO2 c tch in dng c th phn ng vi cc phn t nc b hp ph to cc gc hydroxyl (OH.).

Hnh 8. c ch xut cho kh nng tng cng tnh quang ha ca composite TiO 2-CNT. a) c ch ca Hoffmann, CNT ly electron v ngn khng cho electron ti kt hp vi l trng. b) c ch c xut bi Wang, CNT nhng electron vng dn v ly electron vng ha tr ca TiO2.

4. Kt lun Trong nghin cu ny, chng ti tng hp mt loi xc tc quang ha, trn c s t hp cc vt liu c kch thc micro - nanomet (TiO2 TM v CNT), vi hot tnh cao c th hin qua vic chuyn ha hon ton cc hp cht d vng (DBT v dn xut) kh tch trong du diesel thng mi thnh cc hp cht sulfoxide v sulfone c th d dng c hp ph bi silicagel. Hm lng lu hunh trong du diesel c gim xung rt
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thp ch sau hai gi phn ng. Thnh cng ny gp phn tm ra gii php hn ch s pht thi nhim ca cc hp cht cha lu hunh vo khng kh, p ng c cc tiu chun ngy cng kht khe v mi trng. Xc tc c tng hp t cc nguyn liu c th sn xut ti Vit Nam vi chi ph tng i thp nn gi thnh ca sn phm c gim xung ng k. Composite c tng hp c bn kh tt trong du do trong tng lai qu trnh kh lu hunh bng xc tc quang ha c th c tin hnh lin tc. y chnh l mt yu t quan trng gp phn a nghin cu vo ng dng cng nghip. Cm n s hng dn nhit tnh ca TS. Nguyn nh Lm, s hp tc t cc n v nghin cu v sn xut: Vin Ha Hc Cng Nghip, Phng ha nghim cng ty xng du khu vc V, Trung tm Phn tch v Phn loi hng ha Hi quan Min Trung Tng cc Hi quan, phng th nghim ha du trng i hc Bch Khoa - i hc Nng h tr cho chng ti thc hin cc nghin cu c trng xc tc v sn phm. TI LIU THAM KHO [1] J. Robertson and T.J. Bandosz, Photooxidation of dibenzothiophene on TiO2/hectorite thin films layered catalyst, Journal of Colloid and Interface Science, vol. 299, Jul. 2006, pp. 125-135. [2] S. Matsuzawa, J. Tanaka, S. Sato, and T. Ibusuki, Photocatalytic oxidation of dibenzothiophenes in acetonitrile using TiO2: effect of hydrogen peroxide and ultrasound irradiation, Journal of Photochemistry and Photobiology A: Chemistry, vol. 149, Jun. 2002, pp. 183-189. [3] D. Zhao, J. Zhang, J. Wang, W. Liang, and H. Li, Photocatalytic Oxidation Desulfurization of Diesel Oil Using Ti-containing Zeolite, Petroleum Science and Technology, vol. 27, 2009, p. 1. [4] J. Rabani, Sandwich colloids of zinc oxide and zinc sulfide in aqueous solutions, The Journal of Physical Chemistry, vol. 93, Nov. 1989, pp. 7707-7713. [5] I. Honma, T. Sano, and H. Komiyama, Surface-enhanced Raman scattering (SERS) for semiconductor microcrystallites observed in silver-cadmium sulfide hybrid particles, The Journal of Physical Chemistry, vol. 97, Jun. 1993, pp. 6692-6695. [6] A. Linsebigler, G. Lu, and J.T. Yates Jr., The bimetallic Pt/Mo(110) surface: Structural and CO chemisorption studies, Surface Science, vol. 294, Sep. 1993, pp. 284-296. [7] W. Wang, P. Serp, P. Kalck, and J.L. Faria, Photocatalytic degradation of phenol on MWNT and titania composite catalysts prepared by a modified sol-gel method, Applied Catalysis B: Environmental, vol. 56, Apr. 2005, pp. 305-312. [8] A. Jitianu, T. Cacciaguerra, M. Berger, R. Benoit, F. Bguin, and S. Bonnamy, New carbon multiwall nanotubes - TiO2 nanocomposites obtained by the sol-gel method, Journal of Non-Crystalline Solids, vol. 345-346, Oct. 2004, pp. 596-600. [9] M. Chen, F. Zhang, and W. Oh, Synthesis, characterization, and photocatalytic

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analysis of CNT/TiO2 composites derived from MWCNTs and titanium sources, Carbon, vol. 47, Oct. 2009, p. 2943. [10] Ng Tun Anh, Xc tc quang ha trn c s TiO2-CNTs mang trn vt liu c cu trc, Bo co hi ngh sinh vin nghin cu khoa hc ln th 6, i hc Nng, 2008. [11] S. Aryal, C.K. Kim, K. Kim, M.S. Khil, and H.Y. Kim, Multi-walled carbon nanotubes/TiO2 composite nanofiber by electrospinning, Materials Science and Engineering: C, vol. 28, Jan. 2008, pp. 75-79. [12] J. Cho, S. Schaab, J. Roether, and A. Boccaccini, Nanostructured carbon nanotube/TiO2 composite coatings using electrophoretic deposition (EPD), Journal of Nanoparticle Research, vol. 10, Jan. 2008, pp. 99-105. [13] H. Yu, X. Quan, S. Chen, and H. Zhao, TiO2Multiwalled Carbon Nanotube Heterojunction Arrays and Their Charge Separation Capability, The Journal of Physical Chemistry C, vol. 111, 2007, pp. 12987-12991. [14] M. Corrias, B. Caussat, A. Ayral, J. Durand, Y. Kihn, P. Kalck, and P. Serp, Carbon nanotubes produced by fluidized bed catalytic CVD: first approach of the process, Chemical Engineering Science, vol. 58, Oct. 2003, pp. 4475-4482. [15] Nguyn nh Lm, Nghin cu tng hp vt liu Nano cacbon (nanotube v nanofiber) bng phng php phn hy cc hp cht cha cacbon trong iu kin Vit Nam, Bo co nghim thu ti cp b, 2008. [16] P. Del Gaudio, P. Colombo, G. Colombo, P. Russo, and F. Sonvico, Mechanisms of formation and disintegration of alginate beads obtained by prilling, International Journal of Pharmaceutics, vol. 302, Sep. 2005, pp. 1-9. [17] M.F. Ali, A. Al-Malki, and S. Ahmed, Chemical desulfurization of petroleum fractions for ultra-low sulfur fuels, Fuel Processing Technology, vol. 90, Apr. 2009, pp. 536-544. [18] K. Woan, G. Pyrgiotakis, and W. Sigmund, Photocatalytic Carbon-Nanotube-TiO2 Composites, Advanced Materials, vol. 21, 2009, pp. 2233-2239.

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