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

TNG HP, BIN TNH B MT V NH HNH VT LIU NANO CARBON (CARBONE NANOTUBE) THU C BNG PHNG PHP PHN HY XC TC CC HP CHT CHA CARBON TRONG IU KIN VIT NAM SYNTHESIS, POST-TREATEMENT AND MACROSCOPIC SHAPING THE CARBON NANOMATERIALS (NANTUBES DE CARBONE) OBTAINED BY THE METHOD VAPOR CATALYZED DECOMPOSITION THE COMPOUNDS CONTAINING CARBON IN VIETNAM'S CONDITIONS SVTH: Trn Chu Cm Hong
Lp 05H5, B mn CNHH Du v Kh, Khoa Ha, Trng H Bch Khoa

ThS Hunh Anh Hong

S T nguyn v Mi trng thnh ph Nng

GVHD: TS. Nguyn nh Lm

Khoa Ha, Trng H Bch Khoa
TM TT Phng php s dng tng hp CNTs l phng php phn hy xc tc (CVD) ngun o nguyn liu l hn hp LPG- H2(20-30%), iu kin 710-720 C vi s c mt ca xc tc 20% Fe/ Al2O3 . Kt qu thu c t php chp nh dng Knh hin vi in t truyn qua (TEM) v o b mt ring theo l thuyt BET cho thy rng sn phm thu c l CNTs tinh khit, hu nh khng c tp cht, khng c dng cacbon v nh hnh, c b mt ring BET vo khong 180-200 2 -1 m . g . Sn phm tng hp c tip tc c x l bng NaOH ci thin b mt ring, ng thi c nh hnh di dng ht cho vic ng dng ca vt liu ny trong cng nghip l kh thi hn. ABSTRACT The Carbon Nano Tubes (CNTs) were produced by the Vapor Catalyzed Decomposition (VCD) from the mixture of LPG and H2 as the feedstock at 710 720oC in the presence of the 20%Fe/ -Al2O3 catalyst. The CNT products were characterized by the various physicochemical techniques as Transmission Electronic Microscopy, X-Ray Diffraction and N2 Absorption at 77 K for determining the BET surface area. The CNT products showed a high purity without another carbon allotropic form. The BET surface area of the CNT is about 180 200m2.g-1. The post-treatment of the CNT by the NaOH impregnation followed the thermal treatment leads to the increase considerably their surface areas. The macroscopic sphere shaping of the CNT gives them more opportunity in the industrial applications. . Keywords: CNT, CVD, Synthesis, Post-treatment, macroscopic shaping.

1. Gii thiu Hin nay, cc phng php v ang c nghin cu s dng tng hp carbon nanotube bao gm phng php H quang (Arc Electrique), phng php ct gt Laser (Ablation Laser), phng php kt t ha hc trong pha hi (CVD), trong , phng php CDV vi nhng u im ca n c ti la chn l phng php chnh tng hp CNTs [1]. Tnh cht ca cc vt liu nano cacbon thu c ph thuc nhiu vo s la chn nguyn liu, xc tc cng nh cc iu kin v nhit , thi gian lu ca qu trnh tng hp. Cc dng nano thu c bng phng php ny cha mt
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Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010

lng ng k cc dng th hnh khc ca cacbon: nh cacbon v nh hnh, graphit ngoi ra trong sn phm thu c cn c cha mt s tp cht khc l cc hp cht c s dng lm xc tc. Trong ni dung ti, CNTs tng hp c l CNTs a lp, s dng xc tc 20%Fe/ -Al2O3 , nhit phn ng 710-720oC. Ngun nguyn liu LPG- H2 d kim, gi thnh r, li khng c hi, nn c la chn lm nguyn liu cho ti. Sn phm CNTs thu c nh gi cht lng thng qua nh chp t Knh Hin vi in t truyn qua (TEM), v b mt ring o theo phng php BET. Sn phm tip tc c a qua x l bng NaOH [2][3], mt cch lm tng b mt ring ca vt liu, nhm tng hiu qu s dng ca carbon nano trong cc qu trnh Hp ph. ng thi, CNTs dng bt c nh hnh di dng ht vi ng knh vi mm [4],[5] thun tin cho vic thu hi CNTs qua s dng trong Cng nghip v hn ch cc nguy hi c th gy ra vi sc khe con ngi do kch thc nano ca loi vt liu ny. 2. Chi tit thc nghim 2.1. Chun b xc tc Cht mang -Al2O3 thng mi vi cc kch thc l xp trung bnh (mesoporous) c b mt ring SBET = 200m2g-1 c nghin mn v qua ry thu c c ht t 80 150 m .Cht mang xc tc c ngm tm vi dung dch nc ha tan tin cht Fe(NO3)3.9H2O, sau , hn hp rn c sy 100C trong 12 gi tch nc, sau c nung 450C trong 2 gi phn hy hon ton mui nitrat st thnh o-xyt st [1]. Trc khi s dng xc tc ny tng hp CNTs, cc dng -xit st thu c s c kh trong dng kh hydro ti 450C trong 2 gi kh hon ton -xit st v chng ta s thu c xc tc Fe/ -Al2O3. Nng tnh ton ca st trn xc tc c c nh gi tr 20% khi lng. 2.2. iu kin tng hp (4)

(1)

(2) (3)

Hnh 1: Dy chuyn cng ngh tng hp vt liu Nano carbon bng phng php VCD. (1) : cc bnh kh, (2) L nung ng c iu khin nhit ; (3) ng phn ng bng quartz, (4) Thit b iu khin lu lng.

Trn c s cc nghin cu l thuyt ca qu trnh hnh thnh cc dng vt liu nano

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(3)

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

carbon, kt hp vi tham kho dy chuyn cng ngh tng hp vt liu nano carbon ti cng ty Microphase Nanotechnology ti Nht bn[6], ti ngh mt s tng hp loi vt liu ny nh hnh 1. 2.2.1. Tng hp CNTs Xc tc s dng trong mi th nghim vi lng l 0,2 g, c t trong thuyn bng s v a vo trung tm ca ng phn ng bng quart c ng knh l 4,2 mm v chiu di l 1600mm. H thng s c ui khng kh trong vng 15 pht bng dng H2 trc khi gia nhit ca l phn ng ln 450oC qu trnh kh xc tc din ra trong Fe 3H 2 O vng 1h. Phn ng kh Oxyt st trong ng phn ng nh sau: Fe2 O3 3H 2 Cc tinh th st xut hin sau qu trnh kh bng Hydro c khng nh nh cc peaks nhiu x c trng tng ng 44,6 v 65o2 nh c trnh by trn hnh 2.

Hnh 2 : Ph nhiu x tia X (XRD) ca xc tc sau khi kh bng Hydro 450oC

Sau , hn hp LPG-H2 dn qua ng Quart vi tc nht nh v vi t l nht nh, l nung nng nhit n nhit thc hin phn ng, duy tr trong 2 gi v thu c sn phm CNTs. Sau thi gian phn ng, sn phm trong ng Quart s c lm ngui t nhin n nhit mi trng, vi dng kh tr N2 thi qua. Tnh ton lng CNTs thu c qua i lng M l s gia tng khi lng ca mu nghin cu (khi lng ca CNT to thnh) khi so snh vi khi lng ca xc tc Fe/ -Al2O3 a vo theo cng thc sau:
%M M 2 M1 100 M1

Trong : M1 v M2 l khi lng ca xc tc v sn phm thu c tng ng. 2.2.2. X l b mt ca CNTs tng hp ch ti u, CNTs sau tng hp s c x l bng NaOH [2][3] ci thin

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

b mt ring. u tin, cn lng CNTs va , chun b dung dch NaOH bo ha. Sau , cho CNTs vo dung dch NaOH bo ha, m bo t l khi lng NaOH/CNTs nht nh. Theo ti liu tham kho [2], t l ny c kho st trong khong 0,5-6, trong ni dung ti, la chn t l khi lng NaOH/CNTs l 4-5. Khuy trn cho CNTs tm thm u NaOH ln b mt. Mang hn hp sy 130oC tch nc v NaOH thm ln b mt vt liu, trong 24h, sau nung hn hp hai ch khc nhau: 780oC, trong mi trng kh tr (N2), trong vng 1 h, tc tng nhit: 10oC/ pht. (C NaOH- 780oC). 400oC, trong mi trng khng kh (O2), trong vng 1h, tc tng nhit: 10oC/ pht. (C NaOH 400oC). Sau mu uwocj lm ngui t nhin, ri ra hn hp bng nc ct. Dng axit long HCl.0,1M trung ha lng NaOH cn li. Cui cng, ra li bng nc ct cho n khi pH ca dung dch bng 7 v em sy 100oC trong vng 12h CNTs thu c. 2.2.3. nh hnh CNTs dng ht Nguyn tc ca qu trnh nh hnh CNTs thnh dng ht l s gel ha dung dch huyn ph Alginate- CNTs trong dung dch CaCl2 bo ha [4] [5] c cho vo dung dch Alginate vi nng thch hp, ri c phn tn u vo trong dung dch nh khuy siu m. iu chnh t nht thch hp, hn hp huyn ph CNTs- Alginate c nh git vo dung dch CaCl2, qu trnh gel ha xy ra nhanh chng to lp mng mng bn ngoi ht CNTs- Alginate. Ngm trong dung dch CaCl2 trong thi gian 30 pht, cc ht c mang ra ra li bng nc v sy t nhin tch nc s b, trc khi em sy 120oC trong 4h tch hon ton nc. Sau ht CNTs- Alginate s c nung nhit cao phn hy ton b Alginate, vi 2 ch khc nhau: 600oC, trong mi trng kh tr (N2), trong 5h. 400oC, trong mi trng khng kh (O2), trong 5h. 2.3. Kt qu Tin hnh cc th nghim cc ch khc nhau kho st trn ba yu t nh hng l thnh phn th tch LPG, tc nguyn liu v nhit phn ng, ti xc nh c vng ti u ca cc thng s, c biu th Bng 1.
Bng 1: Cc thng s vn hnh trong min ti u.

Thng s vn hnh %V LPG %V Hydro Nhit (C) Vn tc dng nguyn liu (cm.min-1) Nhit v thi gian kh -xit kim loi Yu cu ca xc tc

Gi tr 20 40 80 60 710 730C 34 450C, 1 gi Tm xc tc lin kt tt vi cht mang

Hnh 3 ch r cu trc nano ca Carbon nano ng. Kt qu chp TEM cc mu

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

iu kin ti u cho thy, nhng mu nhit cng cao th sn phm thu c cho thy si CNT cng di, c ng nht v tinh khit cao, hu nh khng tm thy cc cu trc carbon v nh hnh cng nh cc dng nano carbon khc trong sn phm. (A) (B)

Hnh 3: Cu trc ca sn phm CNTs thu c bng phng php CVD 630C (A) v 710C (B). Kt qu CNTs sau khi x l bng NaOH ng gi bng phng php o b mt ring theo l thuyt BET, c cung cp bng 2, v nh chp TEM nh minh ha hnh 4.
Bng 2: B mt ring BET ca vt liu CNTs trc v sau bin tnh bng NaOH hai ch : C NaOH 780oC v C NaOH 400oC.

Bt CNTs B mt ring BET (m2.g-1)

Trc x l 200

X l bng NaOH X l bng NaOH vi C NaOH 780oC vi C NaOH 400oC 450 380

Theo bng 2, b mt ring ca vt liu c ci thin tt hn khi nung nhit cao 780oC trong mi trng kh tr. Lc , NaOH s nng chy v n mn b mt ca vt liu, to ra nhiu khuyt tt, g lm, lm tng b mt ring ca vt liu. Tuy nhin, so vi ch nung khc nghit, tiu tn nhiu nng lng th ch nung trong khng kh nhit thp hn 400oC cng th hin tnh u vit ca n.

Hnh 4: nh TEM chp CNTs sau khi x l bng NaOH, mu c nung 780oC (N2) (A), v mu c nung 400oC (O2) (B).

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

Qua hnh chp TEM, chng ta c th nhn thy nhiu ng CNTs ph v cc u fullerenes, to ra cc cu trc ng hon chnh. Ngoi ra, mt s ng CNTs cng b ct t thnh cc on ng nh s lm gim kh nng b khng ch khuch tn trong ng nano khi chng c s dng lm cht mang cho xc tc hoc lm cht hp ph. nh gi hiu qu ca qu trnh nh hnh CNTs dng ht, ti cn c trn hnh chp TEM ca vt liu, c minh ha trong hnh 5, hnh 6.

Hnh 5: nh chp CNTs dng bt v CNTs dng ht sau khi c nh hnh

Kt qu chp TEM ca hai mu cho thy: i vi mu nung trong iu kin co O2 nhit 400oC c xut hin cu trc v nh hnh do Alginate phn hy cha hon ton; i vi mu nung trong iu kin kh tr N2 th khng c hin tng xy ra.

Hnh 6 : nh TEM chp cu trc CNTs dng ht nung 600oC trong mi trng kh tr N2 (A), v nung 400oC trong mi trng khng kh c O2 (B)
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Tuyn tp Bo co Hi ngh Sinh vin Nghin cu Khoa hc ln th 7 i hc Nng nm 2010

2.4. Kt lun Nh vy, khi s dng ngun cacbon l LPG tng hp vi xc tc Fe/- Al2O3 sn phm to thnh l cacbon nano dng ng, vi ng knh ngoi ca ng cacbon nano trung bnh t 10-30 nm. B mt ring ca mu CNTs o c theo BET l 180-200 m2/g. Trong cc yu t kho st, nhit l yu t quan trng nht nh hng n hiu sut sn phm. Lng sn phm CNTs to ra nhiu nht khi vng ti u ln cn xung quanh cc gi tr nng LPG l 30-40%; vn tc dng kh trong h l 3-4 cm/pht v nhit tng hp l 710-720 oC. Lc , lng CNTs to thnh ln gp 12,2 ln so vi lng xc tc Fe/- Al2O3. Bin tnh b mt CNTs to thnh bng NaOH t hiu qu cao, vn gi c cu trc nano, ng thi lm tng b mt ring, tng kh nng ng dng ca CNTs trong lnh vc Hp ph, lu tr. ti thnh cng trong nh hnh CNTs dng ht vi ch nung nhit 600oC, trong mi trng N2, to thun li cho vic ng dng CNTs trong Cng nghip. TI LIU THAM KHO [1] Hunh Anh Hong, Nguyn nh Lm. Nghin cu xut quy trnh tng hp carbon nano bng phng php phn hy xc tc cc hp cht cha carbon trong iu kin Vit nam, Tp ch Khoa Hc v Pht trin - S KH&CN nng, 112 (2005) 20. [2] Ru- Ling Tseng, Mesopore control of high surface area NaOH-activated carbon, Journal of Colloid and Interface Science 303 (2006) 494502. [3] Ru-Ling Tseng, Szu-Kung Tseng, Pore structure and adsorption performance of the KOH-activated carbons prepared from corncob, Journal of Colloid and Interface Science 287 (2005) 428437. [4] J.S.Lee, D.S.Cha, H.J.Park, Survival of Freeze-Dried Lactobacillus bulgaricus KFRI 673 in Chitosan-Coated Calcium Alginate Microparticles, J.Agric.Food Chem. 2004, 52, 73007305 [5] A. Blandino, M.Macias, D.Canter, Formation of Calcium Alginate Gel Capsules: Influence of Sodium Alginate and CaC12 Concentration on Gelation Kinetics, Journal of Bioscience and Bioencineering vol. 88, no. 6, 686-689. 1999. [6] www.microphase.jp

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