TP CH KHOA HC, i hc Hu, S 59, 2010

NGHIN CU CHC NNG HO DIATOMITE BNG 3-MERCAPTOPROPYLMETHOXYSILANE

inh Quang Khiu, Trng i hc Khoa hc, i hc Hu Phm nh D, Trng Cao ng S phm Komtum Mai Vn By, Trng i hc S phm, Nng Nguyn Th Dim Chu Chi cc Nui trng Thu sn, tnh Qung Nam ng Xun D Trng PTTH Vinh Xun, Tha Thin Hu

TM TT
Trong nghin cu ny, chng ti trnh by kt qu chc nng ho b mt diatomite bng 3-mercaptopropylmethoxysilane (MPMS). Trc ht, diatomite c x l nhit cc nhit t 100-700oC. Sau , diatomite x l nhit (phng php x l kh) c chc nng ho bng MPMS. Mc khc, diatomite sau khi c x l nhit c a vo mi trng bo ho hi nc (phng php x l m), tip theo cng c chc nng ho bng MPMS. Mu thu c c c trng bng cc phng php SEM, XRD, v TG-DSC. Kt qu cho thy, khi nhit x l nhit cng cao cng lm gim lng MPMS gn kt vo diatomite. Trong iu kin diatomite c x l m, vic gn kt nhm chc ln b mt l thch hp hn trong trng hp diatomite x l kh.

1. Gii thiu Diatomite l khong t nhin c thnh phn ho hc ch yu l SiO2 v mt s tp cht khc tu thuc vo iu kin th nhng hnh thnh n. Diatomite c s dng lm vt liu cch m, cch nhit, cht lc, vt liu mi bng v trong ngnh cng nghip ru bia v xy dng. Diatomite vi hm lng st nh tp cht phn tn trn SiO2 l h xc tc Fenton rn cho phn ng hydroxyl ho phenol v l cht xc tc cho phn ng Fischer-Tropsch [1]. Cc nhm silanol (... Si-OH) trn b mt diatomite c th kt hp vi cc hp cht silane nh 3-mercaptopropylmethoxysilane (MPMS), 3aminopropylmethoxysilane to thnh cc cht xc tc baz rn, axit rn v cht hp ph lai hu c - v c phong ph v a dng. Gn y, Wang v cng s [2] nghin cu chc nng ho b mt diatomite bng MPMS. Kt qu cho thy sn phm merpcaptopropyl diatomite c kh nng hp ph cao thu ngn trong dung dch nc. Tuy nhin, cc tc gi ny cha i su vo cc yu t tng hp ti u ho iu kin tng hp.
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Trong nghin cu ny, chng ti trnh by mt s kt qu kho st nh hng ca nhit v iu kin x l diatomite gn kt MPMS ln b mt to thnh mercaptopropyl diatomite. C ch gn kt MPMS ln b mt diatomite cng c ngh. 2. Thc nghim Diatomite t nhin c ly t vng m trm tch Ty An thuc tnh Ph Yn. MPMS ( tinh khit > 99%, Merk) v CHCl3 (Quangzu, Trung Quc) theo th t l cht c s dng chc nng ho b mt diatomite v dung mi. Thnh phn ho hc ca diatomite c phn tch bng hin vi in t qut kt hp tn x tia X EDX/SEM cng b trong bi bo trc [3] ch ra bng 1.
Bng 1. Thnh phn ho hc ca diatomite ( % khi lng)

O (%) 60,70

Al (%) 5,97

Si (%) 27,84

Ti (%) 0,85

Fe (%) 3,74

CCK* (%) 0,90

CCK: thnh phn ho hc khc

Diatomite sau khi loi cc tp cht th v sy kh 1000C em nung cc nhit 100, 300, 500 v 7000C trong 3 h. Qu trnh chc nng ha diatomite c thc hin theo hai phng php: phng php x l kh da trn ti liu [2]. Tm tt nh sau: cho vo bnh tam gic c nt nhm 36 ml dung dch cloroform + 2 ml silane + 2g diatomite x l nhit, khuy t lin tc trong 4 ngy. Sau , lc thu ly cht rn trn giy lc bng vng, ra cht rn bng 15 ml dung dch cloroform (chia thnh 10 ln, mi ln ra ly 1,5 ml). Cht rn thu c em sy 700C trong 24 h, sau khi sy ngui n nhit phng trc khi cho vo bo qun trong bnh ht m. Cc mu c k hiu l 100D, 300D, 500D v 700D, trong cc ch s 100, 300, 500, 700 cho bit nhit x l diatomite. Phng php x l m da trn ti liu tham kho [4]. Tm tt nh sau: cn 2 g diatomite ( x l nhit) t vo bnh ht m c cha dung dch NaCl bo ho di y trong 2 h. Ln lt cho 50 ml dung dch toluen + 2 ml silane + 2 g diatomite trn vo bnh cu 250 ml, thc hin phn ng 1200C (nhit c gi n nh bng dung dch glyxerin) v khuy t trong bnh cu hi lu trong 2 h. Lc thu ly cht rn trn giy lc bng vng, cht rn c chit soxhlet bng dung mi cloroform khong 4 5 ln. Cht rn thu c em sy 700C trong 24h, sau khi sy ngui n nhit phng trc khi cho vo bo qun trong bnh ht m. Cc mu c k hiu l 100H, 300H, 500H v 700H, trong cc con s 100, 300, 500, 700 cho bit nhit x l diatomite trc khi tin hnh chc nng ho. Thnh phn cc pha c phn tch bng phng php nhiu x tia X (XRD), c ghi bng my 8D Advance Bucker, Germany, dng tia bc x CuK vng qut gc 2 t 10-600. Tng lng MPMS gn kt ln diatomite c xc nh bng phng php phn tch khi lng TG (Labsys TG/DSC SETARAM) trong mi trng khng
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kh. Hnh thi ca diatomite c quan st bng phng php hin vi in t qut (SEM. Jeole-3432).
50 cps quartz

700 C

Cng (cps)

500 C

300 C
o

100 C

10

20

30

40

50

60

2 theta ()

(a)

(b)

Hnh 1. (a) Gin XRD ca diatomite cc nhit x l khc nhau; (b) nh SEM ca diatomite ban u

3. Kt qu v tho lun Hnh 1a trnh by gin XRD ca diatomite c nung 100, 300, 500, 700oC. Diatomite ban u (x l nhit 100oC) ch yu dng cu trc v nh hnh. Khi tng nhit nung ln 300oC, cc nhiu x c trng cho quartz bt u xut hin do SiO2 dng v nh hnh chuyn sang dng tinh th quartz. Khi tip tc tng nhit nung th cng nhiu x ca pha tinh th quartz cng gia tng. Trong khong nhit nung t 300-700oC, thnh phn pha ca diatomite ch yu l v nh hnh v tinh th quartz. Hnh thi ca diatomite trnh by hnh 1b cho thy n cu to t nhng hnh ng vi chiu di t 10 20 m vi ng knh c vi m. Tng ca ng c nhng mao qun nh ng knh khong vi trm nm. Vi cu trc nh vy, diatomite s l cht tr lc v cht mang t nhin l tng trong lnh vc hp ph v xc tc. MPMS thu phn thnh silanol nh s hin din ca lng hi nc m trong toluen. MPMS kt gn vi diatomite do s ngng t ca nhm silanol ca n v nhm silanol trn b mt diatomite. MPMS lin kt cht ch trn b mt diatomite, v vy, silane khng b loi khi b mt do qu trnh ra bng clorofom. Trong nghin cu ny, lng MPMS gn kt vi diatomite c nh lng bng tng mt khi lng tnh theo phng php phn tch khi lng (thermal gravity-TG) nhit >110oC. Hnh 2 biu din gin DSC v TG ca cc mu chc nng ho b mt diatomite iu kin diatomite c x l kh. Gin DSC v TG i vi cc mu u tng t nhau. Cc mu ti 300oC u c peak to nhit, tuy nhin, khng c s mt khi lng, iu ny c gii thch l do s chuyn pha ca silica v nh hnh sang dng tinh th quartz. Quan st ny cng tng ng vi kt qu phn tch XRD m ti khi diatomite c nung 300oC xut hin pha tinh th quart (xem hnh 1a).
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10 V

700D

TG Mt khi lng (%)

5%

500D

700D

To nhit

500D 300D

(V)

300D

100D

DSC

100D

100

200

300

400
o

500

600

700

800

100

200

300

400
o

500

600

700

800

Nhit ( C)

Nhit ( C)

(a)

(b)

Hnh 2. (a) Gin DSC, (b) Gin TG ca mercaptopropyl diatomite c iu ch theo phng php x l kh Bng 2. Lng MPMS gn kt vo diatomite c phn tch bng TG

Diatomite c x l l kh Mu 100D Khi lng mt ti 100oC,(%) Khi lng mt ~ 320oC, (%) Khi lng mt ~ 520oC, (%) Tng khi lng mt > 110oC, (%) 5,67 0,00 5,44 300D 0,00 0,00 3,76 500D 0,00 0,00 2,55 700D 0,00 0,00 1,82

Diatomite c x l m 100H 3,71 0,00 6,99 300H 2,45 2,02 5,69 500H 0,00 1,31 1,70 700H 0,00 0,80 0,99

5,44

3,76

2,55

1,82

6,99

7,71

3,01

1,79

Mt iu ng ch l cc mu 300D - 700D d c nung trn 300oC trong 3 gi trc khi chc nng ho, peak ny vn xut hin. iu ny c gii thch l c th do s phc hi li cu trc (reconstruction) dng v nh hnh ca silica xy ra trong qu trnh chc nng ho silan v chit soxhlet. Peak to nhit ng vi s mt khi lng ti 520oC l do s phn hu / chy ca MPMS gn kt vo diatomite. Lng MPMS kt gn vo diatomite c phn tch bng phn tch nhit khi lng (TG) trnh by bng 2. Lng MPMS dao ng trong khong 5,44 3,76% i vi mu c diatomite x l nhit 100-300oC (D100 v D300) v gim mnh khi tng nhit ln 500 v 700oC.
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10 V

700H

2%

700H

exo

500H
Ignition loss (%) 500H

heat flow (V)

300H

100H
300H 100H
100 200 300 400 500
o

600

700

800

100

200

300

400

500
o

600

700

800

Temperature ( C)

a b (a) (b) Hnh 3. a. Gin DSC; b. Gin TG ca mecaptopropyl diatomite iu ch bng phng php x l m

Temperature ( C)

Hnh 3 ch ra gin TG-DSC chc nng ho b mt diatomite trong iu kin diatomite c x l m. Cc dng ng cong ca cc mu tng t nhau. iu ng ch l ngoi s mt khi lng ~ 520oC nh trong trng hp diatomite x l trong iu kin kh cn xut hin s mt khi lng ~ 320oC trong cc mu 300H, 500H v 700H. Kt qu phn tch lng MPMS gn kt vo diatomite c trnh by bng 2. T bng 2 cho thy, lng MPMS gn kt vo diatomite c x l m cao hn diatomite c x l kh. Tng lng MPMS gn kt cao do c s ng gp ng k ca lng MPMS phn hu ~ 320oC v trong c hai trng hp nhit t 100oC300oC thch hp cho vic chc nng ho diatomite bng MPMS. Yuan v cng s [5] cng b cc dng lin kt ca nhm OH trn b mt diatomite. H ch ra rng c 2 kiu lin kt silanol trn b mt diatomite: silanol lin phn lp (isolated silanols) v silanol lin kt vi nc qua lin kt hydro (H-bonded silanol). nhit phng, c 2 kiu lin kt silanol u l lin kt hydro vi nc. Khi tng nhit , qu trnh kh nc xy ra. u tin, nc bay hi v lm phi by cng nhiu lin kt silanol phn lp, thch hp cho vic silanol ca silane hp ph ln b mt diatomite. iu ny gii thch trong trng hp lng ln MPMS gn kt trn b mt diatomite khi nung nhit 100-300oC. Diatomite sau khi nung t trong mi trng m lm to ra nhiu nhm silanol. Gii thch cho s kin diatomite hp ph MPMS trong iu kin m mnh hn trong iu kin kh. nhit cao hn 300oC, silanol bt u ngng t thnh cu ni siloxane, v vy, khng thch hp cho phn ng ngng t cc nhm silanol. Theo kt qu phn tch nhit TG-DSC, trong trng hp diatomite uc x l trong iu kin m, c 2 qu trnh silane ngng t gn kt ln b mt diatomite tng ng vi hai qu trnh phn hu MPMS hai nhit 320 v 520oC. hiu r iu ny cn c nghin cu su hn sau ny. Da vo kt qu ca Johansson
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cng cng s [6] v s hp ph ca tc nhn xc tc gn kt silane ln b mt cao lanh, chng ti a ra 2 c ch gii thch MPMS gn kt ln b mt diatomite nh sau: C ch 1 bao gm 4 bc: 1. MPMS c chuyn thnh dng silanol hot ng nh phn ng thu phn (R: CH2-CH2-CH2-SH; X: OCH3)

2. S ngng t ca organosilane thnh oligomer

3. Hnh thnh lin kt hydro gia cc oligomer v nhm OH ln b mt diatomite

4. Hnh thnh cc lin kt cng ho tr

C ch 2 bao gm 2 bc: 1. MPMS c chuyn thnh dng silanol hot ng nh phn ng thu phn

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2. Nhm silanol phn ng trc tip vi nhm hydroxyl trn b mt diatomite

Do silane gn kt ln b mt diatomite theo c ch 1 bng nhiu lin kt Si-O-Si hn l theo c ch 2 nn c th gi thit rng silane gn trn b mt diatomite theo c ch 1 bn vng hn so vi c ch 2, do , nhit phn hu ca n phi cao hn. Hai dng lin kt ca MPMS trn b mt diatomite c th c hnh thnh theo hai c ch trn. Trong iu kin x l kh, c th MPMS gn kt vo diatomite theo c ch 1 v s phn hu mecaptopropyl diatomite ch xy ra nhit cao ~ 520oC. Trong khi , diatomite c x l trong mi trng m, vic gn kt MPMS c th xy ra theo c hai c ch. Do c hai dng MPMS gn kt vo diatomite, kt qu l s phn hu mercaptopropyl diatomite xy ra hai nhit khc nhau ~ 320oC v ~ 520oC. nh hng ca thi gian x l m cng c kho st. Nung diatomite trong 3 gi 100oC, sau a vo bnh ht m c cha dung dch NaCl bo ho trong 0, 1, 3, 6, 8, 10 gi. Qu trnh chc nng ho b mt diatomite cng ging trng hp x l m. Kt qu lng MPMS gn kt vo diatomite t phn tch TG c trnh by bng 3.
Bng 3. Lng MPMS gn kt vo diatomite trong iu kin x l m 100oC

Thi gian hydrat (gi) Khi lng mt >110oC, (%)

0 7,10

1 7,91

2 6,99

3 9,88

6 8,04

8 8,90

10 6,59

Ta thy lng MPMS gn kt vo diatomite cao nht khi thi gian x l m trong 3 gi v gim dn khi thi gian x l m tng. iu ny c th do khi ko di thi gian x l m ng ngha lng nc vo trong l xp diatomite tng nhiu, dn n cc phn t MPMS b hydrat ho cng mnh, v ngng t kt hp li vi nhau thay v phi kt hp vi thnh mao qun v MPMS khng gn kt s b loi bng trong qu trnh ra bng dung mi chloroform.V vy, lng MPMS gn kt b gim. 4. Kt lun Diatomite Ph Yn c cu trc ch yu l v nh hnh. Qu trnh chuyn pha t dng v nh hnh sang dng tinh th xy ra nhit ln hn 300oC. X l nhit diatomite trong khong nhit t 100-300oC l thch hp cho vic chc nng ho. Trong iu kin diatomite c x l m th chc nng ha b mt tng ln ng k. MPMS gn kt t kt qu tt nht 9,88 % khi diatomite c lm m trong thi gian 3 gi.
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TI LIU THAM KHO

1. Y. Jia, W. Han, G. Xiong, W. Wang, Diatomite as high performance and environmental friendly catalysts for phenol hydroxylation with H2O2, Sci. Technol. Adv. Mat. 8, (2007) 106-109. 2. B. Wang, T. R. Smith, Performance of diatomite-based sorbent in removing mercucy from aqueous and oil matrices, J. Environ. Eng. Sci. 6, (2007), 469-476. 3. Dinh Quang Khieu and Nguyen Van Hieu, Mt s c trng ha l ca khong diatomite Ph Yn v hot tnh xc tc cho phn ng hydroxyl ha phenol, Vietnamese Journal of Chemistry, Vol. 47, (2009), 342-346. 4. C. Yang, X. Jia, Y, Cao and N. He, Proc. Grafting of swelling clay materials with 3aminopropyltriethoxylane, 8th International Conference on Electronic Materials, Xian, China, (2002), 556-569. 5. P. Yuan, D. Q. Wu, H. P. He, Z. Y. Lin, Characterization of diatomaceous silica by Raman spectroscopy, Appl. Surf. Sci., 237,(2004), 30-37. 6. U. Johansson, A. Holmgren, W. Forsling and R. L. Frost, Adsorption of silane coupling agents onto kaolinite surfaces, Clay Minerals, 34, (1999) 239-248.

STUDY IN THE SYNTHESIS OF MERCAPTOPROPYL-FUNCTIONNALIZED DIATOMITE

Dinh Quang Khieu, College of Sciences, Hue University Pham Dinh Du, KomTum Junior College of Pedagogy Mai Dinh Bay, College of Pedalogy, Danang University Nguyen Thi Diem Chau, Department of Aquaculture, Quang Nam Province Dang Xuan Du Vinh Xuan High School, Thua Thien Hue Province

SUMMARY
The synthesis of mercaptopropyl-functionnalized diatomite is presented. Functionalized diatomite was prepared by the grating of 3-mercaptopropylmethoxysilane (MPMS). The diatomites with thermal treatment from 100-700oC were functionalized by MPMS under dried and humidity conditions. The obtained samples were characterized by Scanning Electron Microscope (SEM), X-ray diffraction (XRD), thermal gravity-differential calorimeter (TG-DSC). The results show that the increase in the treatment temperature seems to reduce the loading of MPMS into diatomite. The humidity of diatomite are favorable to the grafting of functional groups on the surface. The possible mechanisms of MPMS loading to diatomite were also proposed in both case. 72