Nghin cu tng hp, c trng cu trc ca

bentonit Di Linh chng bng mt s oxit kim

loi (Al, Fe, Ti) c hu c ha bi xetyl
trimetyl amoni bromua ng dng lm vt liu
hp ph a nng
Trng nh c
Trng i hc Khoa hc T nhin; Khoa Ha hc
Chuyn ngnh: Ha du v Xc tc Hu c
M s: 62 44 35 01
Ngi hng dn: PGS. TS. Hoa Hu Thu
TS. Nguyn Vn Bng
Nm bo v: 2011
Abstract. Tng quan v cc loi khong st. Thc nghim: iu ch Mont-Na;
tng hp bentonite di linh chng bng cc polyoxocation kim loi Al, Fe, Ti;
tng hp bentonite di linh chng bng cc polyoxocation kim loi Al, Fe, Ti a
du. Trnh by kt qu v c trng bentonite di linh chng bng cc
polyoxocation kim loi Al, Fe, Ti v Al, Fe, Ti a du; ng dng ca cc vt liu
st chng a du tng hp c lm cht hp ph
Keywords. Vt liu hp ph; Khong st; St chng; Ha hc

Content.
A GII THIU LUN N
1. Tnh cp thit ca lun n
Tit kim nc cu ly hnh tinh v to ra tng lai an ton cho nhn loi l iu rt cn
thit hin nay. Vi s ln mnh ca loi ngi, x hi, khoa hc v k thut, th gii chng ta ang tin
ti nhng tm cao mi nhng ci gi m chng ta ang v s phi tr trong tng lai gn chc chn l rt
cao. Hu qu ca qu trnh tng trng nng ny l mi trng b nhim nghim trng. Bn cnh
nhng vn thit yu khc, th yu cu v nc sch gia tng rt nhanh vi cc lnh vc nh nng
nghip, cng nghip v sinh hot ln lt l 70, 22 v 8% v iu ny ko theo h qu pht sinh mt
khi lng ln nc thi cha mt s cht nhim. Trong , nc b nhim cc kim loi nng v
nhim cc cht hu c l ch yu.

Do , vic loi b cc kim loi nng v cc cht nhim hu c ra khi nc thi trc khi
thi nc li mi trng l cn thit. C nhiu phng php tch loi cc cht nhim ra khi ngun
nc, trong hp ph l phng php c s dng rng ri nht do n c u im c v kinh t v k
thut.
c nhiu nghin cu v vic s dng cc vt liu r tin, d kim trong s l ngun nc
thi, v vy lun n ny tp trung nghin cu ch to vt liu hp ph lai v c hu c c kh nng hp
ph c cc ion kim loi nng v cc cht hu c.
2. Mc tiu nghin cu
+ Tinh ch bentonite Di Linh thu c bentonite c hm lng montmorillonite cao.
+ Chuyn bentonite Di Linh sau khi tinh ch v dng thun natri.
+ Tng hp ion Keggin [Al13O4(OH)24]7+ v cc ion tng t ion Keggin ca Fe v Ti (cc ct chng).
+ Tng hp cc bentonite Di Linh chng bi cc oxit kim loi (Al, Fe, Ti) vi cc t l mol khc nhau l
2,5; 5,0; 7,5 v 10,0 mmol kim loi/gam st, to nn vt liu xp c b mt ring ln v c l vi mao
qun.
+ Bin tnh cc bentonite chng bi cc oxit kim loi ni trn bi CTAB thu c cc vt liu st
chng a du, vt liu lai v c hu c.
+ Kho st kh nng hp ph ca cc vt liu tng hp c vi ion kim loi nng (Cu2+) v cc cht
mu hu c c bn cht khc nhau: methylen blue v methyl orange.
3. Nhng ng gp mi ca lun n
+ x l bentonite Di Linh, nghin cu chng bng cc polyoxocation ca mt s kim loi (Al, Fe,
Ti).
+ Ch to vt liu st chng a du bng phng php kh (kinh t v khng gy nhim mi trng),
s dng tc nhn hu c ha l CTAB (xetyl trimetyl amoni bromua), vt liu to ra l cc vt liu lai v
c hu c c kh nng hp ph kim loi nng (Cu2+) v cc cht hu c c hi.
+ S dng phng php 27Al-NMR chng minh iu ch thnh cng ion Keggin t dung dch AlCl 3 v
NaOH.
+ S dng nhiu phng php vt l hin i XRD, SEM, TEM, BET c trng vt liu.
+ Vt liu bentonite bin tnh bi cc polyoxocation (Al, Fe, Ti) CTAB c kh nng hp ph c kim
loi nng (Cu2+) v cc cht mu hu c (metylene blue, metyl orange) c kch thc ln.
4. Cu trc ca lun n
Lun n di 125 trang (khng k ph lc v ti liu tham kho) chia thnh cc phn nh sau: M
u 2 trang, chng 1 tng quan 32 trang, chng 2 thc nghim 24 trang, chng 3 kt qu v tho
lun 64 trang, kt lun 2 trang. C 64 hnh v v th, 16 bng biu, 122 ti liu tham kho.
B NI DUNG CHNH CA LUN N
CHNG 1 TNG QUAN
Phn ny tc gi trnh by tng quan cu trc v phn loi ca cc loi st t nhin, cu trc
ca cc polyoxocation kim loi (Al, Fe, Ti), cc loi st chng bng cc polyoxocation kim loi v st
chng c bin tnh bng cc cation hu c v ng dng ca cc vt liu ny.
CHNG 2: THC NGHIM
Thc nghim c tin hnh ti Phng th nghim, B mn Ha hc Du m - Khoa Ha hc
Trng i hc Khoa hc T nhin HQG H NI.

2.1. IU CH MONT-Na
2.1.1. Tinh ch bentonite Di Linh t nhin
thu c bentonite c hm lng montmorillonite cao t bentonite th, ngi ta thng x
l bentonite th bng nc decation. Quy trnh c tm tt nh sau: Bent-DL th c nghin thnh
bt mn, ha vo nc thu c huyn ph st 10%. Khuy mnh trong 24 gi, lng, gn ly
huyn ph st. Cho mt lng NaCl rn sao cho nng NaCl t c trong dung dch huyn ph l
1M. yn qua m, tch ly Bent-Na. Ra ht Cl- trong dung dch huyn ph st.
2.1.2. Xc nh dung lng trao i ion CEC ca bentonite Di Linh
Xc nh dung lng trao i CEC ca bentonite sau khi tinh ch: Cho 1g st vo bnh nn dung tch
250 ml. Cho vo 20 ml dung dch CH3COONH4 0,5M. Lc k hn hp 12h, gn ly nc trong cho vo
bnh nh mc 0,5 lt. Lp li 5 ln nh th. Gp tt c nc gn trong v nc lc ca ln x l sau cng vo
bnh nh mc 500ml, thm nc n vch mc, sau em phn tch Na+ trn my quang ph AAS. T
tnh c s meq. natri cho 100 gam Bent-Na. Kt qu AAS cho thy CEC ca Mont-Na l 70 mg/100g
st.
2.1.3. Thnh phn khong v thnh phn ha hc ca Bentonite Di Linh
Chng ti phn tch thnh phn khong v thnh phn ha hc ca bentonite Di Linh ti Trung
tm Phn tch a cht, Cc a cht v Khong sn Vit Nam, Thanh Xun, H Ni. Kt qu phn tch
thnh phn khong c trnh by trong bng 2.1.
Bng 2.1. Kt qu phn tch thnh phn khong Bent-DL
Thnh phn khong v hm lng %
Mu

TT
1
2
3

Bent th
Bent x l
nc decation
Bent-DL x
l ha hc

Mont

Illit

Kaolinit

Thch
anh

Felspart

Gtit

Canxit

Khong vt
khc

64,0

6,0

9,5

5,0

3,5

3,0

Hyd., Am

68,0

6,5

8,0

5,5

4,0

4,5

Hyd.,Chlorit

66,5

6,5

8,0

8,0

3,5

3,5

Hyd.

Bng 2.2. Kt qu phn tch thnh phn ha hc ca cc mu Bent-DL

TT
1
2
3

Mu
SiO2
Bent-DL th
50,5
Bent-DL x l nc
50,82
ct
Bent-DL x l ha
54,32
hc

Al2O3
17,67

Thnh phn ha hc ca Bent_DL, %

Fe2O3
TiO2
CaO
MgO
7,0
0,82
0,78
2,83

Na2O
0,54

MKN
18,97

16,52

8,12

0,48

2,16

2,36

0,36

18,93

15,90

6,73

0,26

0,98

1,88

01,39

17,96

2.2. TNG HP BENTONITE DI LINH CHNG BNG CC POLYOXOCATION KIM LOI

Al, Fe, Ti
2.2.1. Tng hp st chng nhm (Al-PICL)
Ha cht dung tng hp ion Keggin 0,1M nh sau: AlCl3.6H2O, NaOH, nc ct. Dung dch
ion Keggin c xc nh cu trc bng phng php 27Al-MAS-NMR. Quy trnh iu ch Al-PICL c tm
tt nh sau: Rt dung dch ion Keggin vo huyn ph st 5% ng thi khuy mnh. Phn ng trao i
xy ra. Kt ta thu c c x l nhit thu c Al-PICL.
2.2.2. Tng hp st chng st (Fe-PICL)

Ha cht dung tng hp polyoxocation st 0,1M nh sau: FeCl3.6H2O, NaOH, nc ct. Quy
trnh iu ch Fe-PICL c tm tt nh sau: Rt dung dch polyoxocation st vo huyn ph st 5% ng
thi khuy mnh. Phn ng trao i xy ra. Kt ta thu c c x l nhit thu c Fe-PICL.
2.2.3. Tng hp st chng titan (Ti-PICL)
Ha cht dung tng hp polyoxocation titan 0,1M nh sau: TiCl4, ancol etylic, glyxerin, HCl
v nc ct. Quy trnh iu ch Ti-PICL c tm tt nh sau: Rt dung dch polyoxocation titan vo
huyn ph st 5% ng thi khuy mnh. Phn ng trao i xy ra. Kt ta thu c c x l nhit,
thu c Ti-PICL.
2.3. TNG HP BENTONITE DI LINH CHNG BNG CC POLYOXOCATION KIM LOI
Al, Fe, Ti A DU
2.3.1. Tng hp st hu c Bent-CTAB
Tng hp Bent-CTAB theo phng php kh s thun li v mt cng ngh: cc thao tc n
gin, khng s dng v thi qu nhiu nc trong qu trnh ch to. V th chng ti chn phng php
kh ch to Bent-CTAB (60%) cho cc th nghim tip theo. Chng ti tm nhit hp l cho
iu ch Bent-CTAB (60%) bng cch: Dng dung mi phn cc l C2H5OH tuyt i (30% theo khi
lng Bent-Na), nhit thay i l 90 oC, 100 oC, 105 oC v 110 oC, thi gian x l l 4 gi.
2.3.2. Tng hp st chng a du
2.3.2.1. Tng hp st chng nhm a du (Al-PICL-CTAB) bng phng php kh
Nguyn liu: Al-PICL ( c iu ch nh 2.2.1), dung mi phn cc aproton, N,Ndimetyl formamit, (CH3)2NCHO, xetyl trimetyl amoni bromua, CTAB, C16H33(CH3)3N+Br-.
2.3.2.2. Tng hp st chng st a du (Fe-PICL-CTAB) bng phng php kh
Nguyn liu: Fe-PICL ( c iu ch nh 2.2.2), dung mi phn cc aproton, N, N
dimetyl fomamit,(CH3)2NCHO, xetyl-trimetylamonibromua, C16H33(CH3)3NBr
2.3.2.3. Tng hp st chng titan a du (Ti-PICL-CTAB)
Nguyn liu: Ti-PICL ( c iu ch nh 2.2.3), dung mi phn cc aproton, N, N
dimetyl fomamit,(CH3)2NCHO, xetyl trimetyl amoni bromua, C16H33(CH3)3N+Br-.
2.4. PHNG PHP NH GI KT QU THC NGHIM
Cc mu sn phm, vt liu hp ph c c trng tnh cht l ha bng cc phng php vt
l hin i nh 27Al-MAS-NMR, hng ngoi, nhiu x tia X, hin vi in t qut (SEM), hin vi in t
truyn qua (TEM), ng nhit hp ph - gii hp N2 (BET).
CHNG 3. KT QU V THO LUN
3.1. C TRNG BENTONITE DI LINH CHNG BNG CC POLYOXOCATION KIM
LOI Al, Fe, Ti
3.1.1. c trng st chng nhm (Al-PICL)
3.1.1.1. c trng cu trc ca ion Keggin v Al-PICL bng 27Al-MAS-NMR
Trong ph cng hng t ht nhn 27Al-MAS-NMR ca ion Keggin, AlO4 c pic trn 60 ppm,
cn Al(OH)6 xut hin pic gn ~ 0 ppm. Ph cng hng t ht nhn 27Al-MAS-NMR ca ion Keggin
v Al-PICL (hnh 3.1a v b). Trn ph 27Al-MAS-NMR ca ion Keggin Al137+ ta thy r AlO4 t din
cho pic gn ~ 66,14 ppm, cn Al(OH)6 bt din cho pic gn 0 ppm. Cc kt qu ny rt ph hp vi
cc ti liu c cng b v khng nh chng ti tng hp thnh cng ion Keggin v Bentonite
chng bng ion Keggin, Al-PICL.

Hnh 3.1: Ph 27Al-MAS-NMR ca ion Keggin [Al13O4(OH)24(H2O)12] 7+ (a) v Al-PICL (b).

3.1.1.2. Kt qu phng php nhit vi sai
Vt liu 5Al-PICL c pic mt nc b hp ph u tin 110 oC sau l mt nc cu trc
510 oC trong khong nhit nghin cu ti 700 oC. y l hai pic thu nhit c trng cho st chng
bng cc polyoxocation kim loi.

Hnh 3.2: Gin phn tch nhit vi sai ca Hnh 3.3: Gin nhiu x tia X ca cc vt
5.0Al-PICL.
liu MONT-Na v x Al-PICL (vi x = 2,5; 5,0;
7,5 v 10,0 mmol Al/gam st).
3.1.1.3. Kt qu phng php nhiu x tia X
Chng ti ghi gin nhiu x tia X ca cc mu xAl-PICL (x = 2,5; 5,0; 7,5 v 10,0 mmol
Al/gam st). Gin nhiu x c trnh by trn hnh 2.3 v bng 3.1 trnh by cc gi tr d 001 ca cc
sn phm thu c. Qua gin nhiu x tia X ca st c x l (hnh 3.3) ta thy rng thnh phn
chnh ca st Di Linh sau khi tinh ch l MONT. Cc tp khong Fe2O3 b loi gn ht khng thy
xut hin trn gin nhiu x. Ch cn xut hin nhiu x ca quartz trn gin nhiu x tia X.
Bng 3.1. Cc gi tr d001thu c t cc gin nhiu x tia X v khong cch gia cc lp st
= d001 - 9,4A0 ca cc mu st.
TT
1
2
3
4
5

Mu st
d001,
Khong cch gia cc lp st = d001- 9,4A0
MONT-Na
12,99
3,59
2,5 Al-PICL
18,25
8,85
5,0 Al-PICL
19,10
9,70
7,5 Al-PICL
19,12
9,72
10,0 Al-PICL
19,11
9,71
Cc nh pic c trng gc 2 = 2 - 40o ca vt liu MONT-Na cho thy khong cch khng

gian c s gia cc lp ca vt liu MONT-Na l 12,99 . Sau qu trnh chng, khong cch gia cc

lp ph thuc vo hm lng ca ion Keggin s dng. Khi cc polyoxocation nhm i vo khong

khng gian gia cc lp st lm cho cc gi tr d001 ca cc vt liu thu c tng ln r rt t 12,99
(MONT-Na) ln 18,25 (2,5 Al-PICL) v t n cao ti a ~19,1 (5,0 Al-PICL) sau gi tr
d001 hu nh khng thay i (xem bng 3.1). Nh vy, ch khi hm lng nhm trong ion Keggin t n
t l 5mmol Al/gam st cc lp st c gin ra n khong 1,91 nm, khong cch ny bng tng b
dy ca mt lp st (0,94 nm) v chiu cao ca mt ion Keggin (0,97 nm) [45, 81, 92].
3.1.1.4. Kt qu phng php ph hng ngoi IR
Chng ti chp ph hng ngoi ca cc mu MONT-Na v x Al-PICL, kt qu c trnh
by trong bng 3.2.
Bng 3.2: Cc vng hp th c trng trong ph hng ngoi ca cc mu: MONT-Na, x AlPICL, cm-1.
Nhm cu trc
Si-OH
H-OH
Si-O
Si-O-Al
Si-O-Mg
Al-OH
Mg-OH
1 MONT-Na
3622
3427-1634
1032
528,2
913,8
615
2 x Al-PICL
3625
3421-1639
1034
528,3
468,7
918,0
679
Hnh 3.4 cho thy cc vt liu MONT-Na v x Al-PICL (vi x = 2,5; 5,0; 7,5 v 10,0) u c
kh nng hp th nc tt th hin trn di ph c bc sng ~3400 cm-1. Tt c cc vt liu thu c
u cha cc nhm -OH cu trc v lin kt Si-O ca lp st vi di ph vng c bc sng t 16341659cm1. Di ph ti bc sng 1032-1035 cm-1 tng ng c xem l dao ng bt i xng ca lin
kt Si-O-Si ca MONT. Di ph t 720 n 839 cm1 c trng nht cho quartz v di ph 423528 cm1
c xem l dao ng ca lin kt O-Si-O kt qu ny cng ph hp vi cc ti liu cng b [21,
64].
Vt liu

1032.8

TT

0.55

0.50

468. 0

0.45

531. 8

0.40

913. 8

3622.9

795. 6

0.20

0.15

0.10

695. 8

1639.3

0.25

3437.5

0.30
3697.6

A bs orbance

0.35

0.05
0.00
4000

3500

3000

2500

2000

1500

1000

500

Wavenumbers (cm-1)

(a)
(b)
Hnh 3.4: Ph hng ngoi ca cc vt liu MONT-Na (a) v x Al-PICL (vi x = 2,5; 5,0; 7,5 v 10,0
mmol Al/gam st) (b).
3.1.1.5. Kt qu c trng cu trc xp ca cc vt liu x Al-PICL
Din tch b mt ca st chng oxt kim loi ph thuc vo hai yu t: phn din tch micropore
(gia cc lp st) v phn din tch mesopore (do cc lp st sp xp thnh cc cu trc nh ca cc
qun c).

(b)
(a)
Hnh 3.5: ng ng nhit hp ph, gii hp nit 77K (a) v ng phn b l ca MONT-Na v
xAl-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Al/gam st).
Bng 3.3: Din tch b mt (BET) ca cc vt liu tng hp c.
MONT-Na
2.5Al-PICL
5.0Al-PICL
7.5Al-PICL
10.0Al-PICL
Vt liu
2
40.09
118.71
184.32
203.30
167.57
SBET (m /g)
3.1.1.6. Phn tch qua nh SEM ca cc vt liu xAl-PICL (vi x = 2,5; 5,0; 7,5 v 10,0)
T nh hin vi in t qut SEM (hnh 3.6), ta thy c cu trc lp ca vt liu st. Cc lp
nhm silicat xp chng ln nhau ph hp vi cu trc ca vt liu MONT. T hnh 3.6, c th thy r
tp hp cc lp st cch nhau r rng hn sau khi chng bng polyoxocation nhm, hnh thnh cc ht
ln c cu trc trt t hn.
3.1.1.7. Phn tch qua nh TEM ca cc vt liu xAl-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Al/gam
st)
T hnh 3.7, chng ti thy rng vt liu st c cu trc lp 2 chiu vi cc lp st cch nhau
mt khong nh. Sau khi c chng bi cc ion Keggin, khong cch gia cc lp gin ra rng hn so
vi trc khi chng. Hn na, c th thy c cc chm nh khong khng gian gia cc lp trong
cc vt liu Al-PICL chnh l cc pillar Al2O3.

Hnh 3.6: nh SEM ca cc mu MONT-Na v cc vt liu 7,5Al-PILC.

Hnh 3.7: nh TEM ca MONT-Na v cc vt liu 7,5Al-PILC

3.1.2. c trng bentonite Di Linh chng st xFe-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Al/g st)
3.1.2.1. Kt qu phng php phn tch nhit vi sai
Kt qu cho thy tnh cht nhit ca st chng oxit kim loi rt c trng: Fe-PICL c hai hiu
ng thu nhit do mt nc b hp ph 154,37 oC v nc cu trc 528,15 oC.
Figure:

Experiment:Fe2O3 Bent

Crucible:PT 100 l

Atmosphere:Air

12/04/2010 Procedure: RT ----> 800C (10C.min-1) (Zone 2)

Labsys TG

Mass (mg): 85.49001

TG/%

HeatFlow/V
Exo

20

d TG/% /min

Peak :528.15 C

15
-25
-4
10

-50

Peak :154.37 C

-8
-75

-5

-100

Mass variation: -17.34 %

-10

-12
-15
-125
Mass variation: -3.15 %

-20

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.8: Gin phn tch nhit vi sai ca 5.0 Hnh 3.9: Gin nhiu x tia X ca cc vt
Fe-PICL.
liu x Fe-PICL (vi x = 2,5; 5,0; 7,5 v 10,0
mmol Fe/gam st).
3.1.2.2. Kt qu ph nhiu x tia X
Kt qu chp nhiu x tia X c trnh by hnh 3.9 v bng 3.4. Sau khi chng cc lp st
bng polyoxocation st, khong cch d001 tng t 12,99 A0 MONT-Na ln 15,45 A0 Fe-PICL, nh
vy khong cch gia hai lp st lin tip cch nhau l 5,56A0 ngha l sau khi chng khong cch gia
hai lp st lin tip tng ln: 5,56A0 3,18A0 = 2,38A0.
3.1.2.3. Kt qu phng php ph hng ngoi IR
Chng ti chp ph hng ngoi ca mu x FePICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Fe/gam
st). Kt qu c trnh by trong hnh 3.10. Di
y l cc vng ph c trng cho cc nhm cu
trc ca Fe-PICL: Sitd OH 3626 cm-1, H-OH
(nc b hp ph) 3425, 1640 cm-1, Sitd O
1036 cm-1, Sitd O Albd 529 cm-1, Sitd O
MgBd 468 cm-1, Albd OH 918 cm-1, Mgbd
OH 678 cm-1.
Hnh 3.10: Ph hng ngoi ca cc vt liu x FePICL.

3.1.2.4. Kt qu c trng cu trc xp ca cc vt liu x Fe-PICL (vi x = 2,5; 5,0; 7,5 v 10,0
mmol Fe/gam st)
Bng 3.4: Din tch b mt (BET) ca cc vt liu tng hp c.
Vt liu

MONT-Na

2.5 Fe-PICL

5.0 Fe-PICL

7.5 Fe-PICL

10.0 Fe-PICL

40,09

102,86

154,04

128,04

95,01

SBET (m /g)

(a)

(b)
Hnh 3.11: ng ng nhit hp ph, gii hp nit 77K v ng phn b l ca MONT-Na v x FePICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Fe/gam st).
3.1.2.5. Kt qu nh SEM ca cc vt liu x Fe-PICL (vi x = 2,5; 5,0; 7,5 v 10,0)
nh SEM ca cc vt liu ny cho thy
Fe-PICL vn gi cu trc lp nh
MONT-Na. Nh vy, mt ln na c th
khng nh MONT sau khi chng bng
Fe3(OH)4Cl5 pH = 1,8 khng b bin
i cu trc.

Hnh 3.12: nh SEM ca vt liu 5FePICL.

3.1.2.6. Kt qu nh TEM ca cc vt liu x Fe-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Fe/gam st)
Hnh 3.13 l hnh nh hin vi in t truyn qua TEM ca 5,0 Fe-PICL. Vt liu st c cu trc
lp 2 chiu vi cc lp st cch nhau mt khong nh. Sau khi c chng bi cc ion tng t ion
Keggin, khong cch gia cc lp gin ra rng hn so vi trc khi chng. Khc vi cc vt liu AlPICL, mt phn Fe3+ b thy phn trn b mt st nn rt kh c th nhn r khong khng gian cc
lp st. Ngoi ra c mt phn cc ion tng t ion Keggin keo t vi nhau, sau phn hy nhit
cao tao thnh cc ht nano Fe2O3 (hnh 3.13).

Hnh 3.13: nh TEM ca vt liu 10Fe-PICL v nano Fe2O3.

3.1.3. c trng bentonite chng titan (Ti-PICL)
3.1.3.1. Kt qu phng php phn tch nhit vi sai ca vt liu Ti-PICL

Hnh 3.14: Gin phn tch nhit vi sai ca Hnh 3.15: Gin nhiu x tia X ca cc vt
vt liu 5,0 Ti-PICL.
liu x Ti-PICL.
Trn ng DTA thng c 3 pic n gin hn so vi st khng chng. Hai pc thu nhit u
tin khong nhit 90 520 oC. Pc u tin tng ng vi s mt nc hp ph ni ln bn cht a
nc ca st chng oxit kim loi. Hiu ng thu nhit th hai tng ng vi s mt nc ca ct chng
v nc cu trc ca st. Vi Ti-PICL hiu ng thu nhit th nht hi thp khong 42% v hiu ng
th hai 516 oC.
3.1.3.2. Kt qu ph nhiu x tia X
Kt qu chp ph nhiu tia X ca cc vt liu Ti-PICL c trnh by trong hnh 3.15 v bng
3.5. T bng 3.5 cho thy khong cch d001 ca Ti-PICL l 18,7 A0, khong cch hai lp st l 9,10 A0.
Nh vy khong cch khng gian gia hai lp st tng ln rt ln chng t chng st bng
polyoxocation [(TiO)8(OH)24]4+ thnh cng.
Bng 3.5: Din tch b mt (BET) v cc gi tr d001 ca cc vt liu x Ti-PICL.
MONT-Na
2.5 Ti-PICL
Vt liu
40,09
109,26
SBET (m2/g)
12,99
17,2
d001 ()
3.1.3.3. Kt qu phn tch ph hng ngoi IR

5.0 Ti-PICL
164,12
18,7

7.5 Ti-PICL
132,87
18,7

10.0 Ti-PICL
97,31
18,6

10

Trong quang ph hp th hng ngoi

(hnh 3.16), chng ta thy rng ti vng c bc
sng 720 cm-1, cng hp th tng ln lt t
vt liu 2,5 Ti-PICL ln 10,0 Ti-PICL ng vi
s tng mt ct chng TiO2. Ngoi ra, trong
vng c bc sng khong 3400 cm-1, s hp
th cng tng ln lt t vt liu 2,5 Ti-PICL
n 10,0 Ti-PICL. iu ny c th c gii
thch l do s hp ph nc tng dn t vt liu
2,5 Ti-PICL n 10,0 Ti-PICL.

Hnh 3.16: Ph hng ngoi ca cc vt liu

xTi-PICL.
Bng 3.6: Cc vng hp th c trng trong ph hng ngoi ca cc mu: MONT-Na, x TiPICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Ti/gam st), cm-1.
TT

Vt liu

Nhm cu trc
Si-OH

H-OH

Si-O

Si-O-Al

Si-O-Mg

Al-OH

Mg-OH

Ti-OH

1 MONT-Na 3622 3427-1634 1032

528,2
913,8
615
2 x Ti-PICL
3625 3421-1639 1034
528,3
468,7
918,0
679
728
3.1.3.4. c trng cu trc xp ca cc vt liu
T bng 3.5 chng ti thy rng din tch b mt ca cc vt liu tng ln trong qu trnh
chng. MONT-Na c din tch b mt l 40,09 m2/g, sau khi chng bi cc cluster titan oxt tng ln
109,26 m2/g (2,5 Ti-PICL), 164,12 m2/g (5,0 Ti-PICL), sau gim dn 132,87 m2/g (7,5 Ti-PICL) v
97,31 m2/g (10,0 Ti-PICL). iu ny chng t rng trong qu trnh chng cc ion tng t ion Keggin
i vo khong khng gian gia cc lp st. Dng cc ng cong tr (hnh 3.17) cho thy s to
thnh cc l trng mao qun trung bnh ca vt liu st chng l khng ng u. Cc kt qu ny c th
gii thch c khi cc lp st c chng ln bng cc ct chng polyoxocation titan th din tch b
mt trong ca cc ht st tng ln (quyt nh din tch phn vi mao qun) v cc kt qu ny cng ph
hp vi cc ti liu cng b.

(b)
(a)
Hnh 3.17: ng ng nhit hp ph, gii hp nit 77K v ng phn b l ca MONT-Na v x TiPICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Ti/gam st).
3.1.3.5. Kt qu nh SEM ca cc vt liu x Ti-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Ti/gam st)

11

Chng ti chp nh SEM ca vt liu 7.5Ti-PICL.

T nh SEM, thy rng vt liu c cu trc lp r rng.
Cc lp c tch ra sau khi chng. Kt qu ny cng
khng nh chc chn cc polyoxocation Titan xen
c vo gia cc lp st. iu ny cng chng minh
rng trong qu trnh chng cc polyoxocation titan
khng lm nh hng n cu trc ca st.
Hnh 3.18: nh SEM ca 7.5 Ti-PICL.
3.1.3.6. Kt qu nh TEM ca cc vt liu x Ti-PICL (vi x = 2,5; 5,0; 7,5 v 10,0 mmol Ti/gam st)
T hnh 3.19, chng ti thy rng vt liu st c
cu trc lp 2 chiu vi cc lp st cch nhau mt
khong nh. Sau khi c chng bi cc ion tng
t ion Keggin, khong cch gia cc lp gin ra
rng hn so vi trc khi chng. Hn na, c th
thy c cc chm nh khong khng gian gia
cc lp trong cc vt liu x Ti-PICL (vi x = 2,5;
5,0; 7,5 v 10,0).
Hnh 3.19: nh TEM ca 5.0Ti-PICL.
3.2. C TRNG BENTONITE DI LINH CHNG BNG CC POLYOXOCATION KIM
LOI Al, Fe, Ti A DU
3.2.1. c trng st hu c Bent-CTAB (Organo-Clay)
3.2.1.1. Kt qu phng php nhiu x tia X
Ph nhiu x tia X ca Bent-CTAB c trnh by trong hnh 3.20 v bng 3.8. T kt qu c
trnh by bng 3.8, chng ti c th thy khi xen k cc phn t CTAB vo gia cc lp st, khong
cch khng gian c s d001 tng ln rt mnh t 12,99 i vi Bent-Na (MONT-Na) tng ln ti 26,76
, nh vy khong cch gia 2 lp lin nhau ca Bent-CTAB l 13,77 . S d khong cch tng rt
mnh l do mch hydrocacbon C16H33- kh di. T kt qu ny cng tng t vi cc kt qu c
cng b trong cc ti liu chuyn ngnh [92].
3.2.1.2. Kt qu phng php phn tch nhit.
Trn gin phn tch nhit vi sai ca Bent-CTAB (hnh 3.21):
Quan st thy hiu ng thu nhit thng thng i vi Bentonite khong 114,85 oC. Nhit
ny cho thy l vt liu Bent-CTAB c nhit gii hp nc cao hn so vi Bentonite thng thng.
iu ny c th do phng php iu ch Bent-CTAB (Organoclay) theo phng php kh khng s
dng nc v nhit x l 105 oC loi ht nc hp ph gia cc lp st, tuy nhin sau thi gian
Bent-CTAB hp ph nc tr li, v qu trnh gii hp nc b cn tr bi cc phn t CTAB co kch
thc ln. Xy ra mt hiu ng pht nhit mnh 251,24 oC v 325,85 oC tng ng vi s chy phn
hy hp cht hu c CTAB. Qu trnh chy ny ta nhit v km theo s gim khi lng mu 11,87 %.

12

Figure:

Experiment:Mau Fe-CTAB

Crucible:PT 100 l

Atmosphere:Air

11/09/2010 Procedure: RT ----> 700C (10 C.min-1) (Zone 2)

Labsys TG

Mass (mg): 31.35

TG/%

BO M ON HOA VAT LIEU-KHOA HOA-TRUONG DHKHTN

HeatFlow/V
Exo
Peak :325.85 C

25

30
15

Mass variation: -4.66 %

Ten may: GX-PerkinElmer-USA

Nguoi do: Phan Thi Tuyet M ai DT:01684097382

Resolution: 4cm-1

M ail: maip lm@y ahoo.com

Date: 11/26/2010

Set huuco - NCS Duc

1.00
1038

20

0.9

0.8

-5
0.7

10
Peak :251.24 C
Peak :114.85 C

0.6

-15

0.5

Mass variation: -11.22 %

-25

3441

469

0.4

-35

Peak :556.01 C

-10

525

0.3
1656
2925
2852

0.2

Mass variation: -11.77 %

916

1390

779

-45

797

0.1

1469

697

1438

-20
-55

0.00
4000.0

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

800

600

400.0

cm-1

50

100

150

200

250

300

350

400

450

500

550

Furnace temperature /C

Hnh 3.21: Gin phn tch nhit vi sai ca Hnh 2.22: Ph hng ngoi ca vt liu st hu
vt liu Bent-CTAB.
c Bent-CTAB (organoclay).
3.2.1.3. Kt qu phng php ph hng ngoi IR
Trn ph IR ca Bent-CTAB chng ti thy cc vng hp th c trng cho Bent-CTAB: Vng
~ 3600 cm-1, c trng cho dao ng ha tr ca nhm OH trong silanol, Si-OH, vng ~ 3441 cm-1 v
1656 cm-1 c trng cho dao ng ha tr bin dng ca phn t nc H-OH b hp ph, vng ~ 1038
cm-1 c trng cho dao ng ha tr ca lin kt SiTd-O, vng ~ 525 cm-1 c trng cho dao ng ca
nhm SiTd- O-AlBd, vng ~ 2852 cm-1 c trng cho dao ng ha tr ca nhm CH2- ca gc C16H33-,
vng ~1438, 1390 cm-1 c trng cho dao ng ha tr ca lin kt C-N.
3.2.2. c trng st chng nhm a du (Al-PICL-CTAB)
3.2.2.1. Kt qu phng php phn tch nhit vi sai
i vi st chng a du, tnh cht nhit ca chng khc vi st chng kim loi tng ng. i
vi Al-PICL-CTAB khi nng nhit xut hin pc thu nhit u tin 119,14 oC gim i 3,46% trng
lng mu tng ng vi s mt nc b hp th. Pc th hai tr nhit khong 254,38 n 301,98 oC l
do CTAB b chy. Qu trnh chy ny lm gim 13,34% v khi lng mu.
Figure:

Crucible:PT 100 l

Experiment:Al-PICl

Atmosphere:Air

14/07/2010 Procedure: 30 ----> 800C (10 C.min-1) (Zone 2)

Labsys TG

Mass (mg): 40.06

TG/%

Peak :119.14 C

20

HeatFlow/V
40
Exo

dTG/% /min

20

-2

Peak :529.90 C
Peak 1 :254.38 C
Peak 2 :301.98 C

10

0
-4

-20
0

-6

Mass variation: -3.46 %

-40
Mass variation: -13.34 %

-10

-8
-60

-20

Mass variation: -10.39 %

100

200

300

400

500

600

700

-10
-80

Furnace temperature /C

Hnh 3.23: Gin phn tch nhit vi sai Hnh 3.24: Gin nhiu x tia X ca cc vt liu
ca vt liu 5.0 Al-PICL-CTAB.
MONT-Na, st hu c, x Al-PICL v x Al-PICLCTAB (x = 2,5; 5,0; 7,5 v 10,0 mmol Al/gam st).
Qu trnh chy CTAB ko di lm gn nh trit tiu hiu ng thu nhit do mt nc cu trc
529,9 oC, vi s mt khi lng khong 10,39%. y mt khong nhit c trng cho nghin cu
tnh cht nhit ca cc cu t hu c xen k gia cc lp st.
3.2.2.2. Kt qu phng php nhiu x tia X
3.2.2.3. Kt qu phng php ph hng ngoi IR

13

Hnh 3.25: Ph hp th hng ngoi ca cc vt Hnh 3.26: nh SEM ca cc mu MONT-Na

liu st hu c, x Al-PICL v x Al-PICL-CTAB v cc vt liu x Al-PILC-CTAB (vi x = 2,5;
(vi x = 2,5; 5,0; 7,5 v 10,0 mmol Al/gam st). 5,0; 7,5 v 10,0 mmol Al/gam st).
Bng 3.7: Cc vng hp th c trng trong ph hng ngoi ca cc mu: MONTNa,organoclay, x Al-PICL v x Al-PICL-CTAB, cm-1.
Vt liu

Nhm dao ng
H-OH

-OH (cu trc)

Si-O

Si-O- Alo

Si-O-Mgo

Alo-OH

Mgo-OH

-CH2-

C-N

MONT-Na

3427

1639

1032

913.8

792.6

Organoclay

3443

1634.1

1033.5

523.9

467.8

910.8

792.3

2.5Al-PICL

3444.2

1650

1034

525.5

469.6

910.8

792.3

2.5Al-PICL-CTAB

3445.7

1653.2

1035.4

526.2

469.6

910.8

796.1

2926-2843.6

1389.6

5.0 Al-PICL

3421

1639

1034

527.5

468.6

918.5

792.6

5.0 Al-PICL-CTAB

3448

1638

1033

527.7

468.8

919.0

792.7

2924-2852

1476

3443.8

1649.6

1035.1

525.4

469.4

919.0

796.4

3447

1659

1035.0

525.0

470.0

910.2

797

2920-2852

1489

3469

1640.1

1035.1

528.2

469.1

910.8

755.5

3444.5

1652.8

1035.1

525.5

468.2

919.0

792.3

2923.3-2851.8

1488.2

7.5 Al-PICL
7.5 Al-PICL-CTAB
10Al-PICL
10Al-PICL-CTAB

3.2.2.4. Kt qu phng php chp nh SEM

T hnh 3.26, c th thy r tp hp cc lp st cch nhau r rng hn sau khi chng bng
polyoxocation nhm, hnh thnh cc ht ln c cu trc trt t hn. T cc hnh nh ny, chng ta thy
r tnh cht lp v hnh hc b mt ca ca ht st t nhin v st chng bng cc oxit kim loi a du.
3.2.2.5. Kt qu phng php chp nh TEM
Sau khi c chng bi cc ion Keggin,
khong cch gia cc lp gin ra rng hn so vi
trc khi chng. Hn na, c th thy c cc
chm nh khong khng gian gia cc lp trong
cc vt liu Al-PICL c th c gii thch l do
cc cluster Al2O3. Khi tm CTAB ln, chng ta
thy rng l ln hn vt liu Al-PICL ban u.
Hnh 3.27: nh HRTEM ca 5.0Al-PILC-CTAB.
3.2.3. c trng bentonite Di Linh chng st a du (Fe-PICL-CTAB)
3.2.3.1. Kt qu phng php phn tch nhit vi sai

14

Figure:

Experiment:Fe2O3 CTAB

Crucible:PT 100 l

Atmosphere:Air

12/04/2010 Procedure: RT ----> 800C (10C.min-1) (Zone 2)

Labsys TG

Mass (mg): 86.71999

TG/%

HeatFlow/V

dTG/% /min

Exo

28
Peak :155.48 C

21
20

Peak :267.26 C

-4

14

-20

-8

Mass variation: -5.70 %

-7

-14
Mass variation: -19.65 %

-60

-12

-21

-28

Mass variation: -5.45 %

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.28: Gin phn tch nhit vi sai ca vt Hnh 3.29: Gin nhiu x tia X ca cc vt
liu 5,0 Fe-PICL-CTAB.
liu x Fe-PICL-CTAB (vi x = 2,5; 5,0; 7,5 v
10,0 mmol Fe/gam st).
i vi Fe-PICL-CTAB, chng ti quan st thy hiu ng thu nhit u tin do mt nc b hp
ph ~155 oC, tng ng vi s gim khi lng mu 5,7 %. Hiu ng th hai pht nhit ~255 oC,
tng ng vi s gim khi lng mu 19,65 %. Hiu ng pht nhit ny l do s chy CTAB gy ra.
Khi nhit tng n 700 oC khng quan st thy s mt nc cu trc ca Fe-PICL-CTAB.
3.2.3.2. Kt qu phng php nhiu x tia X
T hnh 3.29, chng ti thy rng khong cch cc d001 ca cc mu Fe-PICL-CTAB tng ln so
vi vt liu Fe-PICL ban u. iu ny c th gii thch s tng tc lng lo gia cc lp st v cc
cluster oxit st. iu ny dn n s ni rng khong cch gia cc mt silicat lin nhau khi phn t
CTAB xen vo. Nh bit CTAB c gc ankyl C16H35- c kh nng lm tng khong cch gia cc lp
st lin nhau.
3.2.3.3. Kt qu ph hng ngoi

Hnh 3.30: Ph hp th hng ngoi ca cc vt Hnh 3.31: nh SEM ca cc vt liu 5.0Feliu x Fe-PICL v x Fe-PICL-CTAB (vi x = PICL-CTAB.
2,5; 5,0; 7,5 v 10,0 mmol Fe/gam st).
3.2.3.4. Kt qu chp nh SEM
nh SEM ca cc mu Fe-PICL-CTAB cho thy cc ht Fe-PICL-CTAB nh ng u, kch
thc < 2m. Cc ht bao gm cc lp st phng, vi kch thc ht ny sn phm Fe-PICL-CTAB c
th dng ngay lm ph gia cho sn m khng cn ch bin g.
3.2.3.5. Kt qu chp nh TEM

15

T hnh 3.32, chng ti thy rng vt liu st c

cu trc lp 2 chiu vi cc lp st cch nhau mt
khong nh. Sau khi c chng bi cc ion tng
t ion Keggin, khong cch gia cc lp gin ra
rng hn so vi trc khi chng. Hn na, khi tm
CTAB ln, chng ta thy rng l ln hn vt
liu Fe-PICL ban u.

Hnh 3.32: nh HRTEM ca MONT-Na v cc vt

liu 5.0Fe-PILC-CTAB.
3.2.4. c trng bentonite Di Linh chng titan a du (Ti-PICL-CTAB)
3.2.4.1. Kt qu phng php phn tch nhit vi sai
i vi Ti-PICL-CTAB, chng ti quan st thy hiu ng thu nhit u tin do mt nc b hp
ph nhit kh thp so vi cc st chng hu c trn: 115,7 oC, tng ng vi lng nc c
gii phng l 6,00 % trng lng mu. Nhit gii phng nc hp ph mu Ti-PICL-CTAB cao
hn so vi mu Ti-PICL (91,9 oC). Lng nc hp ph c gii phng mu Ti-PICL-CTAB thp
hn so vi mu Ti-PICL (9,321%). iu ny c th c gii thch l do Ti-PICL a nc hn so vi
Ti-PICL tm CTAB. V c th do Ti-PICL a nc v gii phng d dng cc phn t nc b
mt. Hiu ng mt nc hp ph ny cng tng t nh hiu ng th nht thu nhit, mt nc b hp
ph mu Ti-PICL: 91,92 oC. Tip theo l hiu ng th 2 pht nhit 265,65 oC, tng ng vi s
gim trng lng mu ~9,51%. Hiu ng pht nhit ny l do CTAB b chy trong quyn khng kh bao
quanh mu khi t nng. Qu trnh chy CTAB ko di ti~ 4330C mi kt thc. Hiu ng pht nhit
ny c th b lp hiu ng mt nc cu trc ca st.
C th thy rng cc vt liu Al-PICL-CTAB, Fe-PICL-CTAB v Ti-PICL-CTAB c tnh cht
nhit khc nhau. S khc nhau ny c th l do s c mt ca cc cluster oxit kim loi trong cu trc ca
chng khc nhau: Cluster Al2O3, Fe2O3 v TiO2. Cng c th v th tc dng ph gia ca chng cng
khc nhau.
Figure:

Crucible:PT 100 l

Experiment:TiO2-PICL-CTAB

Atmosphere:Air

22/04/2010 Procedure: RT ----> 900C (10C.min-1) (Zone 2)

Labsys TG

Mass (mg): 34.65

TG/%

HeatFlow/V
50
Exo

d TG/% /min

Peak :505.28 C

Peak :115.70 C

30

Peak :265.65 C

-4

30

20

10

-8

10

-10
0

-12
Mass variation: -6.00 %

-30
-10
Mass variation: -9.51 %

-16
-50

-20

Mass variation: -17.39 %

-20
-70

-30

100

200

300

400

500

600

700

Furnace temperature /C

Hnh 3.33: Gin phn tch nhit vi sai ca vt Hnh 3.34: Gin nhiu x tia X ca cc vt
liu 5,0 Ti-PICL-CTAB.
liu MONT-Na, st hu c v x Ti-PICLCTAB.
3.2.4.2. Kt qu ca phng php nhiu x tia X

16

Ph nhiu x tia X ca cc vt liu Ti-PICL-CTAB c trnh by trong hnh 3.34, kt qu cho

thy khong cch kng gian c s d001 ca sn phm Ti-PICL-CTAB l 26,52 A0. Gi tr ny ln hn rt
nhiu so vi cc vt liu Ti-PICL. Gi tr ny l hp l v khi CTAB a vo cc lp st c th lm tch
cc lp st to iu kin cho s khuch tn cc phn t hu c v cc ion khi s dng Ti-PICL-CTAB
lm vt liu hp ph.
3.2.4.3. Kt qu phng php ph hng ngoi

Hnh 3.35: Ph hp th hng ngoi ca cc vt Hnh 3.36: nh SEM ca cc vt liu 5.0Tiliu x Ti-PICL-CTAB (x = 2,5; 5,0; 7,5 v 10 PICL-CTAB.
mmol Ti/gam st).
3.2.4.4. Kt qu chp nh SEM
nh SEM ca mu nghin cu cho thy cc ht st chng hu c c cu trc tng t MONTNa. ht nh hn 2m.
3.2.4.5. Kt qu chp nh TEM
T hnh 3.37, chng ti thy rng vt liu st c cu trc lp 2 chiu vi cc lp st cch nhau
mt khong nh. Sau khi c chng bi cc ion tng t ion Keggin, khong cch gia cc lp gin ra
rng hn so vi trc khi chng. Hn na, khi tm CTAB ln, chng ta thy rng l ln hn vt liu
Ti-PICL ban u.

Hnh 3.37: nh HRTEM ca cc vt liu 5.0Ti-PILC-CTAB v 7.5Ti-PICL-CTAB.

Nh vy, chng ti ch to thnh cng cc vt liu Me-PICL-CTAB, vt liu lai, dn tt, c
tnh cht lng tnh (dual properties) c kh nng hp ph c ion v c (Cu2+) v cc ion hu c (cc
cation v anion hu c).
3.3. NG DNG CA CC VT LIU ST CHNG A DU TNG HP C LM
CHT HP PH
3.3.1. Hp ph Cu2+

17

3.3.1.1. Kt qu hp ph ca cc vt liu Al-PICL v Al-PICL-CTAB

Trong qu trnh hp ph, s hp ph ca cc ion Cu2+ xy ra rt nhanh trong 30 pht u tin v
sau tng chm n 36 gi, thi im c coi t n cn bng hp ph. iu ny c th c gii
thch l do ti thi im ban u cc trung tm hot ng trn b mt ca vt liu hp ph cn trng, s
hp ph xy ra rt nhanh, sau thi gian s lng cc trung tm hot ng gim v vy tc hp ph
ph thuc nhiu hn vo tc chuyn dch ca cc ion Cu2+ t pha th tch n cc trung tm hot
ng cn li. Cc s liu thc nghim cho thy rng vt liu 7,5 Al-PICL l vt liu hp ph tt nht,
iu ny cng ph hp vi cc d kin phn tch vt l cho thy 7,5 Al-PICL c din tch b mt ln
nht (203,03 m2/g).

Hnh 3.38: S thay i hm lng hp ph ca Cu2+ hp ph trn 1 n v vt liu theo

thi gian ti cc pH khc nhau.
Bng 3.10: Ti trng hp ph ion Cu2+ cn bng (qcb) ca cc vt liu st chng nhm v st chng
nhm c bin tnh bi CTAB thu c ti cc gi tr pH khc nhau (n v mg/g).
Gi
tr pH

MontNa

Organoclay

2,5AlPICL

5,0AlPICL

7,5AlPICL

10AlPICL

2,5
3,5
5,0

11,1
12,3
13,7

13,4
14,2
15,5

30,6
32,5
38,7

34,5
36,1
41,5

38,5
42,7
54,1

27,9
29,5
39,2

2,5AlPICLCTAB
27,0
28,1
39,2

5,0AlPICLCTAB
22,5
24,2
38,5

7,5AlPICLCTAB
21,3
22,4
33,5

10AlPICLCTAB
18,8
20,7
31,2

Khi tm CTAB ln cc vt liu ny, kh nng hp ph cc kim loi nng ca cc vt liu ny

gim xung. T s liu thc nghim, chng ti thy kh nng hp ph ca cc vt liu st chng nhm
tm CTAB gim t vt liu 2,5 Al-PICL-CTAB xung n vt liu 10,0 Al-PICL-CTAB. iu ny c
th c gii thch l do khi tm CTAB ln cc vt liu st chng nhm, cc lp st c chng bi cc
phn t CTAB, khong cch gia cc lp st sau khi chng bi CTAB (26,01 9,40 = 16,61 Ao) ln
hn chiu cao ca ct chng Al2O3 (9,72 Ao). Do , vai tr ca cc ct chng oxit kim loi khng cn

18

tc dng trong qu trnh chng, cc ct chng lc ny chim gi cc v tr hp ph. Do , t l ct

chng cng tng th din tch b mt trng cng gim, kh nng hp ph gim.
3.3.1.2. Kt qu hp ph ca cc vt liu Fe-PICL v Fe-PICL-CTAB
Cng ging nh trong qu trnh hp ph ca cc vt liu Al-PICL v Al-PICL-CTAB, s hp
ph ca cc ion Cu2+ ln cc vt liu Fe-PICL v Fe-PICL-CTAB xy ra rt nhanh trong 30 pht u
tin v sau tng chm n 36 gi, thi im c coi t n cn bng hp ph. iu ny c th c
gii thch l do ti thi im ban u cc trung tm hot ng trn b mt ca vt liu hp ph cn trng,
s hp ph xy ra rt nhanh, sau thi gian s lng cc trung tm hot ng gim v vy tc hp ph
ph thuc nhiu hn vo tc chuyn dch ca cc ion Cu2+ t pha th tch n cc trung tm hot
ng cn li. Cc s liu thc nghim cho thy rng vt liu 5,0 Fe-PICL l vt liu hp ph tt nht,
iu ny cng ph hp vi cc d kin phn tch vt l cho thy 5,0 Fe-PICL c din tch b mt ln
nht (154,04 m2/g). Khi tm CTAB ln cc vt liu ny, kh nng hp ph cc kim loi nng ca cc vt
liu ny gim xung. T s liu thc nghim, chng ti thy kh nng hp ph ca cc vt liu st chng
nhm tm CTAB gim t vt liu 2,5 Fe-PICL-CTAB xung n vt liu 10,0 Fe-PICL-CTAB. iu
ny c th c gii thch l do khi tm CTAB ln cc vt liu st chng nhm, cc lp st c chng
bi cc phn t CTAB, vai tr ca cc ct chng oxit kim loi khng cn tc dng trong qu trnh
chng. Do , t l ct chng cng tng th din tch b mt trng cng gim, kh nng hp ph gim.

Hnh 3.39: S thay i hm lng hp ph ca Cu2+ hp ph trn 1 n v vt liu

theo thi gian ti cc pH khc nhau.

19

Bng 3.11: Ti trng hp ph ion Cu2+ cn bng (qcb) ca cc vt liu st chng st v st chng st
bin tnh bi CTAB thu c ti cc gi tr pH khc nhau (n v mg/g).
Gi
tr pH

MontNa

Organoclay

2,5FePICL

5,0FePICL

7,5FePICL

10FePICL

2,5
3,5
5,0

11,1
12,3
13,7

13,4
14,2
15,5

25,7
31,2
34,8

31,2
34,1
41,6

26,5
33,5
38,1

23,6
30,7
33,9

2,5FePICLCTAB
22,1
29,9
33,1

5,0FePICLCTAB
20,3
23,2
31,6

7,5FePICLCTAB
19,5
27,7
30,2

10FePICLCTAB
17,2
24,4
28,8

3.3.1.3. Kt qu hp ph ca cc vt liu Ti-PICL v Ti-PICL-CTAB

Cng ging nh qu trnh hp ph trn cc vt liu st chng nhm, st chng nhm tm CTAB,
st chng st v st chng st tm CTAB, s hp ph ca cc ion Cu2+ ln cc vt liu st chng titan v
st chng titan tm CTAB xy ra rt nhanh trong 30 pht u tin v sau tng chm n 36 gi, thi
im c coi t n cn bng hp ph. Ti thi im ban u cc trung tm hot ng trn b mt ca
vt liu hp ph cn trng, s hp ph xy ra rt nhanh, sau thi gian s lng cc trung tm hot ng
gim v vy tc hp ph ph thuc nhiu hn vo tc chuyn dch ca cc ion Cu2+ t pha th tch
n cc trung tm hot ng cn li. Cc s liu thc nghim cho thy rng vt liu 5,0 Ti-PICL l vt
liu hp ph tt nht, trong s cc vt liu ny iu ny cng ph hp vi cc d kin phn tch vt l
cho thy vt liu 5,0 Ti-PICL c din tch b mt ln nht (164,12 m2/g). Khi tm CTAB ln cc vt liu
ny, kh nng hp ph cc kim loi nng ca cc vt liu ny gim xung. T s liu thc nghim,
chng ti thy kh nng hp ph ca cc vt liu st chng nhm tm CTAB gim t vt liu 2,5 TiPICL-CTAB xung n vt liu 10,0 Ti-PICL-CTAB. iu ny c th c gii thch l do khi tm
CTAB ln cc vt liu st chng nhm, cc lp st c chng bi cc phn t CTAB, vai tr ca cc
ct chng oxit kim loi khng cn tc dng trong qu trnh chng. Do , t l ct chng cng tng th
din tch b mt trng cng gim, kh nng hp ph gim.
Bng 3.12: Ti trng hp ph ion Cu2+ cn bng (qcb) ca cc vt liu st chng titan v st chng titan
bin tnh bi CTAB thu c ti cc gi tr pH khc nhau (n v mg/g).
Gi
tr pH

MontNa

Organoclay

2,5TiPICL

5,0TiPICL

7,5TiPICL

10TiPICL

2,5
3,5
5,0

11,1
12,3
13,7

13,4
14,2
15,5

22,4
34,6
40,4

31,5
35,8
43,1

29,7
34,9
37,7

22,1
32,0
36,3

2,5TiPICLCTAB
23,1
30,5
34,9

5,0TiPICLCTAB
21,8
29,9
32,8

7,5TiPICLCTAB
20,7
28,5
32,2

10TiPICLCTAB
19,3
27,6
31,5

3.3.2. Hp ph methyl orange (Me2N-C6H4-N=N-C6H4-SO3-Na+)

Tnh cht hp ph ca methyl orange trn cc vt liu c thc hin ti pH = 7,0. Do b mt st
mang in tch m nn cc vt liu iu ch c c bin tnh bng CTAB ci thin kh nng hp
ph ca chng. Sau khi c bin tnh bng CTAB, kh nng hp ph ca st hu c (organo-clay) i
vi methyl orange ci thin khng ng k trong khi kh nng hp ph ca cc vt liu x Al-PICLCTAB (vi x = 5,0; 7,5 v 10,0) tng ln rt nhanh. Trong , kh nng hp ph ca vt liu 7,5 AlPICL-CTAB v 10,0 Al-PICL-CTAB l cao nht. iu ny c th c l do trong cc vt liu 7,5 AlPICL-CTAB v 10,0 Al-PICL-CTAB, s c mt ca cc ct chng (Al2O3) nh hng ng k n s
hp ph methyl orange. S c mt ca CTAB nh hng yu hn n tnh cht hp ph ca vt liu.
iu ny c th c chng minh bng kt qu hp ph ca methyl orange trn organoclay thp hn
trn cc vt liu st chng nhm.

20

Hnh 3.40: S thay i hm lng hp ph ca Cu2+ hp ph trn 1 n v vt liu theo

thi gian ti cc pH khc nhau.
Kt qu ny cng tng t i vi cc vt liu st chng titan, st chng titan a du, st chng
st v st chng st a du. T hnh 3.41, chng ta c th thy kh nng hp ph ca st chng titan v
st chng titan a du ln lt cao hn st chng nhm v st chng nhm a du. Tng t nh vy,
kh nng hp ph vi methyl orange ca st chng st v st chng st a du ln lt cao hn st chng
titan v st chng titan a du. iu ny c th c gii thch l do qu trnh hnh thnh cc ct chng
polyoxocation, cc polyoxocation ca nhm gm c 13 nguyn t nhm trong khi cc polyoxocation ca
titan l 8 nguyn t titan v polyoxocation ca st ch c 3 nguyn t st. Do , vi cng t l mol ca
cc kim loi th s lng ct chng polyoxocation s tng t nhm, titan v cao nht l st.
3.3.3. Kt qu hp ph metylene blue
Hnh 3.42 trnh by nh hng ca thi gian hp ph n kh nng hp ph methylene blue ca
cc vt liu st chng nhm, st chng nhm a du, st chng titan, st chng titan a du, st chng
st v st chng st a du.
Kh nng hp ph phm mu ca cc loi vt liu trn u tng theo thi gian x l. Tuy nhin,
kh nng hp ph tng rt nhanh trong 10 pht u, sau tng chm trong 90 pht tip theo v t n
trng thi cn bng. Hin tng ny c th c gii thch l do qu trnh hp ph ph thuc ch yu
vo qu trnh khuch tn ca cc phn t methylene blue qua cc l xp vo b mt trong ca cc vt
liu hp ph. Hn na, do cc vt liu st v st chng c b mt mang in tch m methylene blue l
loi phm mu cation nn tng tc xy ra y chnh l tng tc tnh in do qu trnh hp ph
xy ra rt nhanh.

21

Hnh 3.41: S thay i hm lng hp ph ca metyl orange trn 1 n v vt liu hp ph theo

thi gian, ti pH = 7, tc lc 300 vng/pht.
Khi so snh kh nng hp ph ca cc vt liu c bit cc vt liu lai, st chng a du, MePICL-CTAB (Me = Al, Fe, Ti) i vi cc cht mu hu c th lng cht b hp ph nhiu hn rt
nhiu, c th l do trong vt liu hp ph lai cha CTAB. Mt phn t c 4 nhm ankyl to nn mi
trng hu c ha tan cc cht mu hu c cation (methylene blue) mnh hn so vi mu hu c anion
(methyl orange). chnh l do b mt st hay st chng, chnh yu t ny to iu kin cho cht mu
hu c cation b hp ph nhiu hn so vi mu anion.
Bn cnh c th thy s hp ph cc hp cht hu c t trng thi cn bng xy ra nhanh
hn so vi s hp ph cc vt liu i vi cation trong 60 pht so vi 120 pht. T cc kt qu ny c
th m ra hng vt liu lai, st chng a du c th dng cho qu trnh x l nc, ng thi c cha
cc ion kim loi nng v cc hp cht mu hu c. cng chnh l u im ni bt ca loi vt liu lai
ny.
Sau khi tin hnh x l nc thi nhim cc cht v c, hu c, vic thu hi vt liu hp ph
ban u l mt vn c ngha kinh t ht sc cp thit. Chng ti xut m hnh thu hi cht hp
ph sau khi tch loi cc cht nhim hu c ra khi ngun nc nh trn hnh 3.44. Theo , sau khi
tch loi cc cht hu c ra khi ngun nc thi nhim, chng ti t chy cht hp ph c cha cc
cht nhim hu c trong mi trng khng kh. Cc cht hu c b t chy hon ton to thnh CO 2,
H2O v HX (hnh 3.43), chng ti c th thu c st chng ban u.

22

Hnh 3.42: S thay i hm lng hp ph ca methylene blue trn 1 n v vt liu hp ph

theo thi gian, ti pH = 7, tc lc 300 vng/pht.

Hnh 3.43: S hp ph tch cc hp cht hu c v thu hi cht hp ph - st chng v st chng a

du.

23

KT LUN
Vi mc ch nghin cu, ch to vt liu hp ph a chc nng cho qu trnh x l nc b
nhim cc cht hu c v cc ion kim loi nng t cc ngun nguyn liu r tin, sn c Vit Nam nh
bentonite, chng ti nghin cu mt cch h thng iu ch v c trng cc vt liu hp ph lai v
c - hu c, l cc bentonite Di Linh chng a du v rt ra mt s kt lun di y:
1. Vic tinh ch bentonite Di Linh bng phng php ra vi nc ct thu c bentonite c
hm lng montmorillonite cao hn. Sau , cn phi a bentonite Di Linh thun natri bng cch trao
i bentonite thu c vi NaCl thu c Bent-Na (Mont-Na) lm nguyn liu u cho cc qu trnh
ch to cc vt liu hp ph lai v c hu c.
2. Vic tng hp vt liu xp vi mao qun l thnh cng trong cc iu kin: Cc pillar l ion
Keggin (Al137+) v cc ion tng t ion Keggin ca st v titan theo cc t l khc nhau. Cc bentonite
Di Linh chng thu c din tch b mt ca vt liu st chng tng ln ng k so vi cc vt liu ban
u (MONT-Na 40,09 m2/g, 7,5Al-PICL 203,30 m2/g, 5,0 Fe-PICL 154,04 m2/g, 5,0 Ti-PICL 164,12
m2/g).
3. Thu c cc vt liu hp ph lai v c hu c bng cch a CTAB vi cc hm lng
khc nhau vo cc vt liu bentonite Di Linh chng kim loi Al, Fe, Ti bng phng php kh, n gin,
d ch to.
4. Tt c cc vt liu tng hp u c c trng cu trc bng cc phng php vt l hin i
(phng php nhiu x tia X, phng php phn tch nhit vi sai TG-DTA, phng php ph cng
hng t ht nhn Al27-NMR, phng php ph hng ngoi FT-IR, phng php ng nhit hp ph v
gii hp nit, phng php hin vi in t qut v phng php hin vi in t truyn qua). Bng php
o ng nhit hp ph v gii hp nit cho thy, vt liu 7,5 Al-PICL c din tch b mt ln nht trong
s cc vt liu tng hp c. iu ny c th l do qu trnh iu ch ion Keggin, Al137+ rt thnh cng
v t l Al/gam st bng 7,5 mmol Al/gam st l thch hp cho cc lp st tch bit nhau r rt nht. Nu
tng thm t l Al th s lng cc ct chng tng lm cho din tch b mt gim.
5. Kh nng hp ph a nng ca cc vt liu st chng a du cc vt liu lai tng hp c
vi ion kim loi nng Cu2+, vi phm nhum gc cation (metylene blue) v vi phm nhum gc anion
(methyl orange) l rt kh quan trong cc vt liu thu c. 7,5 Al-PICL-CTAB cho kt qu hp ph
Cu2+ cao nht pH = 5,0, vt liu 10,0 Fe-PICL-CTAB cho kt qu hp ph methyl orange tt nht v
vt liu MONT-Na cho kt qu hp ph methylene blue cao nht.
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