MC LC (B sung s trang nh)

M u
Chng 1: TNG QUAN
1.1. nhim mi trng nc Ngun gc v tc hi
1.1.1.Khi nim nhim nc
1.1.2.Ngun gc nhim nc
1.2. nhim mi trng nc bi cc thuc bo v thc vt
1.2.1. Gii thiu qua v cc thuc bo v thc vt
1.2.2. Cc phng php x l
1.3. Xc tc quang ha
1.3.1.Gii thiu chung v xc tc quang ha
1.3.2. Vt liu TiO2 Xc tc quang ha hiu qu
1.3.3. Mt s phng php ch to xc tc u v nhc im
Chng 2: Thc nghim
2.1. Ha cht, dng c
2.2. Dng c v cc thit b th nghim.
2.3. Ch to xc tc:
2.3.1. Ch to vt liu nn (SiO2, Si-C)
2.3.2. Tng hp MCM-41 thun silic
2.4. Ch to vt liu phn tn TiO2/cht nn
2.4.1. Quy trnh tng hp vt liu TiO2/ SiO2
2.4.2. Quy trnh tng hp vt liu TiO2/ MCM-41
2.4.3. Quy trnh tng hp vt liu TiO2/ Si-C
2.5. Cc phng php c trng xc tc v phn tch sn phm (Nu mc ch s
dng, nguyn tc hot ng, tn thit b, model v ni tin hnh xc nh)
2.5.1. Nhiu x Ronghen (XRD)
1

2.5. 2.5.2. Hin vi in t qut (SEM)

3. Phng php ph tn sc nng lng tia X (EDX) [37]
2.5.4. Hp ph v gii hp N2 (BET)
2.6.Phng php thc hin phn ng quang ha vi cc thuc tr su
2.7. Phng php nh gi hiu qu xc tc
Chng 3: KT QU V THO LUN
3.1. Kt qu tng hp vt liu
3.2. Cc kt qu nghin cu c trng
3.3. Kt qu nh gi hot tnh ca cc h xc tc trong phn ng oxi ha quang
ha cc thuc tr su
KT LUN
PH LC

M U
Nc ta l mt nc xut khu hng u cc sn phm nng ng nghip.
t hiu qu cao trong sn xut nng nghip, ng nghip, vic s dng cc
loi thuc tr su, thuc bo v thc phm, ha cht bo qun ngy cng nhiu
gy nn nhng tn hi n mi trng. Trong , tnh trng nhim nc
v ang din ra nhiu ni, c bit l ti cc khu vc c dn c ng c v
nhiu khu nng ng nghip, khu cng nghip ln nh H Ni, Bnh Dng,
TP.H Ch Minh, Cn Th. Bn cnh , cc hot ng sn xut v sinh hot,
y t, ca con ngi cng thi ra mi trng mt lng ln cc cht hu c v
v c c hi rt kh phn hu. Phn ln lng nc thi u khng c qua h
thng x l hoc thu gom n mt nh my x l nc thi chung m thi thng
ra cc ao, h, sng, sui
Ngoi tc hi ca mt s kim loi nng v cc nguyn t c tnh c bn
cht trong mi trng nc nh Thy ngn, Asen, Ch,th phi k n s c
mt ca cc cht nhim hu c c hi trong nc nh cc ha cht bo v thc
vt, cc hp cht c Clo, pht pho, du m, cc ha cht tng hp trong sn xut
cng nghip, cc loi ha cht dt nhum,[1, 2]. Do vic phn tch nh gi
mc nhim nc v x l lm sch cc cht gy nhim trong nc, c
bit l cht thi hu c c hi lun l nhim v hng u ca cc quc gia ni
chung v cc nh khoa hc ni ring.
Vic nghin cu v pht trin cng ngh xc tc quang thay i quan
nim v vic lm sch. iu d on cho s pht trin mt khi nim mi
trong tng lai gn, l khi nim lm sch bng nh sng light cleaning
cleaning with light. Hai yu t quan trng ca light cleaning l ngun UV v cht
xc tc quang.
3

Trong nhng nm gn y vic s dng vt liu cha TiO2 l vt liu oxi

ha quang ha c nghin cu v ng dng rng ri vi mc ch x l cc
cht hu c kh phn hy trong mi trng nc. y l phng php hon ton
c th ng dng ngoi mi trng t nhin v c ch quang ha ny c th dng
nh sng mt tri (ngun UV t nhin) v cc tc nhn oxy khng kh hoc hi
nc oxi ho cc cht hu c trong nc cho sn phm cui cng l CO 2 v
H2O. Nhng nghin cu khoa hc v vt liu cha TiO 2 vi vai tr l mt cht
xc tc quang c bt u hn ba thp k nay t mt pht minh ca hai nh
khoa hc ngi Nht, Fujishima v Honda vo nm 1972 trong vic phn hy
nc bng phng php in ha quang vi cht xc tc TiO 2 [3]. Sau , hng
lot nhng cng trnh khoa hc v vic s dng cht xc tc quang trong vic
phn hy nc to kh hydro v x l nhim mi trng c cng b. Xu
hng mi trn th gii l nng cao kh nng ng dng vt liu cha TiO2, c th
dng nh sng nhn thy hoc nh sng mt tri thay tia UV nhn to. Chnh v
vy, vt liu TiO2 ni chung rt c quan tm nghin cu v ng dng, cng
l l do chng ti chn ti:
Nghin cu tng hp vt liu xc tc quang ha da trn c s TiO2 ng dng
cho x l mt s hp cht hu c c hi trong nc.

Chng 1: TNG QUAN

1.1. nhim mi trng nc Ngun gc v tc hi

1.1.1.Khi nim nhim nc
nhim nc l s thay i theo chiu xu i cc tnh cht vt l ho hc
sinh hc ca nc, vi s xut hin cc cht l th lng, rn lm cho ngun
nc tr nn c hi vi con ngi v sinh vt, lm gim a dng sinh vt
trong nc. Xt v tc lan truyn v quy m nh hng th nhim nc
l vn ng lo ngi hn nhim t.
nhim nc xy ra khi nc b mt chy qua rc thi sinh hot, nc rc
cng nghip, cc cht nhim trn mt t, ri thm xung nc ngm.
Hin chng chu u v nc nh ngha:
" nhim nc l s bin i ni chung do con ngi i vi cht
lng nc, lm nhim bn nc v gy nguy him cho con ngi, cho cng
nghip, nng nghip, nui c, ngh ngi, gii tr, cho ng vt nui v cc loi
hoang d".
Hin tng nhim nc xy ra khi cc loi ho cht c hi, cc loi
vi khun gy bnh, virut, k sinh trng pht sinh t cc ngun thi khc nhau
nh cht thi cng nghip t cc nh my sn xut, cc loi rc thi ca cc
bnh vin, cc loi rc thi sinh hot bnh thng ca con ngi hay ho cht,
thuc tr su, phn bn hu c... s dng trong sn xut nng nghip c y
ra cc ao, h, sng, sui hoc ngm xung nc di t m khng qua x l
hoc vi khi lng qu ln vt qu kh nng t iu chnh v t lm sch
ca cc loi ao, h, sng, sui.
1.1.2. Cc ngun gc gy nhim mi trng nc
Nc b nhim l do s ph dng xy ra ch yu cc khu vc nc
ngt v cc vng ven bin, vng bin khp kn. Do lng mui khong v
hm lng cc cht hu c qu d tha lm cho cc qun th sinh vt trong
nc khng th ng ho c. Kt qu lm cho hm lng xy trong nc
5

gim t ngt, cc kh c tng ln, tng c ca nc, gy suy thoi thy

vc.
1.1.2.1. nhim t nhin:
L do ma,tuyt tan, l lt,gi bo hoc do cc sn phm hot ng
sng ca sinh vt, k c xc cht ca chng.
Cy ci, sinh vt cht i , chng b vi sinh vt phn hy thnh cht hu
c. Mt phn s ngm vo lng t, sau n su vo nc ngm, gy
nhim. hoc theo dng nc ngm ha vo dng ln.
Lt li c th lm nc mt s trong sch, khuy ng nhng cht d
trong h thng cng rnh, mang theo nhiu cht thi c hi t ni rc, v
cun theo cc loi ho cht trc y c ct gi.
Nc lt c th b nhim do ho cht dng trong nng nghip, k
ngh hoc do cc tc nhn c hi cc khu ph thi.
1.1.2.2. nhim nhn to
* T hot ng sn xut nng, ng nghip
Cc hot ng chn nui gia sc: phn, nc tiu gia sc, thc n tha
khng qua x l a vo mi trng v cc hot ng sn xut nng nghip
khc: thuc tr su, phn bn t cc rung la, da, vn cy, rau cha cc
cht ha hc c hi c th gy nhim ngun nc ngm v nc mt.
Trong qu trnh sn xut nng nghip, a s nng dn u s dng thuc
bo v thc vt (BVTV) gp nhiu ln liu khuyn co. Chng nhng th, nng
dn cn s dng c cc loi thuc tr su b cm nh Aldrin, Thiodol,
Monitor... Trong qu trnh bn phn, phun xt thuc, ngi nng dn khng h
trang b bo h lao ng. a s nng dn khng c kho ct gi bo qun
thuc, thuc khi mua v cha s dng c ct gi khp ni, k c gn nh n,
ging sinh hot... a s v chai thuc sau khi s dng xong b vt ngay ra b
rung, s cn li c gom bn ph liu...
6

Nc ta l nc c b bin di v h thng sng ngi, ao h a dng,

thun li cho ngnh nui trng thy hi sn, tuy nhin cng v m vic
nhim ngun nc do cc h nui trng thy sn gy ra khng phi l nh.
Nguyn nhn l do thc n, nc trong h, ao nui lu ngy b phn
hy khng c x l tt m x thng ra sng sui, bin gy nhim ngun
nc. Cc cht thi nui trng thy sn l ngun thc n d tha thi ra b
phn hy, cc cht tn d s dng nh ha cht v thuc khng sinh, vi v cc
loi khong cht.
Bn cnh , cc xng ch bin mi ngy ch bin hng tn thy hi
sn, tuy nhin trong qu trnh ch bin thi ra mi trng ton b lng
nc thi, bao gm c ha cht, cht bo qun. Ngoi ra, nhiu loi thy hi
sn ch ly mt phn, phn cn li vt xung sng, bin lm nc b
nhim, bc mi hi kh chu.
Mt thc trng ang xy ra vi cc c s nui trng thy sn l hin
tng thc n nui trng thy sn gy nhim. Do thiu quy hoch v
thc v mi trng, cc doanh nghip v c nhn, nc ta c ngh nui c
lng trn bin ang pht trin rt mnh. nhim mi trng bin khu vc
ny ang din bin ht sc phc tp.
* T sinh hot:
Nc thi sinh hot (domestic wastewater): l nc thi pht sinh t cc
h gia nh, bnh vin, khch sn, c quan trng hc, cha cc cht thi
trong qu trnh sinh hot, v sinh ca con ngi.
Thnh phn c bn ca nc thi sinh hot l cc cht hu c d b phn
hy sinh hc (cacbohydrat, protein, du m), cht dinh dng (photpho, nit),
cht rn v vi trng.
Nc thi th (municipal wastewater): l loi nc thi to thnh do
s gp chung nc thi sinh hot, nc thi v sinh v nc thi ca cc c s
7

thng mi, cng nghip nh trong khu th. Nc thi th thng c

thu gom vo h thng cng thi thnh ph, th x l chung. Thng
thng cc th c h thng cng thi, khong 70% n 90% tng lng
nc s dng ca th s tr thnh nc thi th v chy vo ng cng.
Nhn chung, thnh phn c bn ca nc thi th cng gn tng t nc thi
sinh hot.
* T cc hot ng cng nghip:
Nc thi cng nghip (industrial wastewater): l nc thi t cc c s
sn xut cng nghip, tiu th cng nghip, giao thng vn ti. Khc vi nc
thi sinh hot hay nc thi th, nc thi cng nghip khng c thnh phn
c bn ging nhau, m ph thuc vo ngnh sn xut cng nghip c th. V
d: nc thi ca cc x nghip ch bin thc phm thng cha lng ln cc
cht hu c; nc thi ca cc x nghip thuc da ngoi cc cht hu c cn c
cc kim loi nng, sulfua,...
1.2. nhim mi trng nc bi cc thuc bo v thc vt
1.2.1. Gii thiu qua v cc thuc bo v thc vt
Thuc bo v thc vt l cc loi ho cht do con ngi sn xut ra tr
su bnh v c di c hi cho cy trng. Cc loi thuc ny c u im l dit su
bnh, c di nhanh, s dng n gin, nn ngy cng c s dng rng ri trong
nng nghip.
Nhm ho cht bo v thc vt(HCBVTV) hu c.
Hin nay c hng trm, thm ch hng ngn cc loi HCBVTV ang
c sn xut v s dng dit su, cn trng, nm mc, dit c. Trong s
phn ln l cc hp cht hu c, chng c chia thnh cc nhm:
Photpho hu c
Clo hu c
8

 Cacbamat
Phenoxyaxetic
Pyrethroid
Hu ht cc cht ny c tnh cao i vi con ngi v ng vt.
Nhiu nht trong s , c bit l cc photpho, clo hu c b phn hu rt
chm trong mi trng, c kh nng tch lu trong c th sinh vt v con
ngi. Nhiu trong s cc HCBVTV l tc nhn gy ung th. TCVN 59421995 quy nh nmg ti a cho php ca tng cc HCBVTV trong nc b
mt l 0,15 mg/l, ring vi DDT l 0,01 mg/l.
1.2.2. Cc phng php x l
Nc cha thuc tr su rt c hi, kh x l bi thnh phn cha cc hp cht
hu c mch vng nhm clo, nhm Photpho kh phn hy sinh hc. Cc phng
php thng dng:
- Phng php phn hy sinh hc.
- Phng php ha hc s dng cc cht oxi ha.
- Phng php hp ph bng cc si than hot tnh hoc cc vt liu xp.
- Phng php dng phn ng quang ha vi vt liu cha TiO 2 phn hy
thuc tr su.
Trn c s tng quan cc ti liu, trong ti ny chng ti nghin cu, ch
to v s dng h vt liu TiO2/SiO2, TiO2/MCM-41, TiO2/Si-C iu ch c
hp ph v x l nhm ln c trong nc.

1.3. Xc tc quang ha
1.3.1.Gii thiu chung v xc tc quang ha
1.3.1.1. Khi nim v xc tc quang [11, 12, 13, 14, 15]
Cht xc tc l cht tham gia vo cc qu trnh trung gian v lm thay i
nng lng hot ha ca cc qu trnh, dn n lm thay i tc phn ng.
Trong thc t, ngi ta dng nhiu loi xc tc khc nhau nh: xc tc nhit, xc
tc axit-baz, xc tc oxi ha kh, xc tc enzim Trong xc tc quang l
mt loi xc tc c bit, c nhiu nh khoa hc trn th gii quan tm nghin
cu.
Thut ng xc tc quang c dng t nhng nm 1920 m t cc
phn ng c thc y bi s tham gia ng thi ca nh sng v cht xc tc.
Vo gia nm 1920, cht bn dn ZnO c s dng lm cht nhy sng trong
phn ng quang ha phn hy cc hp cht hu c v v c. Ngay sau TiO 2
cng c nghin cu v c im phn hy quang ny. Hu ht cc nghin
cu trong lnh vc ha quang bn dn din ra vo nhng nm 1960, dn n vic
ra i pin ha in quang s dng TiO 2 v Pt lm in cc thc hin qu trnh
phn chia nc, vo u nhng nm 1970. u nhng nm 1980, TiO 2 c s
dng ln u tin xc tc cho cc phn ng quang phn hy cc hp cht hu c.
T , cc nghin cu trong lnh vc xc tc quang ch yu tp trung vo lnh
vc oxi ha cc hp cht hu c trong mi trng nc v tiu dit cc loi vi
khun, hp cht hu c d bay hi trong mi trng kh, ng dng trong x l
mi trng.
Cho ti nay, nhiu cht bn dn c hot tnh xc tc quang c nghin
cu nh: TiO2 (nng lng vng cm bng 3,2 eV); SrTiO 3 (3,4 eV), Fe2O3 (2,2
eV); CdS (2,5 eV); WO3 (2,8 eV); ZnS (3,6 eV); FeTiO3 (2,8 eV); ZrO2 (5 eV);
10

V2O5 (2,8 eV); Nb2O5 (3,4 eV); SnO2 (3,5 eV)...[15]. Trong TiO2 c nghin
cu v s dng nhiu nht v n c cc tnh nng c bit nh nng lng vng
cm trung bnh, khng c, din tch b mt ring cao, gi thnh r, c kh nng
ti ch, hot tnh quang ha cao, bn ha hc v quang ha...Hnh 1 m t v tr
b nng lng vng dn v vng ha tr ca mt s cht bn dn thng thng,
so snh vi mc nng lng trong chn khng v th oxi ha kh chun ca cp
hydro.

Hnh 1. V tr b nng lng vng dn v vng ha tr ca mt s cht bn dn

thng thng, so snh vi mc nng lng trong chn khng v th oxi ha kh
chun ca cp hydro.
1.3.1.2.Xc tc quang trn cht bn dn [6, 9, 16, 17]
* C ch
Xt v kh nng dn in, cc vt liu rn thng c chia thnh cht dn
in, bn dn v cht cch in. Nguyn nhn ca s khc nhau v tnh dn in
l do chng khc nhau v cu trc vng nng lng. kim loi, cc mc nng
lng lin tc, cc electron ha tr d dng b kch thch thnh cc electron dn.
cht bn dn v cht cch in, vng ha tr v vng dn c cch nhau mt
vng trng, khng c mc nng lng no. Vng nng lng trng ny c gi
11

l vng cm. Khi b kch thch vi nng lng thch hp, cc electron trn vng
ha tr c th nhy ln vng dn v hnh thnh mt l trng trn vng ha tr. Cp
electron dn trn vng dn v l trng trn vng ha tr l ht ti in chnh ca
cht bn dn.
Trong xc tc quang, khi cht bn dn b kch thch bi mt photon c nng
lng ln hn nng lng vng cm th mt cp electron l trng c hnh
thnh. Thi gian sng ca l trng v electron dn l rt nh, c nano giy. Sau
khi hnh thnh, cp electron - l trng c th tri qua mt s qu trnh nh: ti
hp sinh ra nhit, l trng v electron di chuyn n b mt v tng tc vi cc
cht cho v cht nhn electron. Trong cc qu trnh trn th qu trnh ti hp lm
cho hiu sut ca qu trnh xc tc quang gim. Qu trnh cho nhn electron trn
b mt cht bn dn s hiu qu hn nu cc tiu phn v c hoc hu c c
hp ph sn trn b mt. Xc sut v tc ca qu trnh oxi ha v kh ca cc
electron v l trng ph thuc vo v tr b vng dn, vng ha tr v th oxi ha
kh ca tiu phn hp ph. Hnh 2 m t cc qu trnh din ra khi cc ht bn dn
c chiu sng vi bc sng thch hp:

12

Hnh 2. Cc qu trnh din ra trong ht bn dn khi b chiu x vi bc sng

thch hp.
1: S kch thch vng cm.
2: S ti hp electron v l trng trong khi.
3: S ti hp electron v l trng trn b mt.
4: S di chuyn electron trong khi.
5: Electron di chuyn ti b mt v tng tc vi cht nhn (acceptor).
6: L trng di chuyn ti b mt v tng tc vi cht cho (donor).
Mt s phn ng xy ra khi c s to thnh electron quang sinh v l trng
quang sinh khi c mt nc v oxy:
Photocat + h h+ + e.
H2O + h+ OH* + H+
2OH. + 2h* *O2. + 2H+
2H+ + e. H2
*

O2. + H+ HO2*

HO2* O2 + H2O2
H2O2 + *O2. *OH + OH. + O2
* Cc qu trnh to ra gc hydroxyl OH* [18]
Do gc hydroxyl OH* c kh nng oxi ha rt mnh, tc phn ng oxi
ha rt nhanh v khng chn la khi phn ng vi cc hp cht khc nhau, nhiu
cng trnh nghin cu trong nhiu nm qua l tm kim cc to ra gc OH* trn
c s cc tc nhn oxi ha thng thng nh hydrogen peroxide thng qua phn
ng ha hc (H2O2/Fe2+, O3/H2O2, O3/xc tc), hay nh nng lng bc x tia
UV (O3/UV, H2O2/UV, O3 + H2O2/UV, TiO2/UV) v cc ngun nng lng cao
(siu m, tia gamma tia X, chm electron). Bng 1 th hin c ch to gc OH*
ca cc qu trnh oxi ha nng cao.
13

Bng 1. C ch to gc OH* ca cc qu trnh oxi ha nng cao

STT

Tc nhn phn

Phn ng c trng

ng
H2O2/Fe2+

H*
H2O2/Fe2+(ion) v Fe3++H2OFe2++H+

H2O2+Fe2+Fe3++OH-+O Fenton (Fenton Process)

H2O2 + Fe2+ Fe3++ OH-

H2O2/Fe3+(phc)

+ OH*
Fe3+(phc)Fe3++(gc

nng

Fenton

(photo-

fenton Process)

photon UV

lng phc)

Quang Fenton bin th

(Modified Photo-Fenton)

H2O2 + Fe2+ Fe3+ (Phc)

photon UV
4

Quang

lng +OH*

nng

Tn qu trnh

+ OH- + OH*
H2O vi anode Fe 1/2O2 + H2O 2OH*

Fenton

(Electrochemical Fenton

nng

lng Nng lng in ha

in

in ha
O3/H2O2

3O2
O3 v cht xc tc 3O3 + H2O2 2OH* + Catozone Process

ha

Process)
H2O2 + 2O3 2OH + Peroxone Process
*

4O2
(Xc tc ng th v d
7

H2O

th)
nng H2O OH*+ H*

lng in ha
8

H2O

nng H2O OH + H

lng siu m
9

H2O

Nng lng in ha
*

Nng lng siu m

(20 - 40 kHz)
nng H2O OH*+ H*
14

Oxi

ha

in

ha

(Electrochemical
Oxidation Process)
Qu trnh siu

(Utrasound process)
Qu trnh bc x nng

lng cao (tia , Nng lng cao

lng cao (Tia , tia X,

tia

chm (1 - 10 MeV)

chm tia electron)

nng H2O2 2OH*

UV/oxi

X,

10

electron)
H2O v

11

lng photon UV ( = 220 nm )

O3 v nng lng O3+H2O2 2OH* + O2

(UV/oxidation Process)
UV/oxi
ha

photon UV

(UV/oxidation Process)

12

( = 253,7 nm )

ha

H2O/O3 v nng O3+H2O2 + H2O 4OH* UV/oxi

lng photon UV

+ O2

ha

(UV/oxidation Process)

( = 253,7 nm )
13

H2O

nng H2O OH*+ H*

lng photon UV Nng lng VUV

chn
14

VUV/oxi

ha

(VUV/oxidation Process)

khng ( < 190 nm )

(VUV)
TiO2 v

nng TiO2e- + h+

lng photon UV

( >187,5 nm )

Quang

xc

tc

bndn(Semiconductor)

* Gc hydroxyl OH* v kh nng oxi ha ca gc hydroxyl [18]

Oxi ha l qu trnh trong electron c chuyn t cht ny sang cht
khc. iu ny to cho ra mt th in cc c biu th bng von (V) trn hiu
th in cc hydro bng 0. Mi cht (tc nhn) oxi ha u c mt th oxi ha
khc nhau v i lng ny dng nh gi tnh oxi ha mnh hay yu khc
nhau ca chng. Kh nng oxi ha c th hin qua th oxi ha v c sp xp
theo th t trong bng 5.
Bng 2. Th oxi ha kh ca mt s tc nhn oxi ha [18]
Tc nhn oxi ha

Th oxi ha, V
15

OH *
O3
H2O2
MnO4Axit HBr
ClO2HClO
HIO
Cl2
Br2
I2

2,8
2,07
1,78
1,68
1,59
1,57
1,49
1,45
1,36
1,09
0,54

Nhng tc nhn oxi ha mnh u l cc gc t do (free radicals), trong

, gc hydroxit OH* l tc nhn oxi ha mnh nht. Th oxi ha ca gc
hydroxit OH* l 2,80, cao nht trong cc tc nhn thng gp, gp 2,05 ln so vi
clo v 1,52 ln so vi ozon.
c tnh ca cc gc t do l trung ha v in trong khi cc ion u mang
in tch dng hay m. Gc t do c to thnh t s tch ra thnh hai phn
bng nhau ca lin kt 2 electron, v d nh quang phn H 2O2 s thu c 2 gc
OH* nh sau:
HO : OH + hv OH* + *OH
Mi gc OH* u khng mang in v c th kt hp tr li thnh HOOH
cng khng mang in. K hiu * cho bit l gc t do v biu th ca 1 electron
l i. Gc t do khng tn ti sn nh cc tc nhn oxi ha thng thng v ch
c sn sinh ti ch v tc thi trong qu trnh phn ng, c thi gian sng rt
ngn, khong vi phn nghn giy nhng lin tc sinh ra trong qu trnh phn
ng.

16

1.3.2. Vt liu TiO2 Xc tc quang ha hiu qu

1.3.2.1. Gii thiu v vt liu TiO2 Ngun gc v cc c tnh l ha
TiO2 tn ti di dng tinh th, c 3 cu trc tinh th chnh l dng rutile,
anatase v brookite. Trong dng anatase v rutile ph bin hn. nhit
t 6000C 11000C th cc dng anatase v brookite s chuyn thnh rutile. Kh
nng xc tc quang tn ti nhiu dng anatase v rutile.
a. Tinh th Rutile thuc h t phng, cu to t cc n v bt din TiO 62gp chung cnh v gc. Pha rutile c rng khe nng lng l 3,05 eV, khi
lng ring 4,2 g/cm3, cu trc tinh th TiO2 dng rutile c trnh by hnh 3.

Hnh 3. Cu trc tinh th ca TiO2, dng rutile.

b. Anatase c cu trc t phng gin di vi cc bt din TiO 62- khng u
n. Anatase c th chuyn thnh dng Rutile cc iu kin nhit thch
hp. Anatase l dng c hot tnh mnh nht trong 3 dng, rng khe nng
lng l 3,25 eV, khi lng ring l 3,84 g/cm 3. Cu trc ca TiO2 dng anatase
c trnh by hnh 4.

17

Hnh 4. Cu trc tinh th ca TiO2, dng anatase.

c. Brookite l mng li cation hnh thoi vi cu trc phc tp hn, thng
him gp v c hot tnh xc tc quang km. Brookite c b rng khe nng lng
3,4 eV, khi lng ring 4,1 g/cm3. Cu trc ca TiO2 dng brookite c trnh
by hnh 5.

Hnh 5. Cu trc tinh th TiO2 , dng brookite.

Cu trc ca rutil v anatase c th c m t bng cc chui bt din
TiO62-. Hai cu trc tinh th ny khc nhau s bin dng ca cc bt din v bi
s sp xp cc chui bt din. Mi ion TiO4+ c bao quanh bi 6 ion O2- ca
hnh bt din. Trong cu trc rutile hnh bt din khng u, hi b bin dng thoi
cn trong cu trc anatase hnh bt din b bin dng ln hn do tnh i xng
km hn.
18

Trong cu trc rutile, mi hnh bt din tip xc vi mi hnh bt din bn

cnh (hai hnh bt din chung cnh oxi v tm hnh bt din chung nh oxi). a
din phi tr ca TiO2 c m t hnh 6.

Hnh 6. a din phi tr ca TiO2.

Do s gn kt a din phi tr khc nhau ca 2 dng th hnh ny dn n s
khc nhau v khi lng ring v c im cu trc tinh th rutile v anatase
c ch ra nh bng 3.
Bng 3. Cc hng s vt l ca TiO2 [6, 8]
Tnh cht
Khong cch Ti-O ()

Dng rutile
1,934/1,980

Dng anatase Dngbrookite

1,949/1,980
-

Khong cch Ti-Ti ()

3,57/2,96

3,79/3,04

a = b = 4,593 a = b = 3,784
Hng s mng ()
c = 2,959
Nng lng vng cm (eV)
Gof (Kcal/mol)

3,0

c = 9,515
3,2

- 212,6

Cc tnh cht vt l ca TiO2 c th hin bi bng 4.

19

- 211,4

a = 5,456
b = 9,182
c = 5.143
-

Bng 4. Mt s tnh cht vt l ca TiO2 dng Anatase v Rutile

TT

Tnh cht vt l

Anatase

Rutile

Cu trc tinh th

T phng

T Phng

Tonc (oC)

1800

1850

Khi lng ring (g/cm3)

3,84

4,20

cng Mohs

5,5-6,0

6,0-7,0

Ch s khc x

2,54

2,75

Hng s in mi

31

114

Nhit dung ring (Cal/mol.oC)

12,96

13,2

Mc nng lng vng cm (eV)

3,25

3,05

Tnh cht ha hc [7]

TiO2 dng c kch thc micromet rt bn v ha hc, khng tan trong cc
axit. Tuy nhin, khi a TiO2 v dng kch thc nanomet, TiO 2 c th tham gia
mt s phn ng vi axit v kim mnh.
Cc dng oxit, hydroxit v cc hp cht ca Ti(IV) u c tnh lng tnh.
1.3.2.2. Kh nng xc tc quang ca TiO2.
Di tc dng ca mt photon c nng lng 3,2eV tng ng vi nh
sng c bc sng khong 387,5 nm (chnh l di bc sng ca UV-A) s xy
ra qu trnh nh sau:
h > 3,2

e-cb + h+vb

TiO2

20

Khi cc l trng quang sinh mang in tch dng (h +VB) xut hin trn vng
ha tr, chng s di chuyn ra b mt ca ht xc tc. Trong mi trng nc s
xy ra nhng phn ng to gc hydroxyl OH* trn b mt ht xc tc nh phn
ng di y:
h+vb + H2O OH* + H+
h+vb + OH- OH*

(*)

Ion OH- li c th tc dng vi h+vb trn vng ha tr to ra thm gc OH*

theo phng trnh (*).
Mt khc, cc e-cb c xu hng ti kt hp vi cc h+vb km theo gii phng
nhit hoc nh sng.
e-cb + h+vb nhit, nh sng

1.3.3. Mt s phng php ch to xc tc u v nhc im

1.3.3.1.Tng hp n TiO2
* Phng php c in [9]
Ngi ta iu ch TiO2 tinh khit bng cch kt ta axit titanic khi cho
NH4OH tc dng ln dung dch TiCl 4 (hoc Ti(SO4)2), ra kt ta, sy kh ri
nung.
TiCl4 + 4NH4OH = Ti(OH)4 + 4NH4Cl
Ti(OH)4 = TiO2 + 2H2O
*Phn hu qung tinh Illmenite
y l phng php u tin c s dng sn xut TiO 2. Nguyn tc
ca phng php l dng H2SO4 m c nhit cao phn hu qung
21

illmenite, chuyn titan v st v dng sunfat ho tan trong dung dch. Sau
mui ca titan s c thy phn v nung to thnh TiO2.
*Phng php tng hp ngn la [27]
TiO2 c sn xut vi qu trnh oxy ha TiCl 4 xy ra trong mt l sol kh
ngn la. Cc ht TiO2 hu ht kt tinh hai dng anatase v rutile. Phn ng
thng c thc hin nhit cao hn 1000 0C thu c sn phm c cht
lng cao.
TiCl4 + O2 = TiO2 + 2Cl2
TiO2 P25 (Degussa) l mt sn phm thng mi c iu ch bng
phng php nhit phn TiCl4 trong ngn la c nhit cao hn 12000C vi s
c mt ca hyro v oxy. TiO2 sau c x l bng dng hi loi b HCl.
1.3.3.2. Cc phng php tng hp h vt liu TiO2 phn tn trn cht mang
* Phng php tm
L phng php ph bin nht, c mt s u im so vi cc phng php
khc l: n gin, lng cc cht thi c hi thp, s dng cc nguyn t hot
ng hiu qu hn. Phng php tm gm cc giai on sau:
- Chn v x l b mt cht rn trc khi tm.
- Tm dung dch cha pha hot tnh ln cht rn v loi b phn dung dch
d.
- X l nhit xc tc (sy, nung)
- Hot ha xc tc.
i vi xc tc TiO2 c th doping cc kim loi pha thm vo h bng
phng php ny.

22

* Phng php sol-gel [29]

Phng php sol-gel do R.Roy xut nm 1956 cho php trn ln cc
cht quy m nguyn t do sn phm thu c c ng nht v tinh
khit cao, b mt ring ln, phn b kch thc ht hp.
S tng hp oxit theo phng php sol-gel c biu din theo s sau:
Dung
dch

sol

Xerogel

gel

Oxide
phc hp

C ch ca phng php ny c cho l din ra theo cc bc sau:

S hnh thnh sol:
u tin cc ion kim loi to phc vi phi t vng cng l axit citric. Trong
qu trnh khuy trn, bay hi dung mi, cc phc n nhn ngng t vi nhau
thnh tp hp phc a nhn. Mng li phc a nhn pht trin thnh cc ht sol
c kch thc micromet. Sol l trng thi phn b d th ng u ca cc ht rn
trong cht lng.
S hnh thnh gel:
Cc ht sol tip tc ln ln, ngng t thnh mng li khng gian ba chiu.
Lc ny, trng thi lng c phn tn ng u trong pha rn.
Bng phng php sol-gel , khng nhng tng hp c oxit siu mn vi
ng nht v tinh khit cao, m cn c th tng hp c cc tinh th c kch
thc c nano, cc pha thy tinh, thy tinh-gm, m nhng phng php nng
chy khng th tng hp c. Do , trong nhng nm gn y phng php
23

sol-gel tr thnh mt trong nhng phng php tng hp oxit quan trng nht
trong lnh vc khoa hc vt liu.
* Phng php ng kt ta
Theo UIPAC, ng kt ta l s kt ta song song ca mt cu t tan bnh
thng vi mt cu t ln (macrocomponent) t cng mt dung dch bng s
hnh thnh cc tinh th hn hp, bng cch hp th, hp ph hay c hc. y l
mt phng php thch hp to nn s phn b ng u cc cu t xc tc. y
cng l mt phng php c s dng rng ri mc d n c mt s bc khng
thun li trong qu trnh xc tc
1.3.4.Phng php hp ph (a ln phn phng php x l thuc tr
su).
Hp ph l s tch ly cht trn b mt phn cch pha. y l phng php
nhit tch cht trong cc cu t xc nh t hn hp lng hoc kh c hp
ph trn b mt cht rn xp.
Ty theo bn cht ca lc tng tc gia cht hp ph v cht b hp ph
m ngi ta chia ra hp ph vt l v hp ph ha hc.
Rt nhiu qu trnh hp ph xy ra ng thi c hai hnh thc hp ph ny.
Hp ph ha hc c coi l trung gian gia hp ph vt l v phn ng ha hc.
Cc cht c gy nhim trong mi trng nc c th c x l bng
phng php hp ph trn cc cht c kh nng hp ph. C rt nhiu loi cht
hp ph, tn ti nhiu dng khc nhau vi cc cu trc khc nhau. Cu trc
mng cht rn c th chia tinh th nh zeolit, graphit; cu trc lp nh cc
khong st, cu trc nh hnh ca mt s oxit kim loi nh: nhm, st, mangan
v cu trc v nh hnhCc cht hp ph thng c din tch b mt ring ln,
xp, c nhiu khe trng to iu kin cho hp ph tt cc cht gy nhim.
24

y l phng php truyn thng dng x l mt s cht c gy nhim mi

trng. Phng php ny c u im cng ngh x l n gin, hiu qu, tc
x l nhanh.
1.3.4. Mt s vt liu nn cha Si
Cng ngh nano l qu trnh tng hp v kim sot cc vt liu kch
thc phn t mt (10-9m). kch thc ny, hot tnh xc tc tng mnh do s
tng cc tm hot ng v cc tnh cht c bit ca vt liu khi kch thc
nano kch thc gn vi phn t cht. Tuy nhin, mt trong nhng kh khn
ca vt liu nano khi lm xc tc l s khng thun li v nhit ng hc. Xu th
co cm thnh cc ht ln rt d xy ra v lm cho vt liu khng cn hot tnh
xc tc. V vy iu quan trng l phi "neo" hoc "gi" cc ht nano ny trn cc
cht mang c hiu ng mao qun hoc c cc hc, rnh, c b mt ring ln c
nh ht nano trnh s co cm ln ln ca ht. Mt s cht mang c s dng
ph bin hin nay l cc vt liu trn c s silic oxit do c tnh b c nhit tt, cc
vt liu polime, .
1.3.4.1. Vt liu silic dioxit SiO2
Silic oxit l mt cht mu trng c im nng chy 1710o
Cc dng tinh th ca SiO2 gm 3 dng chnh: Thch anh, triimit,
cristobalit. Mi dng chnh nh vy cn tn ti di nhiu dng ph:
+Cc dng n tinh: cancedoan, m no, jat(ngc)
+Dng v nh hnh: Thu tinh, thch anh, opal.
Trong t nhin thch anh v iatomite l vt liu silica in hnh. Thch
anh thuc loi khong vt ht sc ph bin. Thch anh t nhin thng l cc tinh
th tng i nh. Tuy nhin ngi ta c th gp nhng tinh th thch anh ln v
pht trin hon ho. quaczit v ct l loi thch anh km tinh khit hn.[2]
25

Oxit silic s dng lm cht nn l SiO 2 v nh hnh c tng hp theo

phng php Sol-Gel do n c din tch b mt tng i ln.
Xt mt phn b mt tinh th hai lp SiO 2 gm c nhng lin kt hp ph yu
vi nc do ht m, m hnh chng chp nhn s thay th Si 4+ trong tinh th bi
nguyn t hiro trong nc v coi b mt c trung ho v hidrat ho hon ton.
C th thy rng cc lin kt SiO trn lp b mt ca silic ixit l khng
nh nhau: xi ca cc lin kt SiOSi khng c cc c tnh cho in t, trong
khi trong cc nhm SiOH th n li l tc nhn cho in t hiu dng. Hai
dng lin kt SiO ny trong silic ixit quy nh mt lot cc tnh cht c
bit ca b mt silic ixit.
Mi dng silica u c cha cc nhm silanol trn b mt v chnh c tnh
lin kt ca nhng nhm ny cng vi cu trc vt l ca b mt silica quyt nh
kh nng hp ph ca silica i vi cc cht tan trong dung dch. Trong s cc
dng silica t nhin v nhn to th silicagel l mt loi vt liu tng hp c ng
dng rt phong ph v a dng..

1.3.4.2. Vt liu mao qun trung bnh MCM-41 thun Si.

Vt liu MCM-41 l i din tiu biu ca h vt liu mao qun trung bnh,
c nhiu ng dng trong nhiu quy trnh cng ngh ho hc [1, 4,22]. MCM-41
c h mao qun ng u kch thc mao qun c 2.5 - 5nm, hnh lc lng, mt
chiu, xp sp xt nhau to nn cu trc t ong, din tch b mt ln nn c p
dng cho cc qu trnh chuyn ho phn t kch thc ln thng gp trong tng
hp hu c m cc vt liu cu trc mao qun nh nh zeolit t ra khng ph
hp. S phn b kch thc l l rt hp ch ra s trt t cao ca cu trc. Do
mao qun ch bao gm MQTB m khng c vi mao qun bn trong thnh nn
dn n s khuch tn mt chiu qua knh mao qun. Chng c din tch b
26

mt ring ln n khong 1000-1200 m2/g. MCM-41 c hnh thnh bng cch

thy nhit silicagel trong s c mt ca cht hot ng b mt, thng l cc
mui amoni bc bn. Hin nay, chng l vt liu ha hn kh nng p dng rng
ri cho nhiu lnh vc: vt liu xc tc, cht hp ph [17, 25]

Hnh 9: Vt liu MCM-41

1.3.4.3. Vt liu silic oxit cha cacbon (Si-C)
Vic a thm cacbon vo cht nn cha silic to nn h vt liu nn SiC c bit n v s dng cch y cha lu [ ], tuy nhin, h vt liu ny
nhanh chng c pht trin bi nhng u im ca n. Bn cnh tnh bn c
hc, bn nhit, kh nng phn tn tt v gi n nh cc vt liu xc tc trong cc
mao qun, trnh gy co cm v khng b tri trong qu trnh phn ng. H cht
nn ny cng khng c tnh axit, nn trnh c cc qu trnh decacboxyl ho,
trnh cc phn ng ngng t,cc phn ng raxemic ha ... Hn na, s c mt
ca thnh phn cacbon to cho vt liu tng tnh hu c, to s tng hp tt
hn trong cc qu trnh phn ng i vi cc hp cht hu c ni chung.
Vi cc qu trnh quang ha, s c mt ca cacbon cng gip cho s hp
th tt hn cc tia UV, lm tng hiu qu xc tc quang [ ]. Chnh v vy, vic
nghin cu v ng dng cht nn Si-C, c bit trong cc qu trnh chuyn ha
cc hp cht hu c, ang ngy cng c ch .

Chng 2: THC NGHIM

27

2.1. Ha cht, dng c

2.1.1. Ha cht (a lm 2 ct cho gn)
- Thy tinh lng cng nghip.
- Tetra etylorthosilicat (TEOS):(C2H5O)4Si (Merck)
- Cht hot ng b mt Cetyl trimethylammonium bromide CTAB (Merck).
- Etanol (Merck)
- Dung dch NH4OH 25%.
- Dung dch TiCl4 c
- Nc ct
- K2Cr2O7
- NH4Cl
- Dung dch H2SO4 c
- HgSO4
- Ag2SO4
- Toluen
- Etylaxetat
- Thuc bo v thc vt nhm ln.

2.1.2. Dng c v cc thit b th nghim.

My o pH: Consort C803 (c)
My o quang (COD)
T sy
My lc, my khuy, my siu m, my ly tm
My lc ht chn khng
28

 May quay ct chn khng

My sc k kh khi ph(GC-MS)
V cc dng c thy tinh trong phng th nghim

2.1.3. Chun b cc dung dch cho th nghim

- Dung dch Ti4+: Ly 160 ml TiCl4 c cho t t vo cc ng 340 ml HCl 3M
thu c 500 ml dung dch Ti(IV) 3M.
- Ha cht cho vic o COD: + Dung dch phn ng: dung dch K 2Cr2O7 0,25N
(cn chnh xc 12,258g K2Cr2O7 sy 105oC trong 2h ri ha tan trong 500 ml
nc ct, thm 167ml dung dch H2SO4 c v 33,3g HgSO4. Lm lnh ri nh
mc ti 1lit).
+ Dung dch axit: Ag2SO4/ H2SO4: Cn 5,5g Ag2SO4 trong mt chai H2SO4 c.
+ Dung dch chun kaliphtalat: sy mt lng kaliphtalat 120 0C. Cn 850mg
kaliphtalat pha nh mc vo bnh 1 lit. Dung dch ny c nng 1mg O 2/lit hay
1000 COD.
+ Cc dung dch dng ng chun trn GC-MS.

2.2. Ch to xc tc: (Thm s cc quy trnh)

2.3.1. Ch to vt liu nn SiO2, Si-C, MCM-41.
2.3.1.1. Quy trnh tng hp vt liu SiO2 xp (M-1, M-2)
Quy trnh 1 (M1):
- Ly 100ml thu tinh lng c d=1,38 g/ml, cha 30%SiO 2. Pha long 5 ln bng
nc ct v khuy u.
- Nh t t NH4Cl 5M vo dung dch trn xut hin kt ta trng thnh dng
mng. Lc kt ta v ra n pH=7 trn my ht chn khng.
29

- Sy mu 100oC trong 5 gi thu c vt liu SiO2 mu trng, k hiu M-1.

Quy trnh 2 (M2):
- Ly 100ml thu tinh lng c d=1,38 g/ml, cha 30%SiO 2. Pha long 5 ln bng
nc ct v khuy u.
- Nh t t dung dch thy tinh lng vo dung dch NH 4Cl 5M xut hin kt ta
trng. Lc kt ta v ra n pH =7 trn my ht chn khng.
- Sy mu 100oC trong 5 gi thu c vt liu SiO2 mu trng, k hiu M-2

2.3.1.2. Tng hp vt liu nn Si-C.(M3)

- Ha tan 5g P123 vo 10 ml nc trong bnh cu, thm vo 10 ml dung dch HCl 6M,
khuy mnh. Sau va khuy va nh t t 10 ml TEOS vo hn hp trn, tip tc
khuy v un hi lu hn hp ny trong 24 gi 40 0C. Sau chuyn hn hp mu
vo autoclave, gi ha mu nhit 1200 C trong 12 gi.
Mu sau khi gi ha c lc thu sn phm kt ta, ra sn phm n pH = 7 ri
sy kh sau nung 4500C trong 4 gi iu kin ym kh thu c cht nn Si-C
xp.
2.3. Phn tn TiO2/cht nn
(Vic phn tn titan i oxit trn c 3 dng cht nn bng quy trnh hon ton ging
nhau nn Chin gp chung li cho rm r, phn lm 2 trng hp: dng tin
cht Ti l TiCl4 3M v ankoxit Ti, trong dng ankoxit Ti cho ht u v nh
hp, trnh s co cm thnh ht ln do c mt ion Cl - . ng thi cng nn thm s
tng hp ca 2 trng hp ny).

2.4.1. Quy trnh tng hp vt liu TiO2/ SiO2

- Pha 5ml dung dch TiCl4 3M , HCl 1M trong 20ml etanol (Merck) c dung
dch A (lng tnh ton sao cho vt liu tng hp thu c cha 10 15% TiO2).

30

- Cho 0,8g SiO2 thm vo 80ml etanol, khuy u bng my khuy t. Thm
dung dch NH3 chnh pH = 10.
- a dung dch A vo buret, nh t t dung dch A vo hn hp ang khuy,
thm tip dung dch NH3 gi n nh pH =10. Nh ht dung dch A sau duy tr
khuy thm 1h, n nh pH = 10.
- Lc kt ta v ra n pH =7 trn my ht chn khng n khi ht clo (th
bng dung dch AgNO3).
- Sy mu 100oC, nung mu 5000C trong 5h thu c bt mn, xp, mu
trng, k hiu l TM1

2.4.2. Quy trnh tng hp vt liu TiO2/ MCM-41

- Pha 5ml dung dch TiCl4 3M , HCl 1M trong 20ml etanol (Merck) c dung
dch A.
- Cho 0,8g MCM-41 thm vo 80ml etanol, khuy u bng my khuy t. Thm
dung dch NH3 chnh pH = 10.
- a dung dch A vo buret, nh t t dung dch A vo hn hp ang khuy,
thm tip dung dch NH3 gi n nh pH =10. Nh ht dung dch A sau duy tr
khuy thm 1h, n nh pH = 10.
- Lc kt ta v ra n pH =7 trn my ht chn khng n khi ht clo (th
bng dung dch AgNO3).
- Sy mu 100oC, nung mu 5000C trong 5h thu c bt mn, xp, mu trng
l 10%TiO2/MCM-41 k hiu TM2.

2.4.3. Quy trnh tng hp vt liu TiO2/ Si-C (tng t nn SiO2), ch khc khi
nung phi thc hin trong iu kin ym kh hoc nung trong dng N2
a tip phn thc hin phn ng ln sau y ri mi ti cc phng php
31

2.5. Cc phng php c trng xc tc v phn tch sn phm

2.5.1. Nhiu x Ronghen (XRD)
Phng php nhiu x Rnghen (XRD) [35,37]
Nguyn tc : Theo l thuyt cu to tinh th, mng li tinh th c cu to
t nhng nguyn t hay ion phn b u n trong khng gian theo mt quy
lut xc nh. Khong cch gia cc nguyn t (hay ion) c vi A o xp x bc
sng tia X. Do khi chm tia X ti p vo b mt tinh th v i vo bn
trong n th mng tinh th ng vai tr mt cch t. Trong mng tinh th cc
nguyn t hay ion c th phn b trn cc mt phng song song nhau. Cc
nguyn t b kch thch bi chm tia X ny s tr thnh nhng tm tn x. Hiu
quang trnh ca hai tn x bt k trn hai mt phng cnh nhau theo iu kin
giao thoa phi bng s nguyn ln di bc sng nh sng.
= 2d(hkl).sin = n
Trong :

d(hkl) : Khong cch gia 2 mt phng song song.

: Gc gia chm tia X vi mt phng phn x.
n : S nguyn.

y l h thc Vulf-Bragg, l phng trnh c bn nghin cu cu trc

mng tinh th. Cn c vo cc i nhiu x trn gin XRD tm c 2, t
tnh c dhkl. M t phn x Bragg t 2 mt phng song song hnh 17.

32

Hnh 12. Phn x Bragg t 2 mt phng song song.

Mi lin quan gia khong cch dhkl v thng s mng l khc nhau i vi
mi cu trc tinh th. Ngi ta c th xc nh kch thc tinh th theo cng thc
Scherrer

d Kch thc tinh th

Bc sng
Gc nhiu x
m rng vch ca mu v rng vch chun tnh theo
Radian
Thc nghim : Cc gin nhiu x tia X ca cc mu nghin cu c
ghi ti Khoa Ha- Trng i Hc Khoa Hc T Nhin- i Hc Quc Gia H
Ni trn my D8- Advance- Bruker- Germany, bc x Cu- K vi bc sng K
= 1,5406 (), cng dng in 30mA, in p 40kV, gc qut 2 t 100 n
700, tc qut 0,030/giy, nhit phng l 25 0C. Hnh 13 chp nh my nhiu
x tia X ti Khoa Ha hc Trng i Hc Khoa Hc T Nhin- i Hc Quc
Gia H Ni.

33

2.5.2. Hin vi in t qut (SEM)

Nguyn tc : Dng chm in t to nh ca mu nghin cu, nh khi
n mn hunh quang c th t phng i theo yu cu. Phng php ny
cho php xc nh hnh dng v kch thc tinh th ca sn phm kt tinh.
Chm in t c to ra t catot (sng in t) qua 2 t quang s c hi
t ln mu nghin cu. Chm in t ny c qut u trn mu. Khi chm in
t p vo mu, trn b mt mu pht ra cc in t pht x th cp. Mi mt
in t pht x ny qua in th gia tc vo phn thu v bin i s bin thnh
mt tn hiu nh sng, chng c khuch i, a vo mng li iu khin to
sng trn mn nh. Mi im trn mu nghin cu cho mt im trn mn
nh. sng ti trn mn nh ty thuc vo lng in th cp pht ra n b
thu v ph thuc tnh trng b mt mu nghin cu. Do c kh nng hi t
chm tia nn chm in t c th i su vo bn trong mu, cho php nghin cu
c phn bn trong ca vt cht.
Thc nghim: nh hin vi in t qut SEM ca cc mu vt liu c ghi
trn my FEI QUANTA 4000, Vin Khoa hc hnh s - B Cng an:
- phng i 4000 ln.

34

Hnh 19. My hin vi in t qut FEI QUANTA 4000

2.5.3. Phng php ph tn sc nng lng tia X (EDX) [37]
Phng php tn sc nng lng tia X, hay phng php tn sc nng
lng l k thut phn tch thnh phn ha hc ca vt rn da vo vic ghi li
gin tia X pht ra t vt rn do tng tc vi cc bc x (m ch yu l chm
in t c nng lng cao trong cc knh hin vi in t). Trong cc ti liu khoa
hc, k thut ny thng c vit tt l EDX hay EDS xut pht t tn gi ting
Anh Energy-dispersive X-ray spectroscopy.
Nguyn tc:

Hinh 20: Nguyn l ca php phn tch EDX.

Anh vi cu trc vt rn c ghi li thng qua vic s dng chm in t c nng
lng cao tng tc vi vt rn. Khi chm in t c nng lng ln c chiu
vo vt rn, n s m xuyn su vo nguyn t vt rn v tng tc vi cc lp
in t bn trong ca nguyn t. Tng tc ny dn n vic to ra cc tia X c
bc sng c trng t l vi nguyn t s (Z) ca nguyn t theo nh lut
Mosley:

35

C ngha l, tn s tia X pht ra l c trng vi nguyn t ca mi cht c mt

trong cht rn. Vic ghi nhn ph tia X pht ra t vt rn s cho thng tin v cc
nguyn t ha hc c mt trong mu ng thi cho cc thng tin v t phn cc
nguyn t ny

ng lm lnh
bng Cu 77K

Khe
mng
ng chun trc

Mu

Hinh 21: S nguyn l ca h ghi nhn tn hiu ph EDX

Tia X pht ra t vt rn (do tng tc vi chm in t) s c nng lng
bin thin trong di rng, s c a n h tn sc v ghi nhn (nng lng)
nh detector dch chuyn (thng l Si, Ge, Li...) c lm lnh bng nit lng,
l mt con chip nh to ra in t th cp do tng tc vi tia X, ri c li vo
mt ant nh. Cng tia X t l vi t phn nguyn t c mt trong mu.
phn gii ca php phn tch ph thuc vo kch c chm in t v nhy ca
detector (vng hot ng tch cc ca detector).
Tuy nhin, EDX t ra khng hiu qu vi cc nguyn t nh (v d B, C...)
v thng xut hin hiu ng chng chp cc nh tia X ca cc nguyn t khc
nhau (mt nguyn t thng pht ra nhiu nh c trng K , K..., v cc nh
ca cc nguyn t khc nhau c th chng chp ln nhau gy kh khn cho phn
tch).
Thc nghim:
Ph tan sc nng lng tia X c o trn my Varian Vista Ax Vin
Khoa hc Vt liu Vin Khoa hc v Cng ngh Vit Nam.

36

2.5.4. Hp ph v gii hp N2 (BET)

Phng php xc nh din tch b mt ca cc vt liu rn da trn gi
thuyt ca Brunauer-Emmett-Teller v phng trnh mang tn tc gi ny
(phng trnh BET (1)). Phng trnh ny c s dng rng ri xc nh din
tch b mt vt liu rn:
1
1
C 1 P

=
+
W [ ( P0 / P ) 1] Wm C Wm C
P0

(1)

Trong : W l khi lng ca kh b hp ph ti p sut tng i P/P0

Wm l khi lng ca kh b hp ph to nn mt n lp trn b
mt vt liu rn.
C l hng s BET, lin quan n nng lng hp ph trong n lp
hp ph u tin v kt qu l gi tr c a ra kh nng tng tc qua li
gia cht hp ph v cht b hp ph.
Thc nghim :
Phng php ng nhit hp phgii hp N2 c ghi trn my
Micromerictics ASAP 2010. Qu trnh hp ph nhit -196 0C (77 K); p sut
770 mmHg; lu lng kh mang 25 ml/pht. Mu c x l chn khng 200 0C
trong 6h trc khi o. ng ng nhit hp ph trong vng P/P 0 nh (0,05
0,35) c ng dng o din tch b mt ring, cn ton b ng ng nhit
hp ph dng xc nh phn b kch thc l xp. ng phn b kch thc
ny c tnh theo cng thc Barrett Joyner Halenda (BJH).
2.6.Phng php thc hin phn ng quang ha vi cc thuc tr su (a ln
sau phn tng hp vt liu )
* Thc nghim x l thuc tr su.:
37

- Ly 0,5g vt liu M2, T2, MCM-41, TM2 lc vi 50ml dung dch thuc tr su
nhm ln 6h.
- Ly 0,5g vt liu c Titan T2, TM2, M3 lc vi 50ml dung dch thuc tr su
nhm ln sau 6h thc hin di nh sng ca n hunh quang. Sau ly mu
ra lc trn phu.
2.7. Phng php nh gi hiu qu xc tc
2.7.1. Phng php o COD
Mc ch:
COD l lng oxi cn thit (tng ng vi cht oxi ha ha hc) cho
qu trnh oxi ha cc cht hu c trong nc thnh CO 2 v H2O. Ni cch
khc COD tng ng vi hm lng cht hu c c th b oxi ha v xc
nh bng vic s dng cht oxi ha mnh nh K2Cr2O7 trong mi trng
H2SO4. COD l mt ch s tiu chun nh gi hm lng cht hu c
trong nc.
Nguyn tc:
Dng K2Cr2O7 l cht oxi ha mnh oxi ha cc hp cht hu c. oxi
ha hon ton cc hp cht hu c mch thng, cc hydrocacbon thm kh b oxi
ha c mt trong nc thi cn cho Ag 2SO4 lm xc tc, 80 90% cht hu c s
c oxi ha. Phn ng oxi ha:
Cht hu c + Cr2O 72 + H+ 2Cr3+ + H2O + CO2
Phn ng c tin hnh vi xc tc Ag 2SO4 trong thi gian ti thiu l 2
gi. Hu ht cc cht hu c b oxi ha bi hn hp si ca K2Cr2O7 v H2SO4.
Nc thi cha ion Cl v cc hp cht khc ca Clo lm nh hng ti
php phn tch: Cr2O72- + 6 Cl- + 14 H+ 2 Cr3+ + 3 Cl- + 7 H2O. Do cn s
dng HgSO4 che ion Cl .
Xy dng ng chun Kaliphtalat:
38

Pha dung dch kaliphtalat vi cc nng 30, 60, 90, 120,180, 240, 300 COD.
Ly 2.5ml mi mu vo ng ph mu ri thm 1.5 ml hn hp phn ng v 3.5
ml thuc th axit vo mu. t cuvet vo l ph mu 148 0C trong 2h. Ly
cuvet ra ngui nhit phng. o mt quang Abs bc sng 605nm .
Bng 2.5: Kt qu o quang xy dng ng chun kaliphtalat
STT
1
2
3
4
5

COD
30
90
120
180
240

Abs
0.014
0.028
0.036
0.065
0.073

0.1

y = 0.0003x + 0.0023
R2 = 0.9958

0.09
0.08

Abs

0.07
0.06
0.05
0.04
0.03
0.02
0.01
0
0

50

100

150

200

250

300

350

COD

Hinh 2.5: ng chun COD ca kaliphtalat

2.7.2 Phng php nh gi GC_MS.
2.7.2.1.Phng php sc k kh
Phng php sc k kh s dng ct mao qun c nh gi l phng
php c nhy cao v c s dng rng ri trong phn tch. Di y l gii
thiu chung v cc nh gi v phng php sc k kh:
Cc thng s k thut ca cc b phn trong thit b sc k kh c th khc
nhau i vi mi hng v mi thi im sn xut khc nhau. Tuy nhin nguyn l
39

cu to chung ca mt thit b GC u bao gm cc b phn chnh c m t

nh sau:

Trong , hai b phn quan trng nht ca GC l ct tch v detect (b

phn d nhn tn hiu).
* Nguyn tc hot ng chung
Tng t nh nh sc k lp mng v cc phng php sc k khc, sc
k kh hn hp cc cht c tch ra trn c s s khc nhau v i lc gia chng
vi pha ng v pha tnh. Tuy nhin khc vi sc k lp mng, sc k kh qu
trnh tch din ra trn mt ct tch bng thy tinh hoc kim loi c cha pha tnh
c iu chnh nhit thch hp trong mt l iu nhit. Thay cho h dung
mi, pha ng trong sc k kh l dng kh gi l kh mang. Khi cc cht khc
nhau c bm vo GC chng s b ha hi b phn Inlet, sau b dng kh
mang y vo ct tch, ti y xy ra qu trnh tch cc cht ra khi nhau sau
tng cu t trong hn hp s n b phn d tm cn gi l detect, b phn d
tm d theo bt c c ch no, cc tn hiu ca cht u th hin di dng pic,
tng hp tt c cc pic ca tng cu t trong hn hp c gi l sc k . Thi
gian t lc bm mu n khi t cc i pic gi l thi gian lu, i lng ny
c trng cho mt cht nht nh v thng nh tnh cht . Din tch hoc

40

chiu cao ca pic t l thun vi lng cht c tch v dng tnh ton a ra
kt qu nh lng.
* Kh mang
Cc kh mang thng dng cho sc k kh bao gm: Heli, nit, hydro,
argon tuy nhin vic la chn cn m bo cc yu cu sau:
- tinh khit phi ph hp vi detect v yu cu tch.
- Khng c tng tc vi mu.
- Khng thay i trng thi l hc khi i qua ct, an ton, kinh t.
2.7.2.2. Detect khi ph (MS)
Khi ph l thit b phn tch da trn c s xc nh khi lng phn t
ca cc hp cht ha hc v cc mnh ca chng bng vic phn tch cc ion
phn t v cc mnh theo t s gia khi lng v in tch (m/z) ca chng. Cc
ion c th to ra bng cch thm hay bt in tch ca chng, cc ion ny c
tch theo t s m/z v pht hin, t c th cho cc thng tin v khi lng
hoc cu trc phn t ca hp cht. C nhiu k thut ion ha, nhng k thut ion
ha bng va chm in t (electron impact) l ph bin hn c. Qu trnh ion ha
c thc hin bi s va chm gia phn t cht phn tch vi dng in t c
nng lng cao (70eV). Qu trnh ny hu nh ch to ra cc ion dng (M + e M+ + 2e-), sau M+ s b b gy thnh cc mnh ion c khi lng nh hn.
Cc ion c thu li v c dn vo b phn tch khi.
C 6 loi thit b phn tch khi lng thng dng l: T cc, thit b t,
phn tch thi gian bay, phn tch phn x electron thi gian bay, cc by ion t
cc v cng hng gia tc ion-chuyn ha Fourier. Nhng thng dng nht l
thit b t cc hoc by ion.
Cc ion to thnh, sau khi tch ra c nhn dng bng detect, thng l
b nhn in t loi chui dynod, c s dng m cc ion, hnh thnh khi
ph. Ion t b phn phn tch khi va chm vo b mt bn dn ca detect gii
41

phng cc in t, qu trnh xy ra lin tc s nhn nn thnh dng thc in t

lm cho h s khuch i c th tng ti hng triu ln.
Trong MSD d liu c th thu c bng 2 cch, qut ton b cc ion
(TIC) hoc ch la chn mt s ion c bn, c trng qut (SIM). Ch TIC
dng nh tnh cc cht cha bit, do mt mt thi gian nht nh qut ton
b cc ion nn nhy ca ch ny thp. Ngc li, ch SIM vi s ion
cn qut t, tc qut nhanh hn v nhy c ci thin nhiu, ngi ta
thng dng ch SIM nh lng mu (LOD ch SIM thng nh hn
ch TIC khong 100 ln). MS cho nhy c phn tch nh tnh v nh
lng c ppb nn rt tt trong vic phn tch lng vt
* Phn tch nh tnh, nh lng.
Nguyn tc ca phn tch nh tnh l da vo mt yu t c trng ca tn
hiu tng ng vi mi cht nhn din. Trong sc k kh, ngi ta s dng i
lng c trng l thi gian lu (t R) ca cu t nhn din, bng cch so snh
thi gian lu ca cu t vi thi gian lu ca mu chun tng ng.
Vic nh lng mt cu t trn sc k kh phi m bo yu cu l cu t
c tch hon ton khi cc cu t khc trong hn hp. Vic nhn bit tt c
cc cu t quan trng cn c xc nhn nhm mc ch trn c s chng ta
tra cu nhng h s hiu chnh tng ng t cc ti liu tham kho hoc sch tra
cu chuyn dng. Ngi ta cng c th xc nh c cc h s hiu chnh bng
thc nghim, nu cc cu t cn quan tm tinh khit.
Trong sc k kh c hai phng php thng c s dng nh lng
mu l: Phng php ngoi chun v phng php ni chun.
- Nguyn tc ca phng php ngoi chun l so snh trc tip ln ca
cc tn hiu (din tch hoc chiu cao pic) trong mu cha bit vi mu chun ca
cht , phng php ny i hi qu trnh chun b mu phn tch v mu chun
42

phi chnh xc, th tch cc ln bm mu phi ging nhau, ni chung n i hi

phi c lp li tt trong cc ln phn tch, nu khng s mc sai s.
- Phng php ni chun da trn s so snh t l tn hiu ca cht cn
phn tch vi mt cht c tnh cht tng t i vi thit b nh cht cn phn
tch m khng gy nh hng n tn hiu ca cht cn phn tch, cht ny c
gi l cht ni chun. Hin nay trn th gii thng dng ngay cht cn phn tch
nhng thay ton b hoc mt s nguyn t hydro bng nguyn t dtri v s
dng cht ny lm cht ni chun. Cht ni chun c a vo mu chun v
mu phn tch mt lng nh nhau nng bit. Nh vy khi xy dng
ng chun, th mt trc s l nng ca cht phn tch, trc kia l t l chiu
cao hoc t l din tch pic gia mu phn tch v mu ni chun.
i vi thit b GC-MS, ngoi vic da vo thi gian lu ca pic th vic nh
tnh v nh lng da trn cng ca cc mnh c trng trong qu trnh bn
ph mu phn tch.
2.7.2.3. iu kin phn tch trn GC-MS:
- Ch MS: fulscan. Khong m/z: 50-550.
- Kh mang heli, tc dng 1,2 ml/pht.
- Nhit bung bm mu: 270oC.
- Chng trnh nhit l sc k: 50 oC (gi 1pht), tng 15oC/pht n
1000C(gi 3pht), tng 5oC/pht n 270oC. Tng thi gian chng trnh sc k l
41,33 pht.
2.7.2.4.Xy dng ng chun trn GC-MS (Phn gii thiu v dimethroat
v cc dung dch li, cn kt qu sc k v din gii a sang phn kt
qu tho lun v y cng l ng gp v mt phng php phn tch).
- Mu i din nhm ln Dimethoat:
43

Dimethoate

Cng thc phn t

C 5 H 12 NO PS 3 2

Mol khi lng

229,26 g / mol

Xut hin

Cht rn kt tinh mu trng xm

Mt

1,3 g / cm 3, rn

im nng chy

43-45 C (316-318 K)

im si

117 C (390 K) ti 10 Pa

ha tan trong nc

2,5 g/100 ml

44

- Cc dung dch chun Dimethoat: 40ppm; 100ppm;150ppm; 250ppm; 400ppm

c phn tch trn thit b GC-MS, da trn kt qu phn tch xy dng c
ng chun ngoi chun trn thit b GC_MS BRUKER(M) ti Trung tm
gim nh Ma ty Vin Khoa hc hnh s - B cng an:

Sc mu chun Dimethoat trn GC-MS:

45

T IC ;

0 ,8

d im e th o a t 9 - 2 1 - 2 0 1 2 p 7 - c 5 4 . x m s ;

F ilte r e d

300

MCps

250

23.260 min

Dimethoat

350

1A

200

150

100

50

0
5

10

15

20

46

25

30

m in u te s

S e a rc h

2 3 .2 8 2 m in , S c a n : 3 0 3 4 , M e rg e d

8 7 .0

100%

75%
9 3 .0

50%

1 2 5 .0
5 8 .1

25%
5 6 .1

1 4 3 .0

0%
M a tc h
100%

C A S N o . 6 0 -5 1 -5 , D im e th o a te
8 7 .0
NH

S
75%

O
9 3 .0
50%

25%
4 7 .0
1 4 3 .0

2 2 9 .0

0%
0
100
R .M a tc h : 8 5 6 , F .M a tc h : 8 2 2

200

300

- Thi gian lu: 23,2pht

- Cc mnh ion c trng: 87,93,125,47,58
- S phn mnh:
- ng chun nh lng Dimethoat:
47

400

500

m /z

2.7.2.5. Kho st v tnh ton hiu sut chit tch Dimethoat ra khi mi
trng nc (Ha cht v cch tin hnh li phn Thc nghim, cn kt
qu a sang phn tho lun kt qu ).
- Chun b dung dch Dimethoat 500ppm.
- Kho st dung mi chit: Etylaxetat, Toluen:
Cch lm: Ly vo ng nghim c lp xoy10ml dung dch mu phn tch,
chit bng 10ml dung mi Etylaxetat(hoc Toluen). a vo my lc xoy 30
pht, phn lp trong 10 pht, ly phn dung mi. Qu trnh chit lp li 3 ln,
gp ton b dch chit vo bnh chuyn dng a vo thit b quay ct chn
48

khng 50oc c cn, thu c sn phm chit Dimethoat ra khi mi trng

nc. Thm vo sn phm chit 5ml dung mi(bng th tch ban u), a vo
my siu m ha tan hon ton, phn tch trn thit b GC-MS vi iu kin
phn tch chn.
- Tnh ton hiu sut chit: (a vo kt qu v tho lun)
Th tch ban u trc khi chit l 10ml, nng u l 500ppm; th tch
sau em i phn tch l 5ml. Nh vy, nng thc sau khi chit bng nng
kt qu phn tch trn GC-MS.
Sc v kt qu tnh nng ca mu cha x l chit bng dung mi
Etylaxetat trn GC-MS nh sau:

Tnh ton hiu sut chit:

49

Nng ban
u (ppm)

Dung mi
chit

500

Etylaxetat

Kt qu nh
lng(ppm)

Hiu sut chit

78,5%

50

Sc v kt qu tnh nng ca mu cha x l chit bng dung mi Toluen

trn GC-MS:

51

Chng 3: KT QU V THO LUN

3.1. Kt qu tng hp vt liu.
Cc mu vt liu c tng hp theo phng php trnh by trong phn thc
nghim (chng II). Cc mu vt liu u c dng mu trng, xp vi cc thnh
Ktrnh
hiuby
mutrong
Cch
phn c
bngtng
3.1.hp
M1
M2
M3
M4
T2
TM2
TM4

SiO2

TiO2

(% khi lng) (% khi lng)

SiO2 quy trnh 1
100
0
SiO2 quy trnh 2
100
0
MCM-41
100
0
Si-C
10%TiO2/ SiO2 52
10%TiO2/ MCM41
10%TiO2/ Si-C

100
90
90

0
10
10

90

10

Bng 3.1: Cc mu vt liu tng hp c

K hiu mu
M1
M2
M3

Cch tng hp

SiO2

TiO2

(% khi lng) (% khi lng)

SiO2 quy trnh 1
100
0
SiO2 quy trnh 2
100
0
MCM-41
100
0

M4
T2
TM2

Si-C
10%TiO2/ SiO2
10%TiO2/ MCM-

100
90
90

0
10
10

TM4

41
10%TiO2/ Si-C

90

10

Cc mu vt liu ny c c trng bng cc k thut XRD, SEM,EDX,

BET v nh gi kh nng hp ph cc cht c hi trong nc theo cc phng
php trnh by phn thc nghim.

3.1.2. Nghin cu c trng cc mu vt liu bng k thut XRD

Phng php XRD thng c s dng xc nh cu trc cng nh
trng thi n lp b mt ca xc tc. C rt nhiu oxit kim loi cng nh kim
loi c th c phn tn trn b mt ca cht mang dng n lp b mt. Khi
chng s tn ti trng thi phn tn cao hoc trng thi v nh hnh. Khi
chuyn sang trng thi a lp b mt, trn b mt xc tc s xut hin cc tinh th
ca oxit kim loi hay kim loi hot ng. Do trn ph XRD s xut hin cc
pic c trng.

53

Gin nhiu x Rnghen ca mu vt liu c th hin trong cc hnh

sau y:
Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 1

2000
1900
1800
1700
1600
1500
1400

Lin (Cps)

1300
1200
1100
1000
900
800
700
600
500
400
300
200
100
0
0.5

10

2-Theta - Scale
File: Duong K53TT mau 1.raw - Type: Locked Coupled - Start: 0.500 - End: 10.004 - Step: 0.008 - Step time: 0.8 s - Temp.: 25 C (Room) - Time Started: 2 s - 2-Theta: 0.500 - Theta: 0.250 - Chi: 0.00

Hnh ..: Gin XRD ca mu SiO2 xp

T gin nhiu x Rnghen, nhn thy vt liu SiO 2 tng hp c
dng v nh hnh [hnh 3.1]. y l vt liu c xp cao, din tch b mt
tng i ln thch hp cho vic hp ph hoc lm cht nn. Hnh ... di y l
gin nhiu x tia X ca mu TiO 2/SiO2. Trn gin xut hin cc tn hiu c
trng cho TiO2 dng anatas ti cc gc 2 = 25.30, 370, 380, 38.50, 480, 540, 550,
62.50...

54

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 3

d=3.515

400

d=1.362

d=1.493
d=1.480

d=1.699

d=1.892

d=1.666

d=2.433

100

d=2.378

200

d=2.332

Lin (Cps)

300

0
20

30

40

50

60

70

2-Theta - Scale
File: Duong K53TT mau 3.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 16 s - 2-Theta: 20.000 - Theta: 10.000 - Chi:
01-078-2486 (C) - Anatase, syn - TiO2 - Y: 98.31 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 3.78450 - b 3.78450 - c 9.51430 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) -

Hnh ..: Gin XRD ca mu TiO2/SiO2

Nh vy, TiO2 mang trn nn SiO2 xp ch yu pha anatas, y l dng c
hot tnh cao ha hn s xc tc tt trong cc qu trnh quang ha. Tng t i
vi mu phn tn TiO2 trn nn Si-C, kt qu XRD cng cho thy TiO2 hnh
thnh ch yu pha anatas vi cc tn hiu c trng (Hnh..)

d=3.510

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau 2

400

200

d=1.493

d=1.363

d=1.480

d=1.698
d=2.327

d=2.425

100

d=1.665

d=2.374

d=1.890

Lin (Cps)

300

0
22

30

40

50

60

70

2-Theta - Scale
File: Duong K53TT mau 2.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 16 s - 2-Theta: 20.000 - Theta: 10.000 - Chi:
01-078-2486 (C) - Anatase, syn - TiO2 - Y: 89.09 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 3.78450 - b 3.78450 - c 9.51430 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) -

Hnh ..: Gin XRD ca mu TiO2/Si-C

55

i vi mu MCM-41, trn gin nhiu x XRD thng xut hin cc tn

hiu c trng cho kch thc mao qun trung bnh ng u (cng ln) v
hnh dng hexagonal (cng nh) ti cc gi tr 2 = 2,1-40 [9]. Hnh ......l
gin XRD ca mu TiO2/MCM-41, kt qu cho thy khi mang TiO2 ln v c
bn khng lm bin i cu trc ca MCM-41.

Hnh ........ : Gin XRD ca mu TiO2/MCM-41

Trn gin nhiu x Rownghen (Hnh...........), nh gc 2 =2,20 c
trng cho mao qun trung bnh ng u ca vt liu vn rt r nt. Tuy nhin
kh nng do cc tinh th TiO2 hnh thnh trong mao qun ca vt liu lm cho
mao qun nn lm cho cc nh c trng cho cu trc hexagonal khng cn
r nt na. Mt khc, vng gc rng ca cc mu khng thy xut hin cc tn
hiu nhiu x ca titan oxit dng tinh th (anatas, brockit, rutin) chng t TiO 2
hnh thnh dng kch thc nh (< 4nm) v tn ti trong mao qun ca MCM41 [8, 10, 16].

3.1.3. Phng php hin vi in t qut (SEM)

Hnh ......... l nh hin vi in t qut (SEM) ca cc mu titan oxit phn
tn trn cc cht nn t ngun tin cht Ti l tetraisopropylorthotitanat (TIPOTi)
56

Hnh: nh SEM ca mu TiO2/SiO2 (T2)

Hnh: nh SEM ca mu TiO2/MCM-41 (TM2)

57

Hnh: nh SEM ca mu TiO2/MCM-41 (TM2)

Hnh: nh SEM ca mu TiO2/Si-C

58

Quan st nh chp SEM cho thy cc mu vt liu tng hp c c kch

thc ht tng i ng u, khong 0,1 0,15 m v c xp cao.
Hnh ..... l nh hin vi in t truyn qua ca cc mu vt liu mu titan
oxit phn tn trn cc cht nn t ngun tin cht Ti l TiCl4

Hnh: nh SEM ca mu TiO2/SiO2 (*)

59

Hnh: nh SEM ca mu TiO2/Si-C (*)

Hnh: nh SEM ca mu TiO2/MCM-41 (*)

60

Kt qu cho thy rng vic phn tn TiO 2 t ngun TiCl4 to vt liu c

kch thc ht ln v khng u, kh nng do s c mt ca cc ion Cl - dn n
s kt ta qu nhanh ca Ti(OH)4 nn to ht ln, mt khc s c mt ca ion ny
(do kh ra trit c) nn gy s co cm mnh ca cc ht vt liu trong qu
trnh nung lm tng kch thc ht vt liu thu c.
T nhn thy rng vic s dng ngun ankoxit titan cho vic tng hp
vt liu s tt hn.
3.1.4. Phng php hp ph v gii hp N2
Mt phng php khc thng c s dng phn tch cc vt liu mao
qun trung bnh l phng php hp ph - gii hp ph nit. Kt qu nhn c
c a ra trong bng:
Bng 3.2: Cc thng s vt l ca cc mu vt liu
Mu vt liu
MCM-41
TiO2/MCM-41

SBET (m2/g)
730
590

TiO2/Si-C
TiO2 /SiO2 (M-2)

442
340

Vt(cm3/g)
0,99
0,58

Dp (nm)
5,4
4,3

Trong : SBET l din tch b mt theo phng php BET a im, V t l

tng th tch l rng, Dp l ng knh mao qun
Theo cc kt qu nhn c, mu vt liu MCM-41 tng hp c din tch b
mt kh ln (730m2/g). Sau khi phn tn TiO 2, tng th tch rng ca vt liu
gim t 0,99 cm3/g xung cn 0,58cm3/g chng t c s chim ch ca cc
ht TiO2 trong mao qun. S chim ch ny cng lm cho ng knh mao qun
gim. Mt khc, s hnh thnh ca cc ht kim loi c trng lng phn t ln
(Ti,48) hn so vi Si (28) lm cho din tch b mt gim cn 590m2/g.
Cc mu vt liu TiO2/Si-C v TiO2 /SiO2 (M-2) cng c din tch b mt ring
kh cao, t 442 m2/g (TiO2/Si-C) v 340 m2/g TiO2 /SiO2 (M-2) chng t vt liu
61

tng hp c l kh tt v ha hn mang nhiu hiu qu trong qu trnh hp ph

x l cc cht hu c hu c trong nc.
3.1.5. Phng php ph tn x EDX
Hnh . l gin EDX ca mu vt liu TiO2/MCM-41, TiO2/Si-C v
TiO2/SiO2 (s dng tin cht ankoxit Ti). Trn gin ch thy xut hin cc pic
c trng ca Si, Ti, v O cho thy xc tc tng hp c l sch v khng b ln
cc ion l khc. C khng xut hin trn gin c th do c nguyn t khi nh
nn d b chng chp vi nh khc, mt khc thng thng vi vic s dng nn
chp thng c cha vt liu C nn nh C hay b ln vi ng nn.

001
SiKa

3900
3600
3300
3000
2700
2100

OKa

Counts

2400
1800

TiKa

600

TiKb

900

TiKesc

1200

TiLsum

TiLl TiLa

1500

300
0
0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

keV

ZAF Method Standardless Quantitative Analysis

Fitting Coefficient : 0.2589
Element

(keV)

Mass%

Error%

Atom%

O K

0.525

55.40

0.37

69.36

54.7951

Si K

1.739

40.65

0.17

28.99

41.1431

Ti K

4.508

3.95

0.33

1.65

4.0619

Total

100.00

100.00

62

Compound

Mass%

Cation

Hnh.Gin EDX ca mu vt liu TiO2/MCM-41

SiKa

004
3600
3300
3000
2700
2100

OKa

Counts

2400
1800

TiKb

TiKa

600

TiKesc

900

TiLsum

1200

TiLl TiLa

1500

300
0
0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

keV

ZAF Method Standardless Quantitative Analysis

Fitting Coefficient : 0.2455
Element

(keV)

Mass%

Error%

Atom%

O K

0.525

50.17

0.47

63.99

49.5252

Si K

1.739

49.17

0.21

35.72

49.8287

Ti K*

4.508

0.66

0.43

0.28

0.6461

Total

100.00

Compound

100.00

Hnh.Gin EDX ca mu vt liu TiO2/SiO2

63

Mass%

Cation

004
SiKa

8000
7200
6400
5600

TiKb

1600

TiKa

2400

TiKesc

3200

TiLsum

4000
TiLl TiLa OKa

Counts

4800

800
0
0.00

1.00

2.00

3.00

4.00

5.00

6.00

7.00

8.00

9.00

10.00

keV
ZAF Method Standardless Quantitative Analysis
Fitting Coefficient : 0.1945
Element

(keV)

Mass%

Error%

Atom%

O K

0.525

50.89

0.35

66.27

45.4186

Si K

1.739

40.32

0.13

29.91

44.6129

Ti K

4.508

8.80

0.25

3.83

9.9685

Total

100.00

Compound

Mass%

Cation

100.00

Hnh.Gin EDX ca mu vt liu TiO2/Si-C

Kt qu xc nh hm lng cc nguyn t trong mu c a ra trong bng
sau: (Ch mu xanh nguyn nh, y l copy nguyn bn t file kt qu)
Mau 1 (TiO2/MCM41)
O

Si

Ti

Total(Mass%)

001

61.07 31.20 7.53

100.00

002

60.43 32.58 6.99

100.00

003

61.65 31.22 7.12

100.00

Mau 2 (TiO2/SiO2)
64

Si

Ti

Total(Mass%)

001

62.00 30.77 7.23

100.00

002

61.43 31.48 7.09

100.00

003

60.52 32.30 7.18

100.00

Mau 4 (TiO2/Si-C)
O

Si

Ti

Total(Mass%)

001

64.07 29.68 6.25

100.00

002

61.84 31.27 6.89

100.00

003

63.43 29.83 6.74

100.00

Kt qu cho thy hm lng TiO2 phn tn t khong 11,6 % . Kt qu xc nh

ti cc im kh trng nhau cng chng t vic TiO2 c phn tn kh ng
u trn b mt cht mang.

004

50.89 40.32 8.80 100.00

3.2. Cc kt qu nghin cu hot tnh xc tc quang ha ca cc vt liu

trong x l mt s thuc tr su nhm ln
3.2.1.Th nghim x l thuc tr su nhm ln nh gi bng phng php
COD.
Bng 3.8: Kt qu kho st x l thuc tr su nhm ln trn cc vt liu
Vt liu
Mu trng
Mu cha x l
M2
MCM-41(M3)
T2
TM2
T2 (quang ha)
TM2 (quang
ha)

C0(ppm)
0
20
20
20
20
20
20
20

COD0
0
235.667
235.667
235.667
235.667
235.667
235.667 65
235.667

ABS
0.033
0.106
0.077
0.068
0.065
0.058
0.05

CODt
0
235.667
139.000
109.000
99.000
75.667
49.000

H (%)

0.046

35.667

84.87

100
41.02
53.75
56.00
67.89
79.20

HIU SUT X L

BIU SO SNH HIU SUT X L XC TC QUANG HA

LIU
Hnh 3.22: Th nghim xVT
l thuc
tr su nhm ln ca cc vt liu

T kt qu thc nghim cho thy: Cc vt liu tng hp c u x l

c thuc tr su nhm ln kh tt. Tuy nhin i vi cc vt liu nn MCM-41
c kh nng hp ph tt hn so vi SiO 2 do c kh nng gi cc hp cht hu c
(thuc tr su nhm ln) trong mao qun bi s ph hp gia kch thc ca cc
hot cht trong thuc tr su nhm ln vi kch thc mao qun ca MCM-41.
Khi c TiO2 trong mao qun kh nng hp ph cc cht tt hn do gim kch
thc ng mao qun [hnh 3.9, 3.10] nn gi c nhiu hot cht thuc tr su
nhm ln hn. Nn vt liu TM2 c th hp ph x l 67,89% lng thuc tr
su, a COD gim xung di 80 t TCVN [3].
c bit khi thc hin x l thuc tr su nhm ln di tc dng ca n
hunh quang vi vt liu cha TiO2 l T2 v TM2 hiu sut tng ln ng k.
iu ny c gii thch l do TiO 2 nano c tnh cht quang ha [mc 1.3.3].
Di tc dng ca nh sng TiO 2 c kh nng oxi ha ct mch cc cht hu c,
66

chuyn ha chng v dng cc cht v c n gin nh CO 2, H2O. Tuy nhin,

phng php nh gi COD ny khng cho chnh xc cao v khng cho bit
trong qu trnh x l quang ha c cho sn phm ph hay khng, sn phm ph
c c hi hay khng.
3.2.2.Th nghim x l thuc tr su nhm ln(i din bng Dimethoat) nh
gi bng phng php GC-MS.
3.2.2.1. Kt qu xy dng ng chun (a kt qu t phn thc nghim
vo y, ch din gii ). Cch xc nh khong tuyn tnh thch hp

3.2.2.2. Nghin cu la chn dung mi chit, th nghim gi vi mu trng

(Nu s qua li cch lm, nhn mnh v cc thuc tr su khng tan, vic s
dng dung mi ha tan c thuc tr su khng kh thi do s oxi ha
quang i vi dung mi d hn oxi ha TTS, hn na mu thc t trong mi
trng thc t thng l trong nc v vy cn phi chit)

3.2.2.3. Kt qu x l quang ha thuc tr su imethroat :

* Mu x l quang ha T2(TiO2/SiO2) : (cn ch thch di cc sc , din
gii cc kt qu, chng hn : trn sc thi gian lu ca cht, ph khi,
..lng cn li trn sc , tnh ton th no ra c bng kt qu, t
nht cng phi din gii chi tit mu u tin, cc mu sau c th ch a sc
v bng kt qu cng c). Ch thch hnh t di, tiu bng t
trn, nh km theo iu kin phn ng (thi gian, nhit , ..)

67

Hnh: .
Bng
Th tch
ban u
V0 (ml)

Th tch
sau
chit
Vs(ml)

Nng
ban u
C0(ppm)

50 ml

48 ml

50 ppm

Nng
sau
x l
Cs(ppm)

Nng thc t
C(ppm)

T l
(%)

54,48

*Mu x l quang ha TM2(TiO2/MCM41) ng kt ta:

68

Hiu
sut
x l
h(%)
45,52

Hnh: .
Bng

Th
Th tch
tch ban
sau
u V0
chit
(ml)
Vs(ml)

Nng
ban u
C0(ppm)

Nng
sau x
l
Cs(ppm)

69

T l
Nng thc t
Ct (ppm)
(%)

Hiu
sut
x l
h(%)

50

47

50 ppm

26,96

*Mu x l quang ha TM3(TiO2/Si-C):

Hnh: .
Bng

70

73,04

Th tch
ban u
V0 (ml)
50

Th tch
Nng
Nng
sau
sau
ban u
chit
x l
C0(ppm)
Vs(ml)
Cs(ppm)
40

Nng thc t
C(ppm)

100

T l
(%)
31,87

Hiu
sut
x l
h(%)
68,13

BIU SO SNH HIU SUT X L XC TC QUANG HA

80

HIU SUT X L

70
60
50
40
30
20
10
0
T2(TiO2/SiO2)

TM4(TiO2/Si-C) TM2(TiO2/MCM41)

VT LIU

T kt kt qu thc nghim cho thy : cc mu vt liu tng hp TiO2/cht

nn u c kh nng x l quang ha tt thuc tr su Dimethoat (t hiu sut
x l cao nht l 73,04% ). Kt qu phn tch cng ch ra trong qu trnh x l
quang ha trn vt liu cha titan tng hp c kh trit , khng c cc

71

sn phm trung gian, nh vy oxi ha quang ct mch c imethroat

thnh cc hp cht v c n gin v khng cn gy c hi cho mi trng.

Tho lun chung :

Nh vy, vi c ba h vt liu tng hp cha khong 10% TiO 2 phn tn
trn cc nn SiO2 xp, nn MCM-41 v nn Si-C, t tin cht Ti l
tetraisopropylorthotitanat (TIPOTi), cho kt qu x l thuc tr su nhm ln (i
din l imethroat) rt kh quan, chng t xc tc trn c s TiO2 thch hp cho
qu trnh ny. Hiu qu x l thu c cao nht trn vt liu TiO2/MCM-41
(73,04% trong 6 gi phn ng ???). Kh nng ny c th do h vt liu TiO2
trn nn MCM-41 c din tch b mt ln hn nn c kh nng hp ph v lu
gi cc cht phn ng trong mao qun (ph hp v kch thc phn t thuocs tr
su vi mao qun ca MCM-41), to thun li cho phn ng hn. Vi h
TiO2/SiO2, hiu qu x l quang ha imethroat thu c l thp nht (45,52%)
kh nng do vt liu ny c din tch b mt thp nn trong qu trnh phn ng c
th lm tng s thiu kt ca cc ht xc tc nano, to xu hng co cm thnh
cc cluster kch thc ln hn nn gim hot tnh xc tc.
H vt liu TiO2/Si-C c kh nng xc tc quang ha cho qu trnh oxi ha
ct mch imethroat tng ng vi vt liu nn MCM41(68,13%). Hiu qu
ny c th l do s c mt ca cacbon trong vt liu nn lm tng tng hp ca
vt liu vi cht hu c (thuc tr su), thu ht tt hn cc cht hu c n cc
tm xc tc to thun li cho phn ng xy ra, ng thi, cacbon cng lm tng
s hp th nh sng dn n qu trnh quang ha din ra c n nh v thun
li hn. y l mt kt qu rt ng ch , a n trin vng ng dng trong
thc t c bi vi cht nn Si-C, c th s dng cc nguyn liu u r hn v
qu trnh tng hp d dng hn so vi MCM-41 rt nhiu.

72

KT LUN

Sau qu trnh thc hin ti lun vn chng ti thu c mt s kt qu

chnh sau:
73

1. tng hp thnh cng h vt liu nano TiO2 t tin cht

tetraisopropylorthotitanat, phn tn trn cc cht nn MCM-41, SiO2 xp v
cht nn Si-C vi hm lng TiO2 khong 10%.
2. s dng cc phng php vt l hin i nh: XRD, SEM, EDX, BET
xc nh c trng vt liu tng hp c, cc mu vt liu thu c c din
tch b mt ring kh ln (340 500 m 2/g), c xp cao, TiO2 phn tn kh
ng u trn b mt cc cht mang.
3. xy dng c phng php phn tch nh tnh v nh lng cc sn
phm ca qu trnh oxi ha quang ha thuc tr su nhm ln (vi i din
imethroat) phng php GC-MS.
4. nghin cu la chn c cc iu kin thch hp cho qu trnh phn tch:
dung mi, khong chun tuyn tnh, . Kt qu th nghim gi trn mu trng
cng minh chng cho chnh xc ca phng php phn tch i vi
thuc tr su nhm ln ny.
5. th nghim kh nng x l quang ha thuc tr su nhm ln trn cc mu
vt liu. Hiu sut x l t t 68 73% sau 6 gi phn ng. c bit qu
trnh oxi ha quang ct mch dimethroat trn cc vt liu tng hp c rt
trit , hon ton thnh cc hp cht v c n gin, khng to cc sn phm
trung gian c hi n mi trng.
+ Trong cc gian on tip sau ca lun vn ny, chng ti s tin hnh nghin
cu k hn kh nng xc tc quang ha ca h vt liu cha Ti i vi qu trnh
x l cc hp cht hu c c hi khc c mt trong nc: c clo, pyrethroit,
khng sinh, .. , hon thin vic nghin cu yu t nh hng n qu trnh x l
nh pH, To, thi gian...
+ i vi vt liu nn Si-C, vi kh nng tng hp hu c v hp th nh sng
tt cng l mt hng nghin cu kh quan. C th s pht trin vi vic a
74

thm mt s kim loi khc ngoi Ti c hiu qu xc tin cho qu trnh quang ha
tt hn nhm tng thm hiu sut x l cho qu trnh ny.

TI LIU THAM KHO

Ting Vit
1. Nguyn nh Bng. Gio trnh cc phng php x l nc, nc thi
Trng HKHTN, HQG HN, 2004.

75

2.

Nguyn Thanh Bnh. Oxi ha hon ton clobenzen trn xc tc perovskite

LaCo0,8Fe0,2O3 c b sung paladium. Journal of Chemistry T48 (4C) 6872,
2010.

3.

Bi Duy Cam (2008), Nghin cu ch to vt liu hp ph bin tnh ng

dng tch mt s ion c hi trong nc ngm mt s khu vc trn a bn
H Ni, ti khoa hc cng ngh cp thnh ph H Ni, M s: L/01
2006 2.

4. TS. Nguyn Th Bch Lc, Nghin cu ch to TiO2 trn vt liu mang,

ti khoa hc m s QG.07.10, Trng i hc Khoa Hc T Nhin, 2009
5. Hong Nhm, Ha hc v c. Tp mt. Nh xut bn gio dc, 2002.
6. Hong Nhm, Ha hc v c. Tp hai. Nh xut bn gio dc, 2002.
7. Hong Nhm, Ha hc v c. Tp ba. Nh xut bn gio dc, 2002.
8. Nguyn Hu Ph (1999), Vt liu v c mao qun trong hp ph v xc
tc, Nh xut bn Khoa hc v K thut, H Ni.
9. Nguyn Vn Ri, Thc tp phn tch ha hc. i hc khoa hc t nhin,
2006.
10.Nguyn nh Triu (2001), Cc phng php phn tch vt l v ho l,
T.1, NXB Khoa hc v K thut, H Ni
11. Phm Hng Vit, Trn T Hiu, Nguyn Vn Ni, Ha hc mi trng c
s, Trng HKHTN, HQG HN, 1999
Ti liu ting Anh:
12.Andrei Y. Khodakov, Vladimir L. Zholobenko, Rafeh Bechara, Dominique
Durand, (2005), Impact of aqueous impregnation on the long-range
ordering and mesoporous structure of cobalt containing MCM-41 and SBA15 materials, Microporous and Mesoporous Materials ,79, pp. 2939
76

13. Brian Wilson, Report Control of Process and Fugitive Emissions in the
Plant and the Community, International Lead Management Center, May
2008.
14. BlackSmith Institute, Report: Rudnaya River Valley Lead Exposure
Mitigation, 2010.
15. D. Dvoranova, V. Brezova, M. Maz , and M. A. Malati, Investigations
of metal-doped titanium dioxide photocatalysts, Applied Catalysis
B:Environmental, vol. 37, no. 2, 91105, 2002.
16.

E. Bae, W. Choi, Highly Enhanced Photoreductive Degradation of

Perchlorinated Compounds on Dye-Sensitized Metal/TiO 2 under Visible
Light Environ. Sci. Technol., Vol.37 p.147-152, 2003.

17. E. Stathatos, T. Petrova, and P. Lianos, Study of the efficiency of visiblelight photocatalytic degradation of basic blue adsorbed on pure and doped
mesoporous titania films, Langmuir, vol. 17, no. 16, pp. 50255030, 2001
18.

H.

Kozuka,

G.

Zhao,

T.

Yoko,

Sol-gel

preparation

and

photoelectrochemical properties of TiO2 films containing Au and Ag metal

particles, Thin Solid Films, Vol. 277, Issues 1-2, 147-154, 1996.
19. I. Ilisz, A. Dombi, Investigation of the photodecomposition of phenol in
near-UV-irradiated aqueous TiO2 suspensions. II. Effect of charge-trapping
species on product distribution, Applied Catalysis A: General, vol. 180,
Issues 1-2, 35-45, 1999.
20.Jiri.Rathouky, Maketa Zukalova (1998), Homogeneous precipitation of
siliceous MCM-41 and Bimodal silica,

Collect.Crech.Chem.Commum,

Vol. 63, p.1893-1906.

21. K Srinivasa Rao et al, Treatment of wastewater containing Pb and Fe
using ion-exchange techniques, Journal of Chemical Technology and
Biotechnology, 80:892 - 898 (2005)].
77

22. Muhamad S.Vohra and allen P. Davis, Report: TiO2- assisted

photocatalysis of lead-EDTA, Wat. Res. Vol. 34, No. 3, pp. 952964,
2000.
23.

M. Muneer , D. Bahnemann , M. Qamar , M.A. Tariq , M. Faisal

(2005),Photocatalysed reaction of few selected organic systems in presence
of titanium dioxide, Applied Catalysis A: General 289 ,224230

24. N H M Kamel et al, Report Removal of Lead, Cobalt and Manganese

from Aqueous Solutions using a new Modified Synthetic Ion Exchanger,

Archives of Applied Science Research, 2011, 3 (2):448-464].
25. R.L. Sawhney, Report: Solar photocatalytic removal of Cu(II), Ni(II),
Zn(II) anh Pb(II): speciation modeling of metal citric acid complexes ,
Journal of hazardous materials 115 (2008) 424-432.
26. R. Venckatesh, Report: Uptake of Pb(II) ion from queous solution using
sikl cotton hull carbon: an agricultural waste biomass, E Journal of
chemistry, Octorber 2006.
27. Sun-Jae Kima, Hee-Gyoun Lee, Seon-Jin Kim, Jong-Kuk Lee , Eun Gu
Lee, Report: Photoredox properties of ultrane rutile TiO2 acicular
powder in aqueous 4-chlorophenol, CuEDTA and PbEDTA solutions,
Applied Catalysis A: General 242 (2003) 8999.
28. YAN Yongsheng, Report: Synthesis, characterization and adsorption
performance of Pb(II) impronted polymer in nano TiO 2 matrix, Journal
of environmental sciences, May 2009. .
29. Yugui Tao, Report: Removal of Pb(II) from qqueous solution on
chitasan/TiO2 hybrid film, Joural of hazardous materials, 161 (2009), 718722.

78

PH LC
(Chin photocopy cc tp sc k, in mt s nh SEM v BET ghp vo phn
ny l Okie, mnh gi km theo lun vn sa ny l 01 mu BET.)
Sc mu chun Dimethoat:

79

T IC ;

0 ,8 d im e th o a t 9 - 2 1 - 2 0 1 2 p 7 - c 5 4 .x m s ;

F ilte r e d

300

MCps

250

23.260 min

Dimethoat

350

1A

200

150

100

50

0
5

10

15

20

25

Sc mu Dimethoat x l quang ha:

Kt qu phn tch GC-MS ti pic c thi gian lu l 17,7 pht:

80

30

m in u te s

c x l d im e th o a t 2 1 1 - 5 -2 0 1 2 th a n g .x m s
100%

1 7 .7 7 1 m in , S c a n : 2 2 4 8 , M e rg e d

7 3 .1

75%

50%

25%
1 4 7 .1
2 8 1 .1
3 2 7 .0

7 4 .1

0%
100

200

300

81

400

500

m /z

S e a rc h
100%

1 3 .3 3 7 m in , S c a n : 1 6 1 6 , M e rg e d

7 3 .1

75%

50%

25%

3 4 1 .0
7 4 .1

1 4 7 .0

4 2 9 .1

0%
M a tc h
100%

C A S N o . 5 4 0 -9 7 -6 , C y c lo h e x a s ilo x a n e , d o d e c a m e th y l7 3 .0

Si

75%

Si O
O

Si

O
O

Si

Si
Si

50%
4 2 9 .0
3 4 1 .0

25%
7 4 .0

4 3 0 .0

1 4 7 .0

3 4 2 .0

0%
0
100
R .M a tc h : 7 4 0 , F .M a tc h : 7 4 0

200

300

82

400

500

m /z