Vt liu vi mao qun

Li cm n!
Vi lng bit n v hn em xin chn thnh
cm n PGS.TS. Trn Th Nh Mai giao ti,
hng dn tn tnh su sc v mt khoa hc v thc
nghm trong sut qu trnh thc hin kho ln tt
nghip.
Em cng xin chn thnh cm n thy c, anh
chi trong b mn ho hc du m cng nh trung
tm ho du thuc khoa Ho- HKHTN ch bo
v ng vin em trong sut thi gian lm kho lun
tt nghip.
Cui cng em xin gi li cm n ba m, anh
ch trong gia nh chu cp v mt ti chnh v
ng vin v mt tinh thn cho em yn tm hc tp.

H Ni, ngy

thng

Sinh vin

Bi Th Minh Thu

nm

T VN
C th ni rng cc vt liu vi mao qun hn 40 nm qua ng mt
vai tr cc k quan trng vi nhiu ng dng trong cng ngh hp ph v xc
tc [6]. Tuy nhin do ng knh mao qun v cc hc rng ca zeolit b hn
ch trong phm vi 4-12, ch thch hp vi cc chuyn ho nhng phn t
nh (parafin trung bnh, hydrocacbon mt vng thm) khng th p ng
cho qu trnh gm nhiu phn t ln (hidrocacbon phn nhnh, a vng
thm). Cng c nhiu cng trnh nghin cu c thc hin. Ngi ta s
dng cc cht to cu trc hu c c kch thc tng i ln nh l cc cht
lm y l trng. Qu trnh tng hp c thc hin theo phng php sol-gel.
Phng php ny t ra khng hiu qu i vi vic tng hp cc cu trc nh
zeolit nhng c ng knh mao qun ln hn 10. Tuy nhin n li kh thnh
cng khi s dng cc nguyn t nh Al, P, Ga trong vai tr l cc nguyn t to
mng (framework elements). Nhng cc zeolit l rng nht cng nh cc vt
liu tng t zeolit bit cng bc l mt s hn ch. iu ny gi cho
vic tng hp cc vt liu cha l trung bnh nm trong cc tinh th zeolit.
Xong din tch b mt hay th tch cc l trung bnh cn thp v h thng l
mesopore khng ng u, cc phn ng din ra trong cc vt liu ny kh c
th kim sot c [2].
Trong nhng nm 1991-1992, mt pht minh mang tnh cch mng ca
hng Mobil l tng hp ra vt liu mao qun trung bnh M41S vi cc knh
rng t 15-100, b mt ring ln ln ti 1400 m2/g v rt ng u, c kh
nng to cc nhm chc b mt khc nhau m ra mt trin vng mi trong
vic tng hp xc tc cho cc qu trnh lc v ho du [2,6,13]. MCM-41 l
thnh vin quan trng nht ca h M41S v c nghin cu su hn c.
[15,20]

Vt liu cha Titan oxit vn c bit n nh mt xc tc tuyt vi.

Vic a Titan ln mao qun trung bnh, c bit l a Titan vo trong khung
cu trc hexagonal to ra cc loi xc tc bin tnh ca MCM-41 thc y
phn ng oxi ho, oxi ho kh, epoxi ho trong chuyn ho cc hidrocacbon c
trong du nng v cc phn t hu c c kch thc cng knh [17, 21].
Epoxit hay cn gi l oxirane l ete vng 3 thnh vin ( threemembered ring). Vng trong nhng phn t ny c sc cng ln lm cho chng
hot ng hn nhng ete khc. Phn ng epoxi ha l phn ng quan trng
trong ha hu c v epoxit l cht trung gian c th chuyn i thnh nhiu sn
phm khc nhau. Thm vo , s hnh thnh epoxit rt hp dn trong tng hp
bt i xng v n c th dn ti hai Cacbon Chiral ch cn mt bc [22].
Trn c s nhng nhn nh s b , trong bn lun vn ny s trnh
by nhng nghin cu v tng hp v c trng Ti-MCM-41 ng thi c
trng xc tc thng qua phn ng epoxi ha du thc vt.

CHNG 1: TNG QUAN

1.1 Vt liu mao qun trung bnh
1.1.1 Gii thiu chung
Trong nhng nm gn y, vt liu nano thu ht s quan tm, u t
cng nh n lc rt ln trn ton th gii trong c hai lnh vc nghin cu
khoa hc v pht trin cng nghip bi ng dng da dng ca chng trong
nhiu lnh vc khc nhau. Vt liu xp nano ( nanoporous) ch l mt phn
trong vt liu nano m thi nhng da vo tnh xp, chng c th dng trong
vic trao i ion, khuch tn, xc tc, sensor, pht hin cc phn t sinh hc v
tinh ch.
Theo International Union of Pure and Applied Chemistry (IUPAC) vt
liu xp c th chia thnh 3 loi sau:
Bng 1: Phn loi cc vt liu mao qun rn [7,15]
Vt liu

kch thc mao qun

V d

()
Mao qun ln

>500

Thu tinh

(Macropore)
Mao qun trung
bnh

M41S, cc aerogel v
20-500

(Mesopore)
Vi mao qun
(Micropore)

cc vt liu tr lp
(pillar-layer)

<20

Zeolit

Nhng nh ngha ny li mu thun vi nh ngha m rng ca vt

liu xp nano. Thut ng nanoporous m ch trc tip nhng vt liu c
ng knh t 1 n 100nm. Nh vy, thc t vt liu xp nano bao gm mt
phn micro v macro cng nh ton b vt liu mesopore.
S pht trin vt liu l xp vi din tch b mt ring ln dn n
mt lnh vc nghin cu rng ri, vi s quan tm c bit ti ng dng tim
nng ca n . V d nh hp ph, sc k, xc tc, cng ngh sensor, v bo
qun kh. S t ph bt u t nm 1992 khi Mobil Oil Company khm ph
ra ngnh silic xp ng u kch thc trung bnh ( periodic mesoporous
silicas) c bit n nh gia nh M41S . Nhng vt liu ny thay th ry
phn t zeolit b gii hn bi kch thc l di 10 . Ging nh zeolit tinh
th micropore, M41S ngnh vt liu ny c c trng bi din tch b mt
ring ln, h thng l u n v s phn b mao qun r rng. Tuy nhin
khc vi zeolit, chng c ng knh l xp x 2 n 10 nm v thnh SiO2 v
nh hnh. Nhng i din din c bit n nhiu nht l MCM-41 ( vi s
sp xp mesopores theo dng hexagonal, nhm khng gian l p6mm), MCM48 (mesopores theo dng cubic, nhm khng gian Ia3d), v MCM-50
(mesopores theo dng cubic, nhm khng gian p2) [14].
-

Cu trc lc lng (hexagonal), v d MCM-41

Cu trc lp phng (cubic), v d MCM-48

Cu trc lp mng (lamilar), v d MCM 50

a)

b)

c)

Hnh 1: Cc dng cu trc ca vt liu MQTB

a) MCM-41 (1D)

b) MCM-48 (3D)

c)MCM-50 (2D)

1.1.2 u im ca vt liu MQTB v ng dng:

MCM-41 c th c dng trc tip lm cht xc tc. Nh trn ni
do gii hn ca kch thc l, zeolit ch thch hp cho vic chuyn ho cc
phn t nh (parafin trung bnh, hydrocacbon mt vng thm). Trong khi
nhu cu s dng phn on nng ngy cng tng cn du nng gim. Bi vy
ngi ta quan tm nhiu n s chuyn ho du cn mt cch c bit hn. Hai
qu trnh chuyn ho su: Crackinh xc tc v Hydrocrackinh xc tc trong du
chng ct chn khng tr nn v cng quan trng [6]. Theo kho st cho thy
khi cracking cc phn t ln trong du chng ct chn khng th hot tnh xc
tc ca MCM-41 gn xp x zeolit v USY, cao hn nhm silicat v nh hnh.
Hn na xc tc ny cho du lng, t kh v cc hn. T thy rng MCM-41
nu khng phi l xc tc chnh cho qu trnh FCC th cng c kh nng to ra
hot tnh xc tc cho cht nn. MCM-41 c dng crackinh s b cc phn
t ln (do kch thc l rng t 20- 100) to ra cc phn t nh hn, d dng
hn cho qu trnh crackinh tip theo su hn bng zeolit (ZSM 5/MCM-41) [2].
Mt khc, MCM-41 cng l vt liu s dng tt cho qu trnh i hi
tnh axit tng i yu. Tin hnh phn ng desunfo ho ca nguyn liu p
sut di 100 bar cho thy hm lng du diesel tng ln ng k ng thi
cng hon thnh vic desunfo ho [2].
Vi b mt ring ln v kh nng c th to ra cc nhm chc b mt
khc nhau, vt liu MQTB l cht mang tt cho nhiu loi xc tc. V d NiMo/ MCM-41 rt hot tnh cho phn ng hydrocracking phn on gasolin.
Trong nhng nm gn y c nhiu nghin cu a kim loi (Ti, Co, Ni, Cr,
Al, Fe) v cc oxit kim loi (TiO2, VOx, ZO2, NiO, MnO, WOX, MoOx)
ln MQTB khc nhau. ng dng ca chng rt phong ph v ngy cng c
trin vng thng mi.
-

Al-MCM-41 c nhiu u im i vi phn ng cracking cc phn on

nng gasoil

Ni-MCM41 c axit trung bnh nhng c hot tnh cao i vi mt s

phn ng nh b gy mch polyetylen thnh hirocacbon sp xp li cc
acetal, cc phn ng ankyl ho Friedel- Crafts, Naphtaler Benzen.

Ti-MCM-41 th hin tnh oxi ho cao i vi phn ng epoxi ho cc olefin

c bit l cc olefin c kch thc ln.

-

V-MCM-41 dng oxi ho xyclododecan, 1-naftol vi H2O2 rt hiu qu.

Ti, V, Cr, Mn, Mo/MCM-41 lm xc tc cho phn ng hyroxyl ha benzen

thnh phenol.
1.1.3 Nhc im v cch khc phc

Nhc im: [1,8,12]
-

axit b mt ca vt liu thp.

Tnh bn thu nhit khng cao.

Kh nng ti sinh km. Bi l i vi xc tc FCC nhit ca qu trnh ti

sinh l 800oC trong s c mt ca hi nc. iu kin ny MCM-41 d b

phn hu. [3]
- Din tch b mt ring ca MCM-41 b gim ng k v km hot ng
750oC v p sut 15 psig.

Cch khc phc: [2]
- Gim hm lng silanol ca vt liu bng cch Silic ho cc nhm -OH b
mt b mt vt liu tr nn k nc hn v bn vng hn trong mi trng
nc.
- Tng b dy thnh mao qun ca vt liu v tng trt t ca h thng mao
qun. V d nh cch bin tng v nh hnh ca MCM-41 bng ZSM-5.
- Thm cc mui v gel tng hp tng cng qu trnh ngng t cc
nhm silanol khi hnh thnh khung mang vt liu s ci thin kh nng lin kt
ngang ca thnh mao qun, gia tng tnh bn vng ca vt liu.
- Chuyn ho cc cu trc v nh hnh thnh pha tinh th.

- To hn hp composit gia vt liu MQTB v zeolit mao qun nh ci tin

tnh bn vng thu nhit v axit.
1.2 Kim loi chuyn tip Ti v Ti-MCM-41
Trong qu trnh pht hnh pht trin cc ng dng vt liu silicat MQTB
ngi ta nhn thy rng vic thay th mt phn Silic mng li bng cc kim
loi chuyn tip c th thay i ng k tnh cht ca chng. Nhng vt liu
ny c phn tn cao dng d th v c kch thc l rng, b mt ln ang
c ch n nh l xc tc oxi ho kh cho cc hp cht hu c cng knh.
Hn na cng nghip ngy nay yu cu phi pht trin nhng loi vt liu va
hiu qu v r tin gim gi thnh sn xut, tng li nhun. Cc kim loi
chuyn tip u c vng in t d cha bo ho nn c kh nng cho nhn in
t d dng thay i trng thi ho tr ca mnh. V vy chng thng c
s dng lm xc tc cho cc phn ng oxi ho chn lc hidrocacbon. Trong
Ti l kim loi chuyn tip c nghin cu nhiu nht. Ti mang trn vt liu
MQTB dng nhiu cho qu trnh epoxi ho cc olefin c bit l cc olefin c
kch thc ln vi chn lc cao.
1.2.1 Gii thiu v Titan, Titan oxit v ng dng ca chng

Gii thiu chung:
Titan l kim loi c mu trng bc, hot tnh ho hc cao, nhit cao
rt d nhim tp cht. Trong khng kh Titan b bao ph bi mt lp mng oxit
TiO2 che ch cho kim loi khi b n mn.
Titan oxit l cht rn mu trng, c 3 dng tinh th khc nhau l Rutin,
Anatase, Brookite. Chng tn ti trong thin nhin di dng khong vt, trong
ph bin nht l Rutin. Chng u c cng thc l TiO2 nhng c cu trc
khc nhau.

Rutin: L loi qung ch yu ca Ti (mt kim loi c s dng cho
cng ngh hp kim cao bi khi lng nh, c bn cao, kh nng chng n

mn ca n). Rutin c mng li t phng, mi ion Ti4+ c ion O2- bao

quanh kiu bt din.
 Anatase: L mt cht a hnh, nhit cao trn 915oC Anatase s
t chuyn sang cu trc dng Rutin. Anatase c nhiu tnh cht tng t v gn
ging vi tnh cht ca Rutin nh nh kim loi, cng, cng t trng v tnh cht
i xng. Nhng do cu trc khc nhau Anatase v Rutin c s khc nhau nh
v hnh th. Tinh th Anatase rt c bit khng ln xn nh cc khong vt
khc. Chng to thnh cc dng bt din do cc nh nhn b ko di ra. S ko
di ra ca cc nh nhn khng r rng phn bit cu trc tinh th ny
vi cu trc bt din. Gia chng c s tng ng.
 Brookite: L cht a hnh nhit cao trn 750oC s t ng
chuyn sang dng Rutin. Chng c nhiu tnh cht tng t vi Rutin nh
cng v t khi.

(b)

(a)

(c)

Hnh 2: Cu trc Titan oxit

a) Rutin

b) Anatase

c) Brookite

Cc ng dng ca TiO2:
TiO2 l mt oxit rn c tnh axit kh mnh, c th s dng lm cht
mang cho cc kim loi xc tc s dng cho cc qu trnh isome ho c bit khi
iu ch sunfat ho. Ngoi vic s dng lm cht mang, oxit Titan c s
dng lm xc tc cho cc phn ng oxi ho xc tc quang ha (photocatalytic

oxidation) v tnh cht cho in t s dng [18, 30, 36]. Titan ang c quan
tm nghin cu nhiu l do tnh cht n nh c v kh nng oxi ho v c c 4
c tnh: oxi ha, kh, oxit, baz. Tnh oxi ho kh ca TiO2 trung bnh nn n
thng c chn lc cho nhng phn ng c tnh oxi ho kh va phi v
thng c chn lc cao. [3,19, 21, 22]
1.2.2 c im ca vt liu Ti-MCM-41
H vt liu oxit Titan mang trn cht nn oxit silic c bit bit n
vo nm 1983 khi cc nh khoa hc tng hp thnh cng zeolit silicalite-1
(TS-1) bng vic thay th ng hnh Ti cho Si4+ trong mng li zeolit khc
nhau. Cng vi vic s dng H2O2 hoc Tert butyl hidro peroxit (TBHP) nh l
tc nhn oxi ho. Trong khi cc dng TS-1, Ti-zeolit, c s dng cho phn
ng oxi ho cc ancol, ankan thp th h TiO2/ MCM-41, Ti- MCM-41 li c
bit c hiu qu cho qu trnh oxi ho chon lc cc olefin to ra cc sn phm
epoxi ho, hn na h xc tc ny rt bn. Ti c tng hp bng cch thay th
ng hnh Si bng kim loi Ti vo mng li ca MCM-41 (T l Si/Ti c th
bin i trong khong rng t 100-10). Nhng iu quan trng nht l cn tm
phng php gn Ti vo mng cu trc tinh th MCM-41 mt cch thnh cng
bi l ion titan khng bn pH cao nn rt d to thnh pha TiO2 anatase
khng tan, m hm lng anatase lm gim hot tnh xc tc v chn lc
ca vt liu Ti-MCM-41.V vy yu cu gn c Titan vo mng cng nhiu
cng tt v loi tr c s to thnh pha anatase.
1.2.3 C ch gn Ti vo trong khung cu trc ca vt liu MCM-41
S hnh thnh ca vt liu mao qun cha Ti l do thu phn v ngng
t nhanh ca TiPT (tetra iso propyl ortho Titanate) v TEOS (tetra etyl ortho
Silicate). gi tr pH=11-12 th s thu phn TiPT din ra nhanh hn so vi
TEOS. Tuy rng cha thng nht nhng c th ra mt c ch nh sau: cc
lp v c bao quanh mixen ca cht to cu trc to thnh cc hnh khi c
bit. Cc hnh khi ny sp xp thnh h thng mao qun ca vt liu. Cc ion
Titan tp trung b mt ca mixen to ra cc tm axit. Bng thc nghim

ngi ta chng minh c Ti nm trong khung cu trc ca vt liu m

khng phi nm ngoi dng TiO2 anatase [3].

OEt

OH M = Si, Ti

CnH2n+1NH2
N

HOM

M = Si, Ti

S hnh thnh mixen

O
O
M

HH

HN
H
N
H
HN
H

M
O
H

HN
H

M
O
H

H H

O
M
O
H

HH
N H
NH

N
H
NH

H H

NH H

Hnh 3: C ch gn Ti vo trong khung cu trc MCM-41

1.2.4 Cc yu t nh hng trong qu trnh tng hp Ti-MCM-41
1.2.4.1 nh hng ca cht HBM
Template, hay cht nh hng cu trc, l tc nhn c kh nng nh
hng mng li cu trc trong qu trnh hnh thnh MCM-41. Tc ng ca
template th hin hai mt:
- nh hng ti qu trnh to gel ho v to nhn: template sp xp li
cc n v TO4 thnh cc khi c bit xung quanh mnh, to hnh thi nh
trc cho qu trnh to nhn v pht trin ca tinh th.

- Lm gim th ho hc ca mng li hnh thnh: s c mt ca

template lm n nh mng li nh cc tng tc mi (lin kt hidro, lin
kt tnh in)
Xt v mt nng lng qu trnh thay i kch thc mao qun cu vt
liu MQTB xy ra thun li. Nu s dng cu trc c di mch cacbon khc
nhau th vt liu iu ch c c din tch b mt ring v kch thc mao
qun khc nhau. ui ankyl cng di th kch thc mao qun cng tng,
nhng thng nh hn 40 . c kch thc mao qun ln hn thng s
dng cc phn t pht trin ui ca cc cht HBM nh 1,3,5 tri metyl
benzen.

Thng

thng

iu

ch

MCM-41

thng

dng

xetyltrimetylamonibromua (CTAB). y l cc phn t tch in cation c kh

nng ho tan silic do l 1 baz mnh, pH cao nn lm tng mc bo ho
ca h.
Theo Vartuli v cc cng s nng cht HBM v t l cht
HBM/Si l yu t chnh nh hng ti s hnh thnh cc cu trc khc nhau
ca vt liu MQTB. V d i vi CTAB, qu trnh hnh thnh cc cu trc pha
tinh th lng khc nhau trong dung dich ph thuc vo nhit v nng
cht HBM nh sau:

Hnh 4 : Biu din s hnh thnh pha tinh th lng khc nhau theo

nhit v nng cht HBM (CTAB).

Khi nng cht hot ng b mt tng qu trnh chuyn pha xy ra
theo hng: lc lng
lp phng
lp. Theo kho st th tng hp vt
liu MQTB MCM-41 th t l tamplate/Si dao ng t 0.1-1, v tt nht khong
0.3 th cu trc mao qun kh u n [13, 15, 34].
1.2.4.2 nh hng ca thi gian, t l OH-/Si, Si/Ti ln hm lng Ti
trong mng:
Hm lng Ti trong mng l mt c trng quan trng quyt nh hat
tnh ca Ti-MCM-41. Quy lut thay th ng hnh ion Si trong mng bi ion Ti
rt phc tp, lin quan n lc cng nng lng ca cc tng tc ion m cho
n nay vn cn tho lun cha khng nh v c ch. Ni chung ngi ta
mun a Titan vo mng cng nhiu cng tt. Hm lng Titantrong mng t
l nghch vi thi gian kt tinh v t l Si/Ti. C th gi thit rng ton b Ti
trong sol s tham gia vo cu trc ngay giai on u. Tuy nhin khi cc ion Ti
thay th ng hnh cc ion Si s lm thay i th tch mng c s v bin
i lc cng lm gim dn kh nng tip tc gn cc ion khc vo mng. V th
nu tip tc tng nng ion trong sol (theo chiu gim t l Si/Ti) hm lng
Titan trong mng cng khng tng. Khi thi gian kt tinh tng hm lng Titan
trong mng cng bt u gim i do c s chuyn dch Ti t dng Ti+4 sang
TiO2 dng anatas c cu trc bn hn v mt nng lng. T l OH-/ Si tng,
hm lng ion Titan trong mng gim c th do bn thn ngun Ti dng
ankoxit trong hn hp sol ban u ca phn ng km bn ti gi tr pH cao.
Ngoi ra hm lng Ti nh hng bi Si/ Ti tc l hm lng Ti gn trong
mng nh hng r rt bi hm lng Ti trong sol ban u ( t s Si/Ti). Khi t
l Si/Ti trong gel ban u gim dn th hm lng Ti trong mng tng dn
(tuyn tnh). Nu tip tc gim t l Si/ Ti tc l tng t l Ti trong sol ban u
th hm lng Ti trong mng khng tng tuyn tnh na m tc tng gim
dn v t cc i mt im ti hn; khi vt qu im ti hn hm lng
Ti trong mng khng tng na v cc ion Ti d trong dung dch chuyn thnh
TiO2 dng anatas [9]

1.2.4.3 nh hng ca nhit [8,12]

Nhit l mt yu t quan trng trong qu trnh tng hp. Qu trnh
tng hp MQTB Si- MCM41 ti u c thc hin trong khong 40-100oC.
nhit phng (25oC) sn phm to ra c trt t km b mt ring thp
(khong 700 m2/g) do qu trnh polime ho ngng t silicat xy ra chm. Nhit
cng cao qu trnh trng ngng hnh thnh cu trc MQTB cng nhanh, thi
gian tng hp cng rt ngn. Tuy nhin nhit ln hn 100oC, vt liu to
thnh l silicagel hoc zeolit. iu ny c th gii thch l nhit cao
chuyn ng nhit ca cc phn t ln dn n thi gian tng tc gia cc
cht HBM v tin cht v c yu.
gin rng mao qun, MCM-41 c iu ch nhit thp hn
70oC sau un nng cht rn trong dung dch nguyn khai ca n.
1.2.4.4 nh hng ca ngun Silic
Ngun Silic c nh hng rt ln n tinh th, kch thc tinh th,
hot tnh v chn lc xc tc ca MCM- 41.
Nu ngun Silic l SiO2 v nh hnh th tinh th ln v khng ng
u. thu c nhng tinh th b, ni chung nn s dng ngun Si ban u
c hm lng silica monome ln v dng ngun Silic cng cho tc kt tinh
cao hn dng ngun polyme. Bi vy hin nay tng hp MCM-41 hu ht
s dng silicon ankoxit (TEOS). y l ngun Silic tinh khit. Do vic gn
Ti hay cc kim loi vo mng ca vt liu s d dng hn v trong gel ban u
v cc kim s phn loi s phn tn tt v ng u gia cc nhm monosilicat,
lm cho hm lng ca kim loi a vo khung cao hn so vi s dng cc
ngun Silic khc [13,15, 20].
1.3 Phn ng Epoxi ha du thc vt
Oxy ha xc tc l mt cng ngh c s dng rng ri sn xut cc
sn phm cha oxi quan trng trong cng nghip, cng ngh ha hc, cng
nghip ha du, cng nghip tng hp cc cht hu c tinh vi. Cc cng ngh

oxi ha c in thng gy nhim mi trng v s dng cc tc nhn oxi

ha nh dicromat, pemanganat. Cc cng ngh dn dn thay th bi cc
cng ngh oxi ha sch hn, hiu sut cao hn, cc cht xc tc ng vai tr rt
ln. Nhng vic la chn cc tc nhn oxi ha cng ht sc cn trng v chng
quyt nh khng nhng hiu sut phn ng m cn lng cht thi nhim
mi trng [21, 22, 27, 31]. Trong cc phn ng ny, phi c phi t bn oxi
ha v n c th lm n nh trng thi ha tr cao ca cc tiu phn oxometal
ging nh cc phi t hu c. chnh l phng php gn cc ion kim loi
trong pha nn v c. Oxi ha xc tc d th trong pha lng vi cht xc tc l
cc ry phn t oxi ha kh c nhng ng dng r rt trong cc phn ng oxi
ha chn lc cc hp cht hu c nhiu nhm chc phc tp, bn nhit
thp. Bn thn cc phn t loi ny cng bn trong mi trng oxi ha, cu
trc mao qun ng u, v tr cc tm kim loi redox tch bit, hn ch s mt
hot xc tc, v c kh nng xc tc chn lc hnh dng, h thng thit b
cng ngh thc hin theo phng php ny n gin v d iu kin hn.
Epoxi ha du thc vt l mt phn ng quan trng v phng din
thng mi v epoxit c th chuyn i thnh nhiu sn phm khc nhau. V d
c th lm tc nhn mn do v nhng cht n nh polime. Nhng epoxit ny
(oleat c epoxi ha) c th c dng nh nhng cht trung gian trong
vic sn xut cc dn xut a dng bi v tnh hot ng cao ca vng epoxi b
cng ra. V d ru bc 1, ru bc 2, cc diolefin, alkoxylalcohol,
hydroxylester, N-hydroxyalkyllamide, mercaptoalcohol, aminoalcohol v
hydroxynitrile c th c sn xut theo ng m vng epoxit vi cc cht
phn ng ph hp [21, 22].
1.3.1 Cc phng php epoxi ha olefin
C 4 k tht c bn c bit n tng hp epoxit t olefin:
(a)

Epoxi ha vi axit percacboxylic (Prileschafew), ng dng rng ri nht

trong cng nghip, c th c xc tc bi axit hoc enzymes

(b)

Epoxi ha vi axir hu c hay v c, bao gm epoxi ha kim (alkaline)

v nitrin hydroperoxit cng nh epoxi ha xc tc kim loi chuyn tip.

(c)

Epoxi ha vi halohydrin, dng axitt hypohalogen (HOX) v mui ca

chng lm tc nhn cho s epoxi ha olefin lin kt I thiu olefin.

(d)

Epoxi ha vi phn t oxi

Halohydrin c chun b bng vic a axit hypohalogen vo olefin, x

l chng vi kim sn xut epoxit. Phng php ny khng thn thin vi

mi trng. Bi l theo ha hc c in s thu c cc dihalides, ete v mui
halogen.
Epoxi ha vi oxi nguyn t c xc tc bi hp cht cha cc nguyn
t nhm IV-VI B th hin chn lc cao nhng hat tnh oxi ha thp. Cn
nguyn t thuc nhm I, VI, VIII B hot tnh cao hn nhng chn lc li thp
hn. Bc l xc tc duy nht cho vic epoxi ha d th etylen vi phn t oxi,
nhng phn ng ch gii hn ch yu mt vi cht nh etylen v butadien;
epoxi ha cc anken khc th kt qu thu c c hiu sut thp. Nhng phn
ng oxi ha chn lc thng c quan st ch vi nhng cht kh n gin
cha mt nhm phn ng. Do , oxi l tc nhn oxi ha chm c phm vi ng
dng hn ch. Trong trng hp du thc vt, oxi ha du bng O2 dn ti
thoi bin du thnh cc hp cht d bay hi nh xeton v andehit hay cc
dicaboxylic mch ngn. V vy phi c phng php thch hp epoxi ha
du thc vt.
1.3.2 Epoxi ha olefin bng xc tc d th
1.3.2.1 Epoxi ha vi percacboxylic ( hay peraxxit)
Epoxi ha vi percacboxylic thng c xc tc bi axit v c d tan
nh axit sulfuric, tungstic hay molybdic. Nhng axt ny thng xc tc
cho s bin i mt axit cacboxylic, v d acetic, 3-chlorobenzoic v
trifluroacetic thnh cc percacboxylic tng ng. Phn ng gia axit
percacboxylic vi olefin to epoxit ma khng cn xc tc no khc. C ch

phn ng n gin tha nhn iu ( th hin trong hnh 5). Bc cui

cng trong phn ng epoxi ha theo phng php ny l s trung ha axit vi
kim, thng l Ca(OH)2 sinh ra mui, do qu trnh ny khng thn thin
vi mi tng. Thm vo s c mt ca cc axit v c mnh lin quan ti
vn n mn. Bi vy phi dng vt liu t tin c kh nng chng n mn.
Nhng thch thc ba u c gii quyt bng cch d th ha xc tc bng cc
axit nha. Qu trnh ny i hi mt lng ln nha polystyrensulfonic axit.
Nhng ngay t u vp phi kh khn do s thoi bin v mt ha hc v
vt l ca nha, phi thay th sau 6-8 ln chy.
Epoxi ha bng enzym cng chng t hiu qu i vi phn ng
epoxi ha du thc vt. Enzym lipaza v esteraza c c nh ha th hin
hot tnh cao trong vic bin i axit bo v etyl este ca n thnh axit
percacboxylic, tc nhn oxi ha l H2O2. Warwel et. al. dng phng php
ny epoxi ha du thc vt vi hiu sut rt cao

Hnh 5: C ch phn ng epoxi ha olefin vi axit percacboxylic

1.3.2.2 Epoxi ha bng hydroperoxit hu c v v c
Phn ng ny c thc hin trong pha ng th s dng nhng xc tc
c hat tnh cao nht l cc dung dich ca cc kim loi chuyn tip TiIV, VV,
MoVI v WVI. Vi cc hydropeoxit hu c, hat tnh xc tc ca lim loi theo
th t MoVI>> Tiiv~Vv> Wvi nhng di vi hydropeoxit khan th xc tc WVI
cao hn hn cc xc tc khc. Mt vi hp cht ca nhng kim loi ny c
d th ha thnh cng, song s d th ha thay i ng k hat tnh ca
chng. Epoxi ha olefin vi hydroperoxit hu c c xc tc bi cc kim loi
chuyn tip bao gm c ch peroxo-metal; trong bc quyt nh tc

phn ng l bc chuyn oxi t mnh peroxometal electrophin (alkyl ) thnh

olefin nucloephin (hnh 6). Tm kim loi khng phi tri qua bt k s thay i
trng thi oxi ha no trong sut qa trnh xc tc . N ng vai tr nh mt
axit Lewis do rt electron t lin kt O-O v do tng tnh electrophin ca
peroxit ng lin kt. Bi vy, trong trng thi oxi ha cao nht, nhng xc tc
c hat tnh l nhng kim loi m tnh axt Lewis mnh v tnh oxi ha kh yu
( trnh mt electron oxi ha ca peroxit). S miu t xc tc d th c
tng hp t nhng kim loi ny c th hin di y:

Hnh 6: C ch peroxo-kim loi i vi epoxi ha olefin bng RO2H

c xc tc bi kim loi chuyn tip
1.3.2.3 Epoxi ha du thc vt bng xc tc Ti-MCM-41
Tnh cht oxi ha ca Ti-MCM-41 c khng nh l do s tn ti
ca cc ion Ti+4 trong mng li tinh th khi thay th ng hnh cc ion silic.
gii thch ngi ta gi thit rng cc ion Titan tn ti hai dng:
+ Cc ion Ti+4 v tr mng li t din trong khung cu trc ca
MCM-41
+ Cc ion Ti+4 nn ngoi mng li di dng anatas.
T l cc dng titan ny ph thuc phc tp vo cc yu t nh hng
ca qu trnh tng hp. S c mt ca Titan dng anatas lm tng t l cc phn
ng ph gy phn hy hydroperoxit (H2O2) thnh O2 v H2O, polime ha to
thnh cht nha. V th vt liu khng c mt dng anatas c hot tnh xc tc

v chn lc cao cho mt s lng ln cc hp cht hu c. Khi Titan thay

th ng hnh cho silic trong mang li tinh th, cu trc ca lin kt Titan vi
cc oxy ca cc Silic ln cn ang l vn tranh ci . Cu trc ca lin kt
Titan gm 2 dng:

Hnh 7: Dng tn ti ca Titan trong mng cu trc

Titan c ha tri 4 l ha tr bn v trong mi trng oxy ha, ha tr ny
vn duy tr v cng c th b khch thch ln s phi tr cao hn. Trong cc
phn ng oxi ha s dng xc tc Ti-MCM-41vi tc nhn oxi ha l H2O2,
ban u cc phn t H2O2 qua cc ca s vo mao qun v hp ph ln tm
Titan hot tnh bn trong mao qun to nn cc phc Titanperoxo.
O
Ti

Si

Si
O

O
Ti

Si
O

Si
O

+ H2O2
- H2O

+ H2O2

Ti

Si
O

O
O

Si
O

OH O
Ti
Si
O
O
O

O
Si

Si

Si
O

Si

Ti

O
O

Si
O

+ H2O2
- H2O
Si

Si

Si

O
H

Ti
O O

O
O
H

Si
O

- H2O
Si

Si

Si

Ti
O O

O
O

Hnh 8: Cc phc titanperoxo gia cc phn t H2O2

v tm hot tnh Titan trong mi trng nc
Corma v cc cng s xut c ch phn ng epoxi ha olefin
trn h xc tc ny, s dng H2O2 theo s sau:

Hnh 9: C ch phn ng epoxi ha ca Ti-MCM-41

Si

CHNG 2: THC NGHIM

2.1 Phng php tng hp

2.1.1 Tng hp vt liu mao qun trung bnh MCM-41
 Nguyn liu:
-

Cht HBM: Cetyltrimetylamonibromua (CTAB)

C16H33(CH3)3NBr (Merck)

Ngun silic: Tetraetylorthosilicat (TEOS ) (C2H5O)4Si (Merck

Ispropanol tuyt i (iPOH): (CH3)2CHOH (Merck)

Dung dch amonihiroxit 25%: NH4OH

Nc ct

 Dng c:
-

My khy t

Cc thu tinh

Pipet

Cng t ht

Bnh nh git

Giy pH

 Qui trnh tng hp:

- Ho tan CTAB vo hn hp iPOH v nc c dung dch 1.
- Thm mt lng nht nh NH4OH vo dung dch 1 sao cho pH = 10.
Khuy mnh hn hp trn trong 15 pht c dung dch 2 c mu trong sut.
- Nh t t TEOS c trn u trong isopropanol vo dung dch 2. Khi
qu trnh hnh thnh gel s bt u. Khuy mnh trong 2h thu gel c mu trng
c. Trong khi khuy lin tc chnh bng NH4OH sao cho pH khng i khong 10.
Sau un hi lu trong 1 ngy ri lm lnh ti nhit phng.

- Lc ra sn phm bng nc ct n khi pH=7. kh qua m nhit

phng ri sy 1100C trong 5h,
- Nung di dng khng kh nhit 550oC, sn phm thu c c mu
trng mn. Cu trc ca mu c xc nh bng ph nhiu x Rnghen (XRD),
ph tn x Raman.
C16TAB

iPOH

khuy 15

dd NH4OH

Dung dch ng th

Gel m u trng c

khuy 2h
un hi lu trong
24h 500C

Lc ra ti pH=7

kh qua m v sy
1100C trong 5h

Nung 550oC

MCM-41

iPOH + TEOS

Hinh 10 : Qui trnh tng hp MCM-41

2.1.2 Tng hp Ti-MCM-41

 Nguyn liu:
-

Ngun Silic: Tetraorthosilicat (TEOS ) (C2H5O)4Si (Merck )

Tetrapropylamonihydroxit 40% ( TPAOH): (C3H7)4NOH (Merck)

Ispropanol tuyt i (iPOH): (CH3)2CHOH (Merck )

Dung dch amonihiroxit 25%: NH4OH

Nc ct

 Dng c:
-

My khy t

Cc thu tinh

Pipet

Cng t ht

Bnh nh git

Giy pH

 Qui trnh tng hp:

- Ho tan CTAB vo hn hp TPAOH v nc c dung dch 1 sao
cho pH=12.
- Khuy mnh hn hp trn trong 15 pht c dung dch c mu
trong sut.
- Nh t t TEOS c trn u trong isopropanol vo dung dich 1
c dung dch 2
- ng thi khy mnh TIPOTi vi isopropanol c dung dch 3.
- Nh tht t t dung dch 3 vo dung dch 2 khuy mnh, pH dung dich
vn khng i
- Chuyn gel vo bnh cu ct hi lu trong 1 ngay nhit 50oC. Sau
lm lnh n nhit phng. Lc ra sn phm ct ti pH=7.
- kh qua m nhit phng ri sy 1100C trong 5h.
- Nung trong khng kh 550oC s thu c bt mu trng mn. Cu
trc ca mu c

- Xc nh bng ph nhiu x Rnghen (XRD), ph tn x Raman.

C16TAB

H2O +
TPAOH
Khuy 2h

TEOS +
isopropanol

Khuy

Dung dich 1

15

TIPOTi +
isopropanol

Dung dich 2

un hi lu trong 24h 500C

Sy kh qua m
90oC

Nung 550oC

Ti-MCM-41

Hnh11: Qui trnh tng hp Ti-MCM-41

2.2 nh gi hot tnh xc tc trong phn ng epoxi ha Metyl oleat
 Nguyn liu:
- Metyl oletat
- Dung dch H2O2
- Xc tc: + Ti-MCM-41 t l Ti/ Si khc nhau
+ TiO2/ MCM-41
- Dung mi: + Metylnitrin (MeCN),
+ imetylfomamit (DMF)

+ n-hecxanol
 Dng c
-

My khuy t

Sinh hn ng

H iu nhit

Nhit k

Bnh cu 3 c 50ml

Cc Pipet vi cc th tch khc nhau.

L ng mu phn tch sc k.

Quy trnh phn ng

- Th nghim thc hin pha lng.
- Phn ng epoxi ha c tin hnh nh bnh cu 3 c t trong bt du
gi nhit mong mun.
- Metyl oleat c dng lm cht u (Merck, 97% trng lng cis-9octandecenoic axit metyl este). Tt c xc tc c hot ha qua m.
- Cht nn v dung mi c trn u 15 pht nhit 700C.
- Sau xc tc c thm vo, hn hp khuy mnh trong 15 pht
phn tn u xc tc.
- Hydroperoxit c thm vo mt ln.
- Thi kh, tc dng kh l 5ml/pht.
- Hn hp phn ng c phn tch trn my sc k kh (GCMS).
T l cc cht u nh sau:
- H2O2/metyl oleat = 1.1 mol
- Metyl oleat/ xc tc = 20g/g
- Dung mi / metyl oleat =1g/g

Etyl oleat +
dung mi
Gia nhit
Khuy 15

Xc tc
hot ha

Hn hp 1
Khuy
H2O2

Hn hp 2

Thi kh

Quay li tm
thu sn phm

Phn tch sn phm

trn GCMS
Hnh 12: Quy trnh phn ng epoxi ha Metyl oleat

Hinh13: S thit b phn ng oxi ha Metyl oleat

2.3 Phn tch sn phm phn ng bng thit b sc k kh ghp ni

khi ph (Gas chromatography Mass Spectrocopy - GC-MS)
Thit b sc k kh khi ph da trn vic ghp ni gia mt thit b sc
k kh v mt thit b khi ph. Sc k kh thc hin vai tr tch cc cht trong
hn hp v khi ph thc hin vic nhn bit cc cht. Mu phn tch sau khi
i qua ct tch, cc cht ln lt c a vo b phn nhn quang ca my
khi ph thc hin vic phn mnh, sau tip tc qua b phn chuyn tn
hiu quang thnh tn hiu in. Cc tn hiu c th hin bng cc vch ph
trn ph . Mi vch ph c trng cho mt mnh ca phn t cht. T
xc nh c cht. Nh vy vic ghp ni gia hai thit b sc k v khi ph
to ra mt thit b va c kh nng tch cht, va c kh nng nhn bit
c cc cht m sc k kh tch ra c. V vy, GC-MS l mt thit b hu
hiu, c s dng rng ri trong vic phn tch cc hn hp sn phm phn
ng. Trong trng hp ny, khi ph c xem nh l tect ca my sc k.
Sn phm ca phn ng c phn tch bng phng php sc k kh
ghp ni khi ph. Thit b phn tch GC-MS HP 6890 vi tect khi ph
MS HP 5689 (M). Ct sc k mao qun HP-5 (5% metyletylsiloxan, 30m x
0,5mm x 0,25m) ti Trung tm Ho du Khoa Ho hc Trng i hc
Khoa hc T nhin
Ch phn tch sc kh:
- Nhit inlet: 2500C
- Nhit MSD: 2500C
- Tc dng kh: 6,2 psi
- Ch phn tch Split
- Ch chy: Scan
- chia dng: 200: 1
- K thut bm mu: bm lng vt

Chng trnh nhit :

3 pht
2800C

post run

50C/ pht
210oC 1 pht
100 C/ pht
1000C
1 pht

2.3 Cc phng php ho l c trng

2.3.1 Phng php ph nhiu x Rnghen (X-ray difraction)
Theo l thuyt cu to tinh th, mng tinh th c xy dng t cc
nguyn t hay cc ion phn b u n trong khng gian theo mt quy lut xc
nh. Khi chiu chm tia rnghen ti b mt tinh th v i su vo bn trong
mng li th mng li ny ng mt vai tr nh mt cch t nhiu x c
bit. Cc nguyn t, ion b kch thch bi chm tia X s thnh cc tm pht ra
tia pht x. Hn na cc nguyn t, ion ny c phn b trn cc mt song
song

Theo iu kin giao thoa, cc sng pht x trn 2 mt phng cng pha
th hiu quang trnh phi bng s nguyn ln di bc sng (). Suy ra:
2d sin = n

( h thc Vulf - Bragg)

Cn c vo cc i nhiu x trn gin (gi tr 2) c th suy ra d theo

biu thc ca V-B. So snh gi tr d tm c vi ng chun s xc nh
c thnh phn cu trc mng tinh th ca cht cn nghin cu. V vy
phng php ny c s dng rng di trong nghin cu cu trc vi tinh th
ca vt cht.
a vo ph X-ray cng c th xc nh c tinh th. l phn
trm t l gia cng pic c trng mu nghin cu so vi cng pic c
trng mu chun.
Trong nghin cu c trng, gin nhiu s Rnghen XRD c ghi
trn my SIMENS D5005 khoa vt l cht rn, trng i hc KHTN, vi ng
pht tia X bng ng, K =1,5406, U=30 Kv, I=25A, nhit 25oC, gc qut
2 (t 1o n 15o), tc qut 0,2 /pht.
2.3.2 Phng php ph tn x Raman
Khi nh sng i qua vt no , phn nh sng b lch i so vi hng
ban u l hin tng tn x. Tn x gm 2 phn : tn x Rayleigh nh sng
n hi theo mi hng v tn x Raman nh sng khng n hi
Tn x Raman l phng php ph bin dng nghin cu cu trc vt
liu. Php o ny cho php xc nh cu trc ca cc ht c kch thc nano v
xc nh lin kt b mt. Theo nh lut Bolzman, iu kin nhit mi
trng hu ht phn t trng thi dao ng c bn. Ch c mt s nh trng
thi dao ng kch thch. Khi chiu mt chm tia sng laser vo mu, s tng
tc gia nh sng vi phn t lm cho lm cho lp v in t ca cc nguyn
t trong phn t b bin dng, dn ti s sai lch v tr ca cc ht nguyn t
trong phn t b dao ng i vi tn s nht nh. Nng lng ca cc tia
Raman bng hiu hay bng tng nng lng ca cc tia kch thch ban u v
nng lng dao ng

E = Eo Ed
Hay

h = ho hd

Trong :
Vch stockes c nng lng tn x thp hn (ng vi du - )
Vch anti- stockes c nng lng tn x cao hn (ng vi du + )
Ph Raman ghi nhn tn hiu c trng cho dao ng phn t ti tn
s xc nh. Php o ph tn x Raman l php o v cng quan trng trong
nghin cu cu trc vt liu. y l phng php vt l khng ph hy mu.
Ph Raman ch ra cc vch c trng, tiu biu cho cc nhm nguyn t v xc
nh ti tn s xc nh. Cng ca cc vch ph t l vi nng tng
thnh phn ring bit ca hn hp.
Trong nghin cu c trng, cc mu c o trn my vi quang ph
Raman ca hng Renishaw (Anh) khoa vt l in t, trng i hc Bch
Khoa H Ni.

CHNG 3: KT QU V THO LUN

3.1 Tng hp vt liu
S dng cht nh hng cu trc (SDAs) to ra bc ngot to ln
i vi cng ngh ch to MCM-41 ni ring v h M41S ni chung. Cht to
cu trc cho php tng hp mt lng ln cc vt liu khng tn ti trong t
nhin v bn trong iu kin nht nh. K t nm 1972 khi ln u tin s
dng template ch to thnh cng zeolit ZSM-5, SDAs khng ngng c
ci tin v pht trin. Hin nay cht to cu trc c chia thnh 2 loi chnh :
loi khng ion (BRIJ-56), lai c ion (cc amin bc 4 v cc mui
ankyltrimetylamoni halogenua).
Cc mu vt liu c tng hp theo phng php c trnh by
trong chng 2 (thc nghim). Tng hp MCM-41 t tin cht Silic TEOS v
cht nh hng cu trc CTAB c thc hin kh thun li. Vi thnh mao
qun siliconat v nh hnh, vt liu ny thng l cht nn phn tn cc h cu
t xc tc. Vic a Titan vo thay th ng hnh Silic trong vt liu nn
MCM-41c thc hin theo t l khc nhau (bng 2), lng CTAB trong tt
c cc mu l nh nhau bng 2,5 g.
Bng 2: Cc mu vt liu c tng hp

K hiu mu

Ti/Si 100%

Nhit
0

Cht to

(tnh theo s mol)

tng hp ( C)

mi trng

M1

50

TPAOH

M2

25

TPAOH

M3

50

TPAOH

M4

4.5

50

TPAOH

M5

50

TPAOH

M6

50

NH4OH

M7

25

TPAOH

M8

10% TiO2/ MCM-41

Cc mu trn c c trng bng k thut vt l hin i XRD,

RAMAN v nh gi hot tnh trong phn ng oxi ha chn lc metyl oleat
thep phng php nu trong chng 2.
3.2 c trng xc tc bng nhiu x tia X ( 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. V MCM- 41 c thnh SiO2 v nh hnh nn XRD
l cng c xc nh cu trc mao qun [12]. Nh phng php ny m
nhng nhn inh ban u v quan trng c xc nh mt cch nhanh chng
v chnh xc.
Gin nhiu x Rnghen ca mu M1, M3, M4, M5 c th hin
trong cc hnh sau y:

Hnh 14: Gin nhiu x tia X ca mu M1

Trn gin thy xut hin cc pic cng ln gc 2 2.20 v 2 pic

c cng nh tng ng vi gc 2 4o v 2 5o l du hiu c trng cho
cu trc lc lng ca vt liu mao qun trung bnh MCM-41 (Theo Kresge v
cc cng s pic vng gc hp 2 <10o c trng cho cu trc hecxagonal).
Nhng pic ny ch mt phn x (ch s Miller) tng ng l cc mt 100, 110
v 200. iu ny khng nh mu tng hp c c cu trc u n [ ].
2400
2300
2200

d=35.59

2100
2000
1900
1800
1700
1600

Lin (Cps)

1500
1400
1300
1200
1100
1000
900

d=21.016

800
700
600
500
400
300
200
100
0
1

10

20

30

40

50

2-Theta - Scale
File: Thuy-KhHoa-Ti-13N.raw - Type: 2Th/Th locked - Start: 0.500 - End: 50.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 03/21/07 17:36:40

Hnh 15: Gin nhiu x tia X ca mu M3

1900
1800
1700

d=35.19

1600
1500
1400
1300

1100
1000
900
800
700

d=21.160

Lin (Cps)

1200

600
500
400
300
200
100
0
1

10

20

30

40

2-Theta - Scale
File: Thuy-KhHoa-Ti-11 N.raw - Type: 2Th/Th locked - Start: 0.500 - End: 50.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 03/21/07 17:54:10

Hnh 16: Gin nhiu x tia X ca mu M4

50

d=36.82

4000

2000

d=21.499
d=18.709

Lin (Cps)

3000

1000

0
1

10

20

30

40

50

2-Theta - Scale
File: Thuy-KhHoa-Ti-12N.raw - Type: 2Th/Th locked - Start: 0.500 - End: 50.000 - Step: 0.030 - Step time: 0.8 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 03/21/07 18:25:19

Hnh 17: Gin nhiu x tia X ca mu M5

Nh trn phn tch vic thay th ng hnh cc ion kim loi vo mng
t din cng vi Silic qua lin kt cu oxi phi tun theo nguyn tc ph hp
v kch thc ion rMe < 0.4 . M bn knh ion ca Titan l rMe <0.34 c th
i vo mao qun hecxagonal to lin kt Ti-O-Si m khng ph v cu trc.
Tuy nhin so vi Si hay Al, vic tng hp MCM-41 c a Titan vo mng
thc hin kh kh khn do tin cht cha Titan dng monome tetraoctotitanat
phi c ha tan trong dung mi thch hp trnh s thy phn tc thi.
Mt khc, ng nn vng gc rng ca cc mu M3, M4, M5 khng
thy xut hin cc tn hiu nhiu x ca titan oxit dng tinh th (anatas, brockit,
rutin).
Trn gin cc nh c trng ca MCM-41 sc nhn. Vic thay i
hm lng Titan cng khng gy nh hng g n cu trc lc lng v trt
t ca mao qun. Qu trnh tin hnh c hiu qu 500C. kho st nh
hng ca kh nng kt hp thy nhit, tin hnh thc hin nhit thng.
Kt qu nh sau:

190
180
170
160
150
140

120
110
100
90

d=32.399

Lin (Counts)

130

80
70
60
50
40
30
20
10
0
0.5

10

2-Theta - Scale
File: thuy-K48B-Mau Ti -5.raw - Start: 0.500 - End: 10.000 - Step: 0.010 - Step time: 0.5 s - 2-Theta: 0.500 - Theta: 0.250 - Anode: Cu - WL1: 1.5406 - Creation: 3/5/2007 12:40:58 PM

Hnh 18: Gin nhiu x tia X ca mu M2

Mau Ti-11N
27 0
26 0
25 0
24 0

d=35.411

23 0
22 0
21 0
20 0
19 0
18 0

Lin (Counts)

17 0
16 0
15 0
14 0
13 0
12 0
11 0
10 0
90
80
70
60
50
40
30
20
10
0
0 .5

2-Theta - Scale
File : th u y-K48 B-Ma u Ti-1 1N.r aw - S tar t: 0 .50 0 - En d: 10.0 00 - Ste p : 0 .01 0 - Ste p tim e: 0 .5 s - 2 -Th eta : 0.5 00 - The ta: 0 .25 0 - A nod e: Cu - W L1 : 1.5 40 6 - Cre ation : 3 /1 2/2 00 7 2 :27 :45 PM

Hnh 19 : Gin nhiu x tia X ca mu M7

10

Kt qu XRD cng xut hin cc pic c trng tuy nhin do cng

nh v dong. Do nhit thng qu polime ha ngng t silicat xy ra
chm, mu cha Ti cng nhiu x thp, nh t hn, cc gc 2 = 40 v 50
r nt, mao qun khng trt t.
so snh nh hng ca mi trng baz ti qu trnh tng hp TiMCM-41 tin hnh thc hin khi cht chnh pH l NH4OH. Kt qu gin tia
X nh sau:

Hnh 20: Gin nhiu x Rnghen ca mu M6

S dng NH4OH cht chnh pH c u im l r tin, tuy nhin vic iu
chnh l rt kh khn, xc sut thnh cng tng i thp. Hn na amonic
lin tc bay hi trong qu trnh tng hp khin h hp gim pH lin tc. Do
tnh ng u km hn so vi vic dng TPAOH.
Thc hin qu trnh tm Titan ln cht mang c b mt ring ln l
MCM-41( mu M1).

50

30

d=39.620

Lin (Counts)

40

20

10

0
0 .5

10

2-Theta - Sc ale
File : th u y-K 48 B -Ma u M CM4 1 -1 0% TiO 2 -2 .ra w - Type : L o cked Co up le d - S tar t: 0 .5 00 - En d : 1 0.0 00 - S tep : 0.0 10 - Ste p tim e: 0 .5 s - Te mp .: 25 C (Ro om ) - Ti me Sta rte d: 11 s - 2 -Th eta : 0.5 00 - The ta: 0

Hnh 21: Gin tia X ca 10% TiO2/ MCM-41 vng gc hp.

25 0
24 0
23 0
22 0
21 0
20 0
19 0
18 0
d=3.513

17 0

15 0
14 0
13 0
12 0
11 0
10 0
90
80

50

30

d=1.701

40

d=1.481

d=1.890

60

d=1.664

70

d=2.390

Lin (Counts)

16 0

20
10
0
20

30

40

50

60

2-Theta - Sc ale
F ile : th u y-K 48 B -M a u M C M 4 1 -1 0% T iO 2 -g oc l on .ra w - T y pe : L o c ked C o up le d - S tar t: 2 0 .0 0 0 - E nd : 70 .01 0 - St e p: 0 . 03 0 - S tep t im e : 0.8 s - T e m p .: 2 5 C ( R oo m ) - T im e S tar ted : 4 s - 2 -T h et a : 20 . 00 0 - T
01 -0 78 -2 4 86 (C ) - An at a s e , s y n - T iO 2 - Y : 7 5. 8 9 % - d x by : 1 . - W L : 1.5 40 6 - T etr ag on a l - a 3 . 78 4 50 - b 3 . 78 45 0 - c 9.5 14 3 0 - a lp ha 90 .00 0 - be t a 9 0. 0 00 - g am m a 90 . 00 0 - B o dy - c en t er ed - I 41 / am d ( 14 1) -

Hnh 22: Gin tia X ca 10% TiO2/ MCM-41 vng gc rng.

70

Qua hnh ta thy trt t mao qun c s thay i do cng tn hiu

gc 2 2,20 khng cn sc nt nh mu cha tm. Nh vy khi tm cc oxit
kim loi lm cht nn, cc oxit phn b bn trong mao qun lm kch thc
mao qun thay i v khng cn ng u. vng gc ln tn ti pha TiO2 th
hin trong gin XRD qua cc nhiu x gc 2 bng 25.30, 370, 380, 38.50,
480, 540, 550, 62.50...
Vi nghin cu c trng vt liu bng Rnghen, Ti-MCM-41 cho thy
kh nng Titan i vo mng t din, ng hnh cng Silic, lin kt vi Silic qua
cu oxi. Cc mu trn gin nh sc nt, s che lp ca anatas khng xc
nhn, ta thu c Mespore. Tuy nhin phng php ny cha c trng cho
kh nng thay th Titan trong mng t din. Do phi nhn dng Ti+4 bng
phng php Raman hay UV-VIS. Bi v ph UV-VIS khng nhy trong vic
pht hin nhng mnh Titan do trong khun kh bi kho lun ny tin
hnh o Ti-MCM-41 theo phng php Raman
3.3 Nhn dng Ti+4 trong v ngoi mng MCM-41 bng ph tn x
Raman
Ti- MCM-41 l cht xc tc c hot tnh v chn lc cao cho phn
ng oxi ho chn lc cc hp cht hu c trong iu kin mn, bi n kt hp
nhng u im ca kh nng phi tr cao ca ion Ti(IV) vi tnh k nc ca
mng li silicat. Trong vt liu Ti-MCM-41, Titan c th tn ti hai dng:
Titan trong mng tinh th v Titan ngoi mng tinh th dng TiO2 (anatas).
Hot tnh xc tc ca Ti-MCM-41 tng theo hm lng Ti trong mng, trong
khi dng Ti ngoi mng lm gim b mt ring, hot tnh v chn lc xc
tc. V vy, vn nhn dng v xc nh cc dng Titan trong vt liu rt
quan trng i vi qu trnh tng hp xc tc [11]
Php o ph tn x Raman l mt php o v cng quan trng trong
nghin cu cu trc vt l. Ngoi u iim khng ph h mu n cn c kh
nng xc nh cu trc nano v cc mt lin kt trn b mt vt liu. Ph
Raman ch ra cc vch c trng, tiu biu cho cc nhm nguyn t ti tn s
xc nh. Cng vch ph t l vi thnh phn ring bit ca hn hp.

R a m a n M C M -4 1

100000

4 8 0 .1 4
4 2 9 .3 5

counts

90000

80000

1 5 0 .3 5

70000

60000
200

400

600

800

R a m a n s h if t/ c m

1000

1200

-1

Hnh 23: Ph tn x Raman ca mu M1

R a m a n T i- M C M - 4 1
1 5 0 .9 9
13000
12000

4 2 9 .5 4
4 8 0 .6 1

11000

counts

10000

6 1 0 .1 2

9000

8 0 4 .3 5

9 6 9 .8 6

8000
7000
6000
5000
200

400

600

R a m a n s h if t/ c m

800
-1

1000

Hnh 24: Ph tn x Raman ca mu M3

R a m a n T i- M C M - 4 1
1 5 0 .4 1
5000

4 8 0 .0 6
4 3 0 .0 5

4000

6 0 9 .8 9
8 1 0 .3 2

9 7 0 .0 2

3500

3000

2500
200

400

600

800

R a m a n s h if t / c m

1000

-1

Hnh 25: Ph tn x Raman ca mu M4

R a m a n T I- M C M - 4 1

20000

19500

1 5 0 .2 6

9 7 0 .2 5

4 7 8 .8 6
4 2 8 .3 5

19000

6 1 0 .1 2
counts

counts

4500

8 1 2 .6 5

18500

18000

17500

17000
200

400

600

800

R a m a n s h ift/ c m

-1

1000

1200

Hnh 26: Ph Raman ca mu M5

Ph Raman ca mu MCM-41 vi nhng pic c trng 150, 430 v 480
cm-1. Trong khi ph Raman ca Ti-MCM-41 gm cc pic c trng cho dao
ng bt i xng ca lin kt Si-O-Ti trong mng cu trc MCM-41 nh 810
cm-1 v c bit l 970 cm-1. Hm lng Titan trong mng t l thun vi
cng nhm pic ny. Ngoi ra trn nh ph thy pic 610 cm-1 th hin s c
mt ca Titan anatas. iu ny khng h mu thun vi kt qu XRD. Bi l
trong gin nhiu x tia X s c mt ca Titan anatas qu nh (di 5%),
khng th nhn bit c. Qua mt ln na khng nh nhiu x Raman l
mt phng php rt nhy c dng c hiu qu trong vic nhn bit s c
mt ca Titan trong v ngoi mng.
3.4 nh gi hot tnh xc tc ca vt liu Ti-MCM-41 trong phn
ng oxi ha chon lc metyl oleat.
Cc xc tc mang Titan cha 2% TiO2 v khi lng mang trn Silic
c pht trin u tin bi Shell l xc tc epoxi ha di th thc s u tin
c s dng lin tc trong pha lng. Nhng xc tc ny dng epoxi ha
thng mi propen vi Hydroperoxit cho hiu sut 93-94% v 96% tnh chn
lc hydroperoxit. Ngc vi hp cht cha dung dich TiIV (xc tc n gin),
TiIV/ SiO2 th hin hot tnh v chn lc cao so vi Molypden ng th.
Phi tha nhn rng tm Titan tn cng vo t nht ba nhm sylanoxy trn b
mt lin kt Silic. Hot tnh cao ca TiIV/ SiO2 do tng ng thi tnh axit
Lewis ca TiIV, phi tr li cc electron that ra t cc nhm sylanoxy
(sylanoxy ligands); mt khc l do cc tm Titan ring bit nm v tr c lp
ngn cn s oligome ha thnh cc mnh -oxo khng hot ng. Tng t
nh cc xc tc ng th cha Titan, TiIV/ SiO2 rt d b mt hat tnh, do
nn TiIV/ SiO2 l xc tc khng hiu qu i vi phn ng epoxi ha bng
H2O2. Vn mi c khc phc gn y nh vic khm ph ra TS-1
(Titansilicalit-1). Bi tnh ht nc, n l xc tc hiu qu cho phn ng epoxi
ha chn lc bng H2O2 thng qua nhiu iu kin trung gian. Nh trn
phn tch do gii hn ca ng knh ng hc dn ti vic kt hp TiIV vo

cc ry phn t l rng hnh thnh Ti-MCM-41, Ti-MCM-48, Ti-. Ty vo

kch thc cht hot ng b mt dung d tng hp m Ti-MCM-41 c ng
knh mao khong 20-50 nn c th epoxi ha cc cht ln nh metyloleat.
c trng v tnh cht ca h xc tc Ti-MCM-41 mt ln na c
nghin cu thng qua tnh cht ha hc ca qu trnh chuyn ha hp cht
cha ni i. Metyloleat c nhiu trong ht ci du c s dng rng ri, l
nguyn liu u trong tng hp hu. Sn phm chuyn ha ca n c nhiu
ng dng quan trng trong cng ngh cht nh hng, cht trung gian cho cc
qu trnh ha dc v nhiu tng s dng sn phm epoxi ha v hidro ha
cho qu trnh ch to cht hot ng b mt khng ion khi kt hp vi nhng
ph gia khc...[ ]. Tuy nhin phn ng epoxi ha olefin ni chung v oxi ha
metyloleat ni ring l phn ng kh khim sot v cho nhiu sn phn trung
gian phc tp, kh dng li giai on s cp m c th thc hin cc qu
trnh th cp oxi ha su. Metyl oleat l i din cho du thc vt. N c
dng kh ph bin, ng thi c kch thc phn t ph hp vi cc nghin
cu kho st chuyn ha trn c s vt liu xc tc mao qun trung bnh TiMCM-41
(d1= 9.478, d2= 4.107, d3= 9.594).

Hnh 27 : Cu to khng gian ca Metyl oleat

3.4.1 Phn ng oxi ha Metyl oleat trn nhng mu xc tc khc

nhau.
Phn ng oxi ha Metyl oleat thc hin trn hai xc tc khc nhau l
TiO2/ MCM-41 v Ti-MCM-41. Kt qu nh sau:
Bng 3: Phn ng epoxi ha Metyl oleat trn hai xc tc khc nhau,
dung mi n- hecxanol, nhit 700C, thi gian phn ng 3h.
Mu xc tc

chuyn ha (%)

chn lc sn phm (%)

TiO2/ MCM-41

37.21

3.82

Ti-MCM-41 (M3)

26.17

10.31

Phn ng epoxi ha bng xc tc TiO2/ MCM-41 cho chuyn ha cao

v chn lc sn phm thp hn Ti-MCM-41. iu ny han ton ph hp
vi l thuyt thng thng. Bi l TiO2/ MCM-41 c kh nng phn ng mnh
v gy nhiu phn ng ph, phn ng th cp. nh hng phn ng khng ch
n thun xy ra theo hng oxi ha v tr ni i m cn phn ng oxi ha ct
mch, hidroxi ha m vng epoxi...Ngc li Ti-MCM-41 nh trn ni l
mt xc tc oxi ha m du.
Tuy nhin phi cng nhn rng phn ng xc tc d th l mt qu trnh
rt phc tp xy ra qua nhiu giai on. Cc cht tham gia phn ng trc khi
tng tc vi nhau cc tm xc tc trn b mt phn cch pha cn phi c
khuch tn n v hp ph trn cc tm . Mt khc qu trnh cn ph thuc
vo cu trc mao qun v tnh cht ha l b mt cht rn, iu kin thc hin
qu trnh nh nhit , thi gian, dung mi v nng cc cht tham gia phn
ng.
3.4.2 Kho st nh hng ca dung mi ti phn ng oxi ha Metyl
oleat.

Thc hin phn ng oxi ho metyl oleat bng xc tc Ti-MCM-41 (M3)

trn hai h dung mi khc nhau l Metyl nitrin + imetylfomamit v
n -hecxanol. Kt qu nh sau :
Bng 4: Phn ng epoxi ha Metyl oleat trn hai dung mi khc nhau,
nhit 700C, thi gian phn ng 3h, xc tc Ti-MCM-41
Dung mi

chuyn ha

chn lc

MeCN + DMF

Vt

Vt

n- hecxaol

26.17

10.31

Metyloleat l este ca axit khng no mch di, do n rt k nc.

Trong khi tc nhn oxi ha l dung dch H2O2. trnh s phn tch pha
phi s dng dung mi phn cc. Theo L.A.Rios th dung mi phn cc c
proton th c hiu qu hn dung mi phn cc khng proton. iu ny mt ln
na c khng nh qua thc nghim. R rng dung mi n-hecxanol cho
chuyn ha v chn lc hn hn dung mi MeCN v DMF. Tuy nhin c
hai dung mi ny vn cho kt qu khng cao. iu ny c th khc ph khi
dng tc nhn oxi ha l terbutylhidroperoxit (TBHP) v dung mi l n-hexan
hay toluen. Khi s trnh s phn tch pha, tng tc gia cc cu t phn
ng s d dng hn. Do vy phn ng epoxi ha Metyl oleat s cn c tip
tc nghin cu su hn na.

CHNG 4: KT LUN

T cc kt qu thc nghim v c trng xc tc, c th a ra

cc kt lun sau:

tng hp thnh cng vt liu mao qun trung bnh

MCM-41 v Ti-MCM-41 vi t l khc nhau. S dng cc tin cht c

tinh khit cao nh ngun Titan hu c v silicon ankoxit cht to
cu trc l amin bc 4 (CTAB).


Kho st mt s iu kin nh hng ti qu trnh tng

hp nh nhit , cht to mi trng baz (NH4OH v TPAOH) trong

qu trnh tng hp.


ng dng cc phng php vt l hin i nh: ph

nhiu x Rnghen (XRD), ph tn x Raman trong nghin cu c

trng xc tc.


chng minh c vt liu c mao qun trung bnh.

Titan thay th ng hnh Silic trong khung cu trc. C s xut hin

ca TiO2 ngoi mng tinh th.


nh gi hot tnh ca xc tc TiO2/ MCM-41 v Ti-

MCM-41 thng qua phn ng oxi ha Metyloleat. Thc hin qu

trnh iu kin nhit thch hp v c s kho st dung mi.
Phn ng bc u c kt qu v nh hng cho nhng nghin
cu su hn.

CHNG 5: TI LIU THAM KHO

1. Phm Thanh Huyn, o Vn Tng, Hong Trng Ym,
Nghin cu v c trng mt s h xc tc oxit kim loi chuyn tip mang trn
oxit Titan bng phng php XRD v TPR, tp ch ho hc, T.42 (3), Tr.298302, 2004.
2. L Th Hoi Nam, Trn Th Nh Mai, Nguyn Thi Phng, Mt
s c trng ca vt liu mao qun trung bnh, tng hp vt liu ZSM-5/MCM41, hi ngh cng ngh ho du trong th k XX-XXI, Tr 346-361, 2002
3. L Th Hoi Nam, Trn Th Nh Mai, Nguyn Hu Th Anh,
tng hp v c trng vt liu mao qun trung bnh Si-MCM-41, Ti-MCM-41,
tp ch ho hc s 2, 2002.
4. L Thi Hoai Nam, Nguyn Hu Ph, Tng hp v c trng ca
vt liu mao qun trung bnh Al-Si-MCM-41, Tp ch ha hc T.43 (4), Tr.406410, 2005.
5. Trn Th Nh Mai, Nguyn Th H, Nguyn Minh Th, Ng
Quc Tun, Phn ng oxi ho - spinen trn h xc tc a oxit V2O5- ZrO2/
MCM-41, hi ngh hp ph xc tc ln th 2, Hu, 9-2005
6. Nguyn Hu Ph, Cng ngh ho hc du m trong tng lai, Vai
tr ca xc tc (zeolit v cc vt liu xc tc khc) trong lc- ho du, hi
ngh cng ngh ho du trong th k XX-XXI, Tr 52-67, 2002.
7. Nguyn Vit Sn, Nghin cu h xc tc perovkit/vt liu mao qun
trung bnh tng hp, c trng v tnh cht xc tc trong phn ng oxi ho
hon ton metan, lun n tin s ho hc , 2005
8. Mai Tuyn, Xc tc zeolit trong ho du, NXB KHKT, 2004

9. Nguyn nh Tuyn, Tng hp v tnh cht xc tc oxy ho ca

Titan silicalit-1, lun n tin s ho hc, 2002.
10. Nguyn nh Tuyn, L Th Hoi Nam, Nguyn Hu Ph,
Nguyn Xun Ngha, Nhn dng Titan trong v ngoi mng tinh th TS-1
bng ph IR v Raman, tp ch ho hc, T.43 (5) Tr.539-543, 2005
11. Nguyn nh Triu, Cc phng php vt l ng dng trong ho
hc, nh xut bn HQGHN, 1999
12. Agnes Szegedi, Zoltn Knya, Dra Mhn, Edit Solymar,
Gabriella Pl- Borbly, Zsolt E.Horvth, Lszl P.Bir, Imre Kirici,
Spherical mesoporous MCM-41 materials containing translation metals:
synthesis and characterization, Applied catalysis A: General 272 ( 2004) 257266
13. Chi- Feng Cheng, Dong Ho Park and Jacek Klinowski, Optimal
parameters for the synthesis of mesoporous molecular sieve {Si]-MCM-41, J.
Chem.Soc., Faraday Trans., 93 (997) 193-197.
14. Frank Hoffmann, Maximilian Cornelius, Jurgen Morell, and
Michael

Froba,

Silica-Based

Mesoporous

Organic-Inorganic

Hydrid

Materials, Angew.Chem.Int.Ed 45 (2006)3216-3251

15. Hong-Ping Lin, Yah-Ru-Cheng, Chung-Rong-Lin, Feng-Yin Li,
Chang-Li Chen, She-Tin Wong, Soofin Cheng, Shang- Bin Lui, Ben-Zu
Wan, Chung- Yuan Mou, Chin- Yuan Tang and Ching- Yen Lin, The
synthesis and application of the Mesoporous molecular sieves MCM-41/ a
review, J.chem. Sos, Vol 46, No 3, 1999
16. Ja Hun Kwak, Jose E. Herrera, Jian Zhi Hu, Yo Wang, C.H.F.
Peden, A new class of highly dispersed VOX catalysts on mesoporous silica:
Synhesis, characterization, and catalytic activity in the partial oxidation of
ethanol, Applied Catalysis A: General 300 (2006) 109-119.

17. Jean Marcel R. Gallo, Icaro S.Paulino, Ulf Schuchardt,

Cycloocten epoxiation using Nb-MCM-41 and Ti-MCM-41 synthesized at room
temperature, Aplied Catalysis A: General 266 (2004) 223-227.
18. J.P Da Silva, I. Ferreira Machado, J.P, Lourenco, L.F Vieira
Ferreira,

Photochemistry of benzophenone on Ti-MCM-41 surfaces,

Micropous and Mesoporous Material 89 (2006) 143-149

19. J. Wang, S. Uma, K.J. Klabunde, Visible light photocatalysis in
transition metal incorporated titania-silica aerogel, Applied Catalysis B:
Environmental 48(2004) 151-154.
20. Karuna Chaudhari, Synthesis, characterization and catalytic
properties of mesoporous molecular sieves, a thesis for the degree of doctor of
philosophy in Chemistry, May 2003
21. L.A, Rios, P,Weckes, H.Schuster, W,F, Hoelderich, Mesoporous
and amorphous Ti-silicas on the epoxidation of vegetable oils, Journal of
Catalysis (2005) 19-26
22. Luis Alberto Rios, Heterogenously catalyzed reactions with
vegetable oils: Epoxidation and Nucleophillic epoxide ring-opening with
alcohols, a thesis for the degree of doctor of philosophy in Chemistry, 11 April
2003.
23. M.A.Zanjaanchi, A. Ebrahimian, Z. Alimohammadi, A
spectroscopic on the adsorption of cationic dyes into mesoporous AlMCM-41
materials, Optical Materials (2006) -.
24. Marcelo J. B. Souza, Antonio S.Araujo, Anne M.G. Pedrosa,
Bojan A. Marinkovic, Paula M. Jardim, Edission Morgado Jr, Textural
features of highly ordered Al-MCM-41 molecular sieve studied by X-ray
diffraction, nitrogen adsorption and transmission electron microscopy,
Material Letters (2006) -.

25. M. Selvaraj, P.K. Sinba, K. Lee, I. Ahn, A. Panfurangan, T.G.

Lee,

synthesis and characterization of Mn-MCM-41 and Zr-MZM-41,

Microporous and Mesoporous Material 78 (2005)139-149.

26.Peng Wu and Masakazu Iwaoto, Metal- ion- planted MCM-41.
Part 3: incorporation of titanium species by atom- plating method, J.
Chem.Soc., Faraday Trans., 94 (1998) 2871-2875
27. Peng Wu, Duangamol Nuntasri, Juanfang Ruan, Yueming Liu,
Minyuan He, Weibin Fan, Osamu Terasaki, and Takshi Tatsumi,
Delamination of Ti-MWW and high efficieney in epoxiation of alkenes with
various molecular sizes, J.Phys.Chem.B 108 (2004) 19126-19131.
28. P. Smet, J. Riondato, T. Pawels, L.Moens, L. Verdonek,
Preperation and characterization of a titanium (IV) silsesquioxane epoxidation
catayst

anchored

into

mesoporous

MCM-41,

Inorganic

chemistry

Communication, 27 (2000) 557-562

29. Rejendra Srivastava,

Activation of

small molecules

for

cycloaddition and coupling reactions over transition metal catalysts, a thesis

for the degree of doctor of philosophy in Chemistry, august 2005
30. R.L. Putnam, N. Nakagawa, K.M. McGrath, N. Yao, I.A.Aksay,
S.M. Gruner, and A. Navrotsky, Titanium Dioxide-Surfactant Mesophases
and Ti-TMS1, Chem.Mater 9 (1997) 2690-2693.
31. R.M Lambert, F.J. William,

R.L.cropley, A.Palermo,

Heterogeneous alkene epxidation: past, present and future, Journal of

Molecular Catalysis A: Chemical, 228 (2005) 27-33
32. Le T.Son, Tran T.Nhu Mai, Nguyen Thi Ha, Preparation and
charaterization of ZrO2 and V2O5 systems supported on MCM-41, International
chemical congress of pacific basin societics, 2005.
33. T.D. Conesa, J.M. Hidalgo, R. Luque, J. M. Campelo, A.A.
Romero, Influence of the acid-base properties in Si-MCM-41 and B-MCM-41

mesoporous materials on the activity and selectivity of -caprolactam

synthesis, Applied catalysis A: General 299 (2006)224-234.
34. T.Linssen, K.Cassier, P.Cool, E.F. Vansant, Mesoporous template
silicates: an overview of their synthesis, catalytic activation and evaluation of
the stability, Advances in Colloid and Interface Science 103 (2003)121-147.
35. Valrie Caps, Shi Chik Tsang, Heterogenisation of Os species on
MCM-41 structure for epoxiation of trans-stilbene, Applied Catalysis A:
Genera l 248 (2003) 19-23.
36. Xuxu Wang, Wenhao Lian, Xianzhi Fu, Jean-Marie Basset,
Frdric Lefebvre, Structure, preparation and photocatalytic activity of
titanium oxides on MCM-41 surface, Journal of catalysis 238 (2006) 13-20.

MC LC

Trang

T VN

CHNG 1: TNG QUAN

1.1 Vt liu mao qun trung bnh

1.1.1 Gii thiu chung

1.1.2 u im ca vt liu MQTB v ng dng

1.1.3 Nhc im v cch khc phc

1.2 Kim loi chuyn tip Ti v Ti-MCM-41

1.2.1 Gii thiu v Titan, Titan oxit v ng dng ca chng

1.2.2 c im ca vt liu Ti-MCM-41

10

1.2.3 C ch gn Ti vo trong khung cu trc ca vt liu MCM-

10

41
1.2.4 Cc yu t nh hng trong qu trnh tng hp Ti-MCM-41

11

1.2.4.1 nh hng ca cht HBM

11

1.2.4.2 nh hng ca thi gian, t l OH-/Si, Si/Ti ln hm lng

13

Ti trong mng
1.2.4.3 nh hng ca nhit

13

1.2.4.4 nh hng ca ngun Silic

14

1.3 Phn ng Epoxi ha du thc vt

14

1.3.1 Cc phng php epoxi ha olefin

15

1.3.2 Epoxi ha olefin bng xc tc d th

16

1.3.2.1 Epoxi ha vi percacboxylic

16

1.3.2.2 Epoxi ha bng hydroperoxit hu c v v c

17

1.3.2.3 Epoxi ha du thc vt bng xc tc Ti-MCM-41

18

CHNG 2: THC NGHIM

21

2.1 Phng php tng hp

21

2.1.1 Tng hp vt liu mao qun trung bnh MCM-41

21

2.1.2 Tng hp Ti-MCM-41

23

2.2 nh gi hot tnh xc tc trong phn ng epoxi ha Metyl

24

oleat
2.3 Phn tch sn phm phn ng bng thit b sc k kh ghp
ni khi ph (Gas chromatography Mass Spectrocopy - GC-

27

MS)
2.3 Cc phng php ho l c trng

28

2.3.1 Phng php ph nhiu x Rnghen (X-ray difraction)

28

2.3.2 Phng php ph tn x Raman

29

CHNG 3: KT QU V THO LUN

31

3.1 Tng hp vt liu

31

3.2 c trng xc tc bng nhiu x tia X ( XRD)

32

3.3 Nhn dng Ti+4 trong v ngoi mng MCM-41 bng ph

38

tn x Raman
3.4 nh gi hot tnh xc tc ca vt liu Ti-MCM-41 trong

41

phn ng oxi ha chon lc metyl oleat.

3.4.1 Phn ng oxi ha Metyl oleat trn nhng mu xc tc khc

43

nhau.
3.4.2 Kho st nh hng ca dung mi ti phn ng oxi ha

43

Metyl oleat.

CHNG 4: KT LUN

45

CHNG 5: TI LIU THAM KHO

46