Hop Chat TiO2 Va Ung Dung

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MC LC
MC LC................................ ................................ ................................ .............. 1
DANH MC CC BNG ................................ ................................ ..................... 3
DANH MC HNH NH................................ ................................ ...................... 4
M U ................................ ................................ ................................ ................ 7
PHN 1: TNG QUAN ................................ ................................ ........................ 8
CHNG 1: C S L THUYT................................ ................................ ......8
1.1 Phng php sol-gel................................ ................................ ................... 8
1.1.1 Gii thiu................................ ................................ ............................. 8
1.1.2 Cc qu trnh chnh xy ra trong Sol-Gel ................................ ............. 9
1.1.3 u im v nhc im ca qu trnh Sol-Gel ................................ ..13
1.1.4 Mt s ng dng hin nay ca phng php sol-gel ......................... 14
1.1.5 Cc phng php to mng ................................ ............................... 16
1.2 Hp cht TiO2 v cc ng dng................................ ................................ 20
1.2.1 Cc tnh cht l-ha ................................ ................................ .......... 20
1.2.2 Tnh nng quang xc tc ................................ ................................ ... 22
1.2.3 S lc v vt liu t lm sch ................................ .......................... 26
1.2.3.1 Gc tip xc ................................ ................................ ................ 26
1.2.3.2 Tnh k nc ................................ ................................ ............... 27
1.2.3.3 Tnh a nc ................................ ................................ ............... 28
1.3 Cc phng php phn tch m u trong kha lun ................................ ..... 32
1.3.1 Nguyn l v ng dng ca ph UV-VIS................................ ........... 32
1.3.2 Nguyn l v ng dng ca ph nhiu x tia X (XRD) ...................... 33
1.3.3 Nguyn l v ng dng ca cc knh hin vi TEM, SEM, AFM......... 35
1.3.3.1 Knh hin vi in t truyn qua (TEM)................................ ........ 35
1.3.3.2 Knh hin vi in t qut (SEM)................................ .................. 36
1.3.3.3 Knh hin vi lc nguyn t (AFM) ................................ .............. 38
PHN 2: THC NGHIM ................................ ................................ ................. 40
CHNG II: TO V KHO ST TNH CHT VT LIU ....................... 40
2.1 To vt liu TiO2 ................................ ................................ ...................... 40
2.1.1 Qu trnh to sol ................................ ................................ ................ 40
2.1.1.1 Chun b................................ ................................ ...................... 40
Ha cht ................................ ................................ ................................ ...... 40
Dng c th nghim ................................ ................................ ..................... 40
SVTH: Hunh Ch Cng
2.1.1.2 Thc hin ................................ ................................ .................... 41

To sol SnO 2................................ ................................ ................................ 41
To sol TiO 2 pha tp SnO2 ................................ ................................ ........... 42
2.1.2 Qu trnh to mng v bt:................................ ................................ .44
2.1.3 X l nhit................................ ................................ .......................... 47
2.2 Kho st cc tnh cht................................ ................................ ............... 47
2.2.1 Kho st nng lng vng cm Eg................................ ..................... 48
2.2.2 Kho st cc thnh phn trong mu................................ .................... 48
2.2.3 Kho st cc tnh cht v kch thc v b mt mu: ......................... 48
2.2.4 Th tnh nng quang xc tc: ................................ ............................. 48
CHNG III: KT QU V BN LUN ................................ ....................... 51
3.1 Thay i mc nng lng hp thu ................................ ............................ 51
3.2 Hnh thnh tinh th TiO2,SnO2 ................................ ................................ .53
3.3 Tnh nng quang xc tc ................................ ................................ ........... 58
3.3.1 Kh nng phn hy MB ................................ ................................ ..... 58
3.3.2 Tnh siu a nc ca mng ................................ .............................. 61
3.3.3 Kh nng dit khun ................................ ................................ .......... 63
KT LUN ................................ ................................ ................................ .......... 64
Ti liu tham kho................................ ................................ ............................... 66
SVTH: Hunh Ch Cng
DANH MC CC BNG
Bng 1.1
Tnh cht quang ca TiO2 ................................ ................................ .20
Bng 1.2
S liu v tnh cht v cu trc ca TiO2 ................................ ........... 21
Bng 3.1
Bng kt qu gc thm t ca cc mu ................................ ............ 62
SVTH: Hunh Ch Cng
DANH MC HNH NH
Hnh 1.1
Phn ng thy phn ................................ ................................ ............ 10
Hnh 1.2
Phn ng ngng t................................ ................................ .............. 11
Hnh 1.3
S pht trin cu trc tinh th trong iu kin xc tc acid ................. 12
Hnh 1.4
S pht trin cu trc tinh th trong iu kin xc tc base ................. 12
Hnh 1.5
S pht trin cu trc mng trong qu trnh sol -gel............................. 13
Hnh 1.6
Cc nhm sn phm ca phng php sol-gel ................................ .... 15
Hnh 1.7
Phng php ph quay (spin coating) ................................ ................. 16
Hnh 1.8
Cc giai on ca phng php ph quay................................ ........... 16
Hnh 1.9
S pht trin dy mng ph ................................ ........................... 18
Hnh 1.10 Qu trnh ph nhng ................................ ................................ ........... 18

Hnh 1.11 Thit b ph phun (sng phun) ................................ ............................ 19
Hnh 1.12 H thng ph chy dng ................................ ................................ ..... 19
Hnh 1.13 Cu trc pha tinh th rutile ................................ ................................ .21
Hnh 1.14 Cu trc pha tinh th Anatase ................................ ............................. 22
Hnh 1.15 Cu trc pha tinh th brookite................................ ............................. 22
Hnh 1.16 Cc c ch dch chuyn in t ................................ .......................... 23
Hnh 1.17 Qu trnh quang ho vi s kch hot ca cc phn t TiO2 ................ 24
Hnh 1.18 B rng khe nng lng ca mt s cht bn dn ............................... 25
Hnh 1.19 Cu trc b mt ca l sen ................................ ................................ ..27
Hnh 1.20 Hiu ng l sen................................ ................................ ................... 27
Hnh 1.21 C ch chuyn t tnh k nc sang tnh a nc ca TiO 2 khi c
chiu sng................................ ................................ ........................... 29
Hnh 1.22 B mt k nc ca TiO2................................ ................................ .... 30
Hnh 1.23 S phn hu cc cht hu c lm l nhm OH ................................ .30
Hnh 1.24 Qu trnh hp ph vt l cc phn t nc................................ .......... 30
Hnh 1.25 Nc khuch tn vo trong b mt vt liu ................................ ......... 31
Hnh 1.26 C ch t lm sch kt hp tnh cht siu thm t ............................ 32
SVTH: Hunh Ch Cng
Hnh 1.27 Cng tia sng trong phng php o UV-VIS ............................. 33
Hnh 1.28 My UV-Vis Cary 100 Conc - Variant ................................ ............... 33
Hnh 1.29 S tn x tia X bi nguyn t................................ ......................... 34
Hnh 1.30 S nhiu x tia X bi tinh th. ................................ ....................... 34
Hnh 1.31 My chp ph XRD ................................ ................................ ........... 35
Hnh 1.32 S cu to my TEM ................................ ................................ ..... 35
Hnh 1.33 My JEM 1400 ................................ ................................ ................ 36
Hnh 1.34 S cu to my SEM ................................ ................................ ..... 37
Hnh 1.35 My Jeol 6600 ................................ ................................ .................... 38
Hnh 1.36 My Nanotec Electronica S.L ................................ ............................. 38
Hnh 1.37 S cu to my AFM ................................ ................................ ..... 39
Hnh 1.38 th cc vng hot ng ca mi d................................ ................ 39
Hnh 2.1
S to sol SnO 2 ................................ ................................ .............. 41
Hnh 2.2
S to sol TiO 2:SnO2 ................................ ................................ ..... 44
Hnh 2.3
My nhng mng (dipcoating) ................................ .......................... 46
Hnh 2.4
My OCA-20 Dataphysics ................................ ............................... 49
Hnh 3.1
Ph UV-VIS ca mng ng vi cc nng ................................ ...... 51
Hnh 3.2
S dch chuyn in t trong TiO 2:SnO2................................ ........ 52
Hnh 3.3
Ph hp thu ca cc mng TiO 2:SnO2 pha tp vi cc nng khc

nhu ti 5000C ................................ ................................ .................... 53
Hnh 3.4
Ph nhiu x tia X ca mu bt TiO2 ti cc nhit khc nhau......... 54
Hnh 3.5
Ph nhiu x tia X ca mu bt TiO2:SnO2 vi cc nng pha tp

khc nhau ti 5000C................................ ................................ ............ 55
Hnh 3.6
nh TEM ca mu TiO 2:SnO2................................ ............................ 56
Hnh 3.7
nh SEM ca mu TiO 2:SnO2 ................................ ............................ 57
Hnh 3.8
nh AFM ca mu mng TiO 2:SnO2 (30%) ti 5000C........................ 57
Hnh 3.9
th biu din nng MB theo thi gian ng vi cc mu pha tp

SnO2 khc nhau ................................ ................................ .................. 58
SVTH: Hunh Ch Cng
Hnh 3.10 th kho st nng MB theo thi gian xc tc mu TiO 2 v

TiO2:SnO2 ................................ ................................ .......................... 59
Hnh 3.11 S mt mu ca dung dch MB trn lam knh theo th i gian............... 60
Hnh 3.12 Gc thm t trn lam knh cha ph mng ................................ ....... 61
Hnh 3.13 Gc thm t trn mng TiO 2:SnO2 trong iu kin bnh thng....... 61
Hnh 3.14 Gc thm t trn mng TiO 2:SnO2 chiu sng 2 gi (a) v mng TiO 2
chiu UV (b)................................ ................................ ....................... 62
Hnh 3.15 Hnh nh khun lc trn a petri ................................ ........................ 63
SVTH: Hunh Ch Cng
M U
Vt liu TiO2 l cht bn dn c tnh nng quang xc tc rt mnh trong vic
ng dng mi trng, c rt nhiu cng trnh trong v ngoi n c nghin cu vt
liu ny [1,6,34]. Ch bng vic chiu sng, cc nh nghin cu nhn thy cc cht
hu c, cc cht bn b phn hu. c bit trong mi trng nc, di tc dng
ca nh sng v s c mt ca TiO 2, cc hp cht nhim d dng b phn hy.
Tnh cht ny c p dng lm sch nc, khng kh v dit khun.
Vi rng vng cm khong 3,2eV 3,5eV, vt liu TiO2 ch c th cho
hiu ng xc tc trong vng nh sng t ngoi (UV). Tuy nhin, bc x UV ch
chim khong 4%-5% nng lng mt tri nn hiu ng xc tc ngoi tri thp [26].
s dng trc tip nng lng mt tri c hiu qu hn, cn m rng ph hp thu
TiO2 v vng nh sng kh kin (loi bc x chim gn 45% nng lng mt tri)
[26], nhiu tc gi pha tp N vi TiO2 bng phng php phn x magnetron,
phng php ny i hi thit b t tin v kh pha tp N vi nng cao.
khc phc nhng hn ch ca vt liu TiO2 c tnh quang xc tc tt trong vng nh
sng kh kin, chng ti tng hp mng v bt TiO2 pha tp vi SnO2 bng phng
php sol gel, y l phng php cho tinh khit cao v c th pha tp vi nng
cao [16,21,22,24]. Sau chng ti dng cc phng php quang ph nghin
cu tnh cht quang ca vt liu TiO2 pha tp SnO2.
SVTH: Hunh Ch Cng
PHN 1
TNG QUAN
CHNG I:
C S L THUYT
1.1
Phng php sol-gel:
1.1.1
Gii thiu:
Phng php sol gel l mt k thut tng hp ha keo to ra cc vt liu

c hnh dng mong mun nhit thp. N c hnh thnh trn c s phn ng
thy phn v phn ng ngng t t cc cht gc (alkoxide precursors) [17].
Lch s pht trin:
Gia nm 1800 s quan tm phng php sol gel to gm s v knh
c bt u vi Ebelman v Graham khi nghin cu v gel Silic. Nm 1950 - 1960
Roy v cc cng tc s dng phng php sol gel to ra gm s mi vi
thnh phn l cc ng cht ha hc, bao gm: Si, Al, Zr.. m khng s dng
phng php gm truyn thng. Bt, si, dy mng v thu knh quang hc th
c to bi phng php sol gel [1].
Cc khi nim c bn:[1]
Mt h Sol l mt s phn tn ca cc ht rn c kch thc khong 0.1 n
1m trong mt cht lng, trong ch c chuyn ng Brown lm l lng cc ht.
a) Kch thc ht qu nh nn lc ht l khng ng k.
b) Lc tng tc gia cc ht l lc Val der Waals.
c) Cc ht c chuyn ng ngu nhi n Brown do trong dung dch cc ht
va chm ln nhau.
Sol c thi gian bo qun gii hn v cc ht Sol ht nhau dn n ng t
cc ht keo.
SVTH: Hunh Ch Cng
Mt h Gel l mt trng thi m cht lng v rn phn tn vo nhau, trong

mt mng li cht rn cha cc thnh phn cht lng
Precursor l nhng phn t ban u to nhng ht keo (sol). N c to
thnh t cc thnh t kim loi hay kim, c bao quanh bi nhng ligand khc
nhau. Cc precursor c th l cht v c kim loi hay hu c kim loi.
Cng thc chung ca precursor : M(OR) X
M l kim loi
R l nhm alkyl c cng th c: CnH2n+1.
Nhng cht hu c kim loi c s dng ph bin nht l cc alkoxysilans,
nh l Tetramethoxysilan (TMOS),Tetraethoxysilan (TEOS). D nhin nhng
alkoxy khc nh l cc Aluminate, Titanate, v Borat c ng c s dng ph bin
trong qu trnh Sol-gel.
1.1.2
Cc qu trnh chnh xy ra trong Sol-Gel:
Qu trnh sol-gel l mt phng php ha hc t tng hp cc phn t huyn

ph dng keo rn trong cht lng v sau to thnh nguyn liu lng pha ca b
khung cht rn, c cha y dung mi cho n khi xy ra qu trnh chuyn tip
sol-gel [1].
Trong qu trnh sol-gel cc phn t trung tm tri qua 2 phn ng ha hc c
bn: phn ng thy phn v phn ng ngng t (di xc tc axit hoc baz)
hnh thnh mt mng li trong ton dung dch [17].
Phn ng thy phn[1]:
Phn ng thy phn thay th nhm alkoxide (-OR) trong lin kt kim loialkoxide bng nhm hydroxyl (-OH) to thnh lin kt kim loi-hydroxyl.
SVTH: Hunh Ch Cng
Hnh 1.1
10
Phn ng thy phn
M(OR)n + xHOH M(OR) n-x (OH)x + xROH
(1.1)
Phn ng ngng t [1]:

Phn ng ngng t to nn lin kt kim loi-oxide-kim loi, l c s cu trc
cho cc mng oxide kim lo i. Hin tng ngng t din ra lin tc lm cho lin kt
kim loi-oxide-kim loi khng ngng tng ln cho n khi to ra mt mng li
kim loi-oxide-kim loi trong ton dung dch. Phn ng ngng t din ra theo 2
kiu:
Ngng t ru:
M(OH)(OR) n-1 + M(OR) n (OR)n-1M-O-M(OR)n-1 + ROH
(1.2)
Ngng t nc:
M(OH)(OR) n-1 + M(OH)(OR) n-1 (OR) n-1M-O-M(OR)n-1 + H2O (1.3)
SVTH: Hunh Ch Cng
Hnh 1.2
11
Phn ng ngng t
Cc giai on chnh [17]:
To dung dch sol: alkoxide kim loi b thy phn v ngng t, to
thnh dung dch sol gm nhng ht oxide kim loi nh (ht sol) phn tn trong dung
dch sol. Dung dch c th c dng ph mng bng phng php ph quay (spin
coating) hay ph nhng (dip coating).
Gel ha (gelation): gia cc ht sol hnh thnh lin kt. nht ca
dung dch tin ra v hn do c s hnh thnh mng li oxide kim loi (M-O-M) ba
chiu trong dung dch.
Thiu kt (sintering): y l qu trnh kt cht khi mng, c iu
khin bi nng lng phn gii. Thng qua qu trnh ny gel s chuyn t pha v
nh hnh sang pha tinh th di tc dng ca nhit cao.
Trong ton b qu trnh, hai phn ng thu phnngng t l hai phn ng
quyt nh cu trc v tnh cht ca sn phm sau cng. Do , trong phng php
sol-gel, vic kim sot tc phn ng thu phn-ngng t l rt quan trng.
SVTH: Hunh Ch Cng
12
S pht trin cu trc tinh th trong qu trnh Gel ha [20]:

Sol ch tn ti trong mt khong thi gian. n mt thi im nht nh th
cc ht ht ln nhau tr thnh nhng phn t ln hn. Cc phn t ny tip tc
pht trin n kch thc c 1nm th ty theo xc tc c m t trong dung dch m
pht trin theo nhng hng khc nhau.
Hnh 1.3
S pht trin cu trc tinh th trong iu kin xc tc acid
Di iu kin xc tc acid ht s pht trin thnh polymer mch nhnh ngu

nhin hoc mch thng c bn, an xen vo nhau
Hnh 1.4
S pht trin cu trc tinh th trong iu kin xc tc base
Di iu kin xc tc baz cc ht pht trin th nh cc cluster phn nhnh

mc cao nhiu hn, khng xen vo nhau tr c khi to thnh Gel, chng th hin
nh nhng cluster ring bit.
Nh vy, vi cc loi xc tc khc nhau, chiu hng pht trin ca ht Sol
cng c phn khc bit
SVTH: Hunh Ch Cng
13
S pht trin ca cc ht trong dung dch l s ngng t, lm tng s lin kt

Kim loi- Oxide- Kim loi to thnh mt mng li trong khp dung dch.
Hnh 1.5 S pht trin cu trc mng trong qu trnh sol -gel
1.1.3
u im v nhc im ca qu trnh Sol-Gel [2]:
u im:
C th to ra mng ph lin kt mng mang n s dnh cht rt tt gia
vt liu kim loi v mng.
C th to ra mng dy cung cp cho qu trnh chng s n mn.
C th d dng to hnh cc vt liu c hnh dng phc tp.
C th sn sut c nhng sn phm c tinh khit cao.
Kh nng thiu kt nhit thp, thng l 200 600 .
C th iu khin cc cu trc vt liu.
To c hp cht vi pha tp ln.
SVTH: Hunh Ch Cng
14
khuych tn ng u cao.
Ch to nano thay i thnh phn d
Lm vic nhit thp hiu qu, kinh t, n gin sn xut nhng mng
c cht lng cao.
u im ni tri nht ca phng php sol-gel l kh nng ch to c
nhng vt liu mi c cu trc ng u: vt liu xp, vt liu microballoon ...
Nhc im:
S lin kt trong mng yu.
C thm thu cao.
Rt kh iu khin xp.
D b rn nt trong qu trnh nung sy.
1.1.4
Mt s ng dng hin nay ca phng php sol-gel [2]:
Phng php sol-gel c s dng rng ri trong ch to v nghin cu vt

liu oxide kim loi tinh khit. Nhng nghin cu ca phng php sol-gel ch yu
l ch to gel khi SiO2 (silica) v sau m rng ch to cc oxide kim loi
chuyn tip khc nh TiO 2 (titania), ZrO 2 (zirconia), Hin nay, phng php solgel thnh cng trong vic ch to vt liu oxide a thnh phn (multicomponent
oxide: SiO 2-TiO2, TiO2:SnO2) v ch to vt liu lai hu c-v c (hybrid
materials).
SVTH: Hunh Ch Cng
Hnh 1.6
15
Cc nhm sn phm ca phng php sol-gel
Cc nhm sn phm chnh t phng php sol-gel, c m t trong Hnh 1.6,

bao gm:
Mng mng (thin film): ch to mng mng c cu trc ng u vi
nhiu ng dng trong quang hc, in t, pin mt tri
Gel khi (monolithic gel): c s dng ch to cc oxide a kim
loi cc dng c quang hc: gng nng (hot mirror), gng l nh (cold mirror),
thu knh v b tch tia (beam splitter)
Gel kh (Aerogel): thu c bng cch sy siu ti hn gel t (wet
gel). Gel kh c ng dng trong nhiu lnh vc: hp th nng lng mt tri (silica
aerogel), xc tc (alumina (Al 2O3) aerogel c pha tp kim loi), cht cch in v
cch nhit (silica aerogel)
Ht nano: n thnh phn v a thnh phn c kch thc ng u c
th thu c bng cch to kt ta trong giai on thy phn - ngng t.
SVTH: Hunh Ch Cng
1.1.5
16
Si ceramic: si quang cht lng cao v si ceramic cch nhit.

Cc phng php to mng [2]:
Ph quay (spin coating):

Phng php ph quay c m t trong hnh 1.7. Dung dch sol c nh
git ln v cho quay. Di tc dng ca lc ly tm, dung dch s lan u tr n
v to thnh mng mng.
Hnh 1.7
Phng php ph quay (spin coating)
Qu trnh ph quay gm 3 giai on xy ra li n tip (hnh 1.8).
Hnh 1.8
Cc giai on ca phng php ph quay
i) Giai on 1 (Fluid dispense): dung dch c nh git ln . Lng dung

dch s dng thng nhiu hn lng dung dch cn thit hnh thnh mng.
SVTH: Hunh Ch Cng
17
ii) Giai on 2 (Ramp-up, spreading): c gia tc n vn tc quay cn

thit. Mt phn dung dch b vng ra khi . nht dung dch quyt nh dy
mng. quay vi vn tc khng i, dung dch tip tc chy lan trn di tc
dng ca nht v lc ly tm.
iii) Giai on 3 (Evaporation): s bay hi dung mi quyt nh dy mng.
tip tc quay vi vn tc khng i nhng dng chy nht khng ng k.
Theo Meyerhofer, do dung mi bay hi ra kh i mng, nht dung dch tng
dn n s gel ha ca dung dch sol trn b mt .
dy mng thu c t phng php ph quay kh ng u. Meyerhofer
v mt s tc gi khc a ra cng thc tnh dy mng ph thuc vo nht,
tc bay hi ca dung dch v tc quay ca .
Ph nhng (dip coating):

Phng php ph nhng c th c m t nh l mt qu trnh trong
cn ph c nhng vo dung dch lp ph v sau c ko ra vi mt vn tc
thch hp di nhng iu kin v nhit v p sut ph hp. dy mng ph
thuc ch yu vo tc ko, lng vt cht rn v nht ca dung dch. d y
mng ph c th c tnh theo cng thc Landau -Levich:
(1.4)
vi
h: dy lp ph.
: nht dung dch.
: sc cng b mt lng-hi.
: t trng.
g: lc hp dn.
SVTH: Hunh Ch Cng
Hnh 1.9
18
S pht trin dy mng ph
Qu trnh ph nhng gm 3 giai on (hnh1.9):

i) Nhng vo dung dch lp ph.
ii) c ko ra khi dung dch lp ph vi vn tc thch hp, hnh thnh
lp ph t trn b mt .
iii) S bay hi dung mi dn n s gel ha ca dung dch sol trn b mt ,
hnh thnh mng.
Hnh 1.10 Qu trnh ph nhng
SVTH: Hunh Ch Cng
19
Tuy nhin phng php ny c m t s nhc im nh: dy mng khng

ng u, vic khng ch dy mng ph thuc vo nhiu yu t (gc ko, tc
ko).
Ph phun (spray coating):
Phng php ph phun c s dng rng ri trong cng nghip sn du.
Thit b bao gm mt sng phun c gn vi vi phun p sut thp (hnh 1.11),
dung dch lp ph c vo bnh cha sau c phun trc tip ln .
Hnh 1.11 Thit b ph phun (sng phun)
Ph chy dng (flow coating):

M hnh h thng ca phng php ny nh sau ( hnh 1.12):
Hnh 1.12 H thng ph chy dng
SVTH: Hunh Ch Cng
20
dy mng ph thuc vo gc nghing ca , nht ca dung dch ph

v tc bay hi ca dung mi. Phng php ph chy hin nay ch yu c s
dng ph cc trang thit b bng thy tinh ca xe t.
1.2
Hp cht TiO2 v cc ng dng:
1.2.1
Cc tnh cht l-ha [5]:
Tnh cht ha hc:

TiO2 tr v mt ha hc, c tnh cht lng tnh, khng tc dng vi nc,
dung dch axit long (tr HF) v kim, ch tc dng chm vi axit khi un nng lu
v tc dng vi kim nng chy. B H2SO4 c nng, HCl, kim c nng phn hy.
Tnh cht vt l:
iu kin thng TiO 2 l cht rn mu trng tr nn vng khi un nng.
TiO2 cng, kh nng chy v bn nhit.
Cng thc phn t: TiO2
Khi lng phn t (M): 79,88
Nhit nng chy 1870 0C
TiO2 xut hin trong t nhin khng bao gi dng nguyn cht, n tn ti
ch yu trong hp kim (vi Fe), trong khong cht v trong cc qung ng.
Bng 1.1
Tnh cht quang ca TiO2 [4]
Pha
Chit sut
Khi lng ring (g.cm-3)
Cu trc tinh th
Anatase
2.49
3.84
Tetragonal
Rutile
2.903
4.26
Tetragonal
SVTH: Hunh Ch Cng
Bng 1.2
21
S liu v tnh cht v cu trc ca TiO2 [4]
H tinh th
Rutile
Anatase
Brookite
Tet
Tet
Orth
4.5845
3.7842
9.184
n v
a(Ao)
b(Ao)
5.447
c(Ao)
2.9533
9.5146
5.145
Vol
62.07
136.25
257.38
Density
4.2743
3.895
4.123
H s n nhit (theo th tch)

alpha
a0
28.9
0.2890
TiO2 l cht bn dn tn ti 3 dng c bn sau: Rutile, Anatase, Brookite.

Rutile: l trng thi tinh th bn ca TiO2, pha rutile c rng khe nng
lng 3,02 eV. Rutile l pha c xp cht cao nht so vi 2 pha cn li, khi
lng ring 4,2 g/cm 3. Rutile c kiu mng Bravais t phng vi cc hnh bt din
xp tip xc nhau cc nh (hnh 1.13).
Hnh 1.13 Cu trc pha tinh th rutile

SVTH: Hunh Ch Cng
22
Anatase: l pha c hot tnh quang ho mnh nht trong 3 dng tn ti ca

TiO2. Anatase c rng khe nng lng 3,23 eV v khi lng ring 3,9 g/cm 3.
Anatase cng c kiu mng Bravais t phng nh rutile nhng cc h nh bt din
xp tip xc cnh vi nhau v trc c ca tinh th b ko di (hnh 1.13).
Hnh 1.14 Cu trc pha tinh th Anatase
Brookite: c hot tnh quang ho rt yu. Brookite c rng khe nng lng
3,4 eV, khi lng ring 4,1 g/cm 3 (hnh 1.15).
Do vt liu mng mng v ht nano TiO 2 ch tn ti dng th hnh anatase
v rutile, hn na kh nng xc tc quang ca brookite hu nh khng c nn ta s
khng xt n pha brookite trong phn cn li ca ti.
Hnh 1.15 Cu trc pha tinh th brookite
1.2.2
Tnh nng quang xc tc [34]:
Cht xc tc quang l cht lm tng tc phn ng quang ho. Khi c

chiu nh sng vi cng thch hp cht xc tc quang s y nhanh tc phn
ng quang ho bng cch tng tc vi cht nn trng thi n nh hay trng
SVTH: Hunh Ch Cng
23
thi b kch thch hoc vi cc sn phm ca phn ng quang ho tu thuc vo c

ch ca phn ng.. Cht xc tc quang khi c chiu bng nh sng thch hp c
th to ra mt lot qui trnh ging nh phn ng oxy ho-kh v cc phn t dng
chuyn tip c kh nng oxy ho-kh mnh.
Ht mang in linh ng c th c to ra bng 3 c ch khc nhau: kch
thch nhit, kch thch quang v qu trnh pha t p cht. Nu b rng khe nng lng
Eg nh (nh hn eV) qu trnh kch thch nhit c th lm electron nhy t
vng ho tr ln vng dn. Vi c ch tng t, mt electron c th nhy t vng
ho tr ln vng dn bng cch hp th mt photon c nng lng ln hn hay t
nht l bng nng lng Eg (qu trnh kch thch quang). C ch th 3 to cc
ht mang in linh ng l pha cc tp cht thch hp (hnh 1.16). S dch chuyn
ca cc ht mang in linh ng ny dn ti qu trnh oxy ho-kh ca cc cht hp
th trn b mt cht bn dn.
Hnh 1.16 Cc c ch dch chuyn in t

Khi photon c nng lng ln hn nng lng Eg, electron (e) c th nhy t
vng ho tr ln vng dn v li l trng (h+) trong vng ho tr. Mt phn cc
cp e l trng sn sinh ra t qu trnh xc tc quang khu ch tn ti b mt ca
cht xc tc (cp e l trng s b by ti b mt) v tham gia vo qu trnh ph n
SVTH: Hunh Ch Cng
24
ng ho hc vi cc phn t cht cho (D-donor) hay cht nhn (A-acceptor) (hnh

1.17). Electron vng dn c th kh cc phn t thch hp nhn electron (phn
ng kh 1.5) trong khi l trng c th oxy ho cc phn t cho electron (phn ng
oxy ho 1.6)
Hnh 1.17 Qu trnh quang ho vi s kch hot ca cc phn t TiO2

A + e A
(1.5)
D + h + D+
(1.6)
Mt tnh cht c trng ca cht bn dn oxyt kim loi l kh nng oxy ho

mnh ca l trng h+. Cc l trng ny c th phn ng trc tip vi H2O (1.7)
to ra gc hydroxyl c hot tnh cao (OH). C l trng v gc hydroxyl u c kh
nng oxy ho rt mnh, chng c th oxy ho hu ht cc cht bn hu c bm ln
b mt:
H 2O + h+ OH + h +
(1.7)
Ni chung, oxy trong khng kh ng vai tr l cht nhn electron (1.8) to

thnh ion super-oxide O 2. Super-oxide cng l phn t c hot tnh cao, n c th
c dng oxy ho cc cht hu c.
O 2 + e O 2
(1.8)
TiO2 khi c chiu sng UV s to ra cc phn t mang in linh ng

(electron vng dn v l trng vng ho tr).
SVTH: Hunh Ch Cng
25
TiO2 + h h+ + e
(1.9)
Hnh 1.18 B rng khe nng lng ca mt s cht bn dn
Kh nng chuyn e v l trng h+ t cht bn dn n nhng cht bn bm

trn b mt ph thuc vo v tr di nng lng ca cht bn dn so vi th oxy hokh ca cc cht b ht bm. Th oxy ho-kh ca cht nhn phi thp hn mc
nng lng thp nht ca vng dn trng thi cn bng nhit ng. Trong khi ,
th oxy ho-kh ca cht cho phi cao hn mc nng lng cao nht ca vng ho
tr.
Hnh 1.18 trnh by v tr di nng lng ca mt s cht bn dn thng gp.
Quan st hnh 1.18 ta c th gii thch v sao pha TiO 2 li l cht xc tc quang
mnh. TiO 2 c chiu sng vi photon c nng lng ln hn nng lng Eg
(bc sng < 388 nm) s to ra cp in t-l trng linh ng. Nh ta bit
trong kh quyn c rt nhiu hi nc, oxy; m th oxy ho-kh ca nc v oxy
tho mn yu cu trn nn nc ng vai tr l cht cho (1.7) v kh oxy ng vai
tr l cht nhn (1.7) to ra cc cht mi c tnh oxy ho-kh mnh (OH, O 2)
c th oxy ho hu ht cc cht hu c b ht bm ln b mt vt liu.
SVTH: Hunh Ch Cng
26
Hai yu t quyt nh tnh nng quang xc tc c a mng l din tch b mt

hiu dng v bc tinh th.
* Din tch b mt hiu dng
B mt mng l ni cu trc tinh th dang d - ni sai hng mng. Tnh nng
quang xc tc ca mng TiO 2 mnh hay yu, ph thuc vo hai din tin xy ra
ng thi trn b mt mng lin quan n hot ng ca cc cp in t-l trng:
din tin tch cc l phn ng oxy ho-kh v din tin tiu cc l s ti hp.
Do , mng TiO 2 c tnh nng quang xc tc m nh ng k ch khi n c
din tch b mt hiu dng ln. Din tch b mt hiu dng ca mng TiO 2 c th
c xc nh thng qua thit b AFM o g gh cn qun phng (Rrms) c a
mu .
*
Bc tinh th
Bc tinh th l khi nim ch xa ca trt t sp xp tinh th trong vt l
cht rn. Mng TiO 2 cu trc v nh hnh c trt t sp xp tinh th gn nn c

bc tinh th thp khng ng k. Mng TiO2 a tinh th c trt t sp xp tinh th
xa nn c bc tinh th cao ng k.
Mng TiO 2 c bc tinh th cng cao, mt cc cp in t-l trng cng
nhiu, tnh nng quang xc tc cng m nh
1.2.3
S lc v vt liu t lm sch[1]:
1.2.3.1 Gc tip xc:

Khi nh mt git cht lng ln b mt mt vt liu rn, gc tip xc l gc o
gia b mt vt liu rn v ng thng vung gc vi bn knh ca git cht lng
ti im tip xc ca git cht lng vi b mt rn ca vt liu v mi trng kh
quyn. Gc tip xc lin quan ti sc cng b mt c tnh t phng trnh Young
thng qua vic nghin cu tng tc rn-lng. Gc tip xc bng 00 i vi vt liu
thm t hon ton, gc tip xc nm trong khong gia 00 v 900 lm cho git cht
SVTH: Hunh Ch Cng
27
lng tri rng ra trn b mt. Cui cng, gc tip xc ln hn 90 0 tc l cht lng c
khuynh hng to thnh git hoc ngng t trn b mt vt liu rn.
1.2.3.2 Tnh k nc:
Vt liu c tnh cht ny s t hoc khng thm nc. Khi nc nh ln b mt
vt liu k nc s c khuynh hng ngng t thnh nhng git ri rc trn b mt
vt liu. Vt liu k nc c gc tip xc ln hn 70 0. Gc tip xc cng ln, nng
lng dnh t cng nh. Kh nng t lm sch ca vt liu da trn tnh siu k
nc c bit n rt lu t vic nghin cu b mt t lm sch ca l cy, in
hnh l l sen. Gn y, vi vic quan st cu trc b mt ca l sen cc nh nghin
cu c th gii thch v ch to vt liu t lm sch da trn hiu ng l sen. Trn
b mt l sen c rt nhiu vi cu trc nh (hnh 1.19), cc vi cu trc ny lm cho
gc tip xc ca nc trn b mt ln hn 130 0. iu ny c ngha l bm dnh
ca nc cng nh ca cc phn t gim i rt nhiu. Khi nc tip xc vi b mt
vt liu ny s ngay lp tc co cm li to thnh git. Cc phn t cht bn do
bm dnh vi b mt vt liu ny rt thp; khi c nc, cc phn t cht bn ny s
bm dnh vi cc git nc tt hn v chng s b cun i cng git nc lm cho
b mt vt liu tr nn sch s (hnh 1.20).
20nm
50nm
Hnh 1.19 Cu trc b mt ca l sen
Hnh 1.20 Hiu ng l sen

SVTH: Hunh Ch Cng
28
Kh nng t lm sch ca vt liu da trn hiu ng l sen lm cho b mt vt

liu khng b dnh bn v b thm t khi nc chy ra khi b mt. Tuy nhin,
nc trn b mt vt liu ch chy i khi c tc dng ca lc c hc nh rung, lc,
hay nghing b mt vt liu i. Nu khng c cc lc c hc ny, cc git nc vn
nm ri rc trn b mt. Nhng git nc ny lm cho hnh nh truyn qua knh
(knh ca s, knh cn, hay knh xe t) b m, khng c r nt.
1.2.3.3 Tnh a nc:
Vt liu c tnh a nc th hin i lc i vi nc. Vt liu a nc hiu
theo mt cch nm na l vt liu sn sng ht bm nc. B mt ha hc cho php
vt liu ny b thm t v to thnh lp phim nc mng trn b mt. Tri vi vt
liu k nc, vt liu a nc c sc cng b mt ca nc ln v c kh nng to
lin kt hydro vi nc.
TiO2 trng thi bnh thng (khng c chiu sng) c tnh k nc nhng
khi c chiu sng (nh sng trong vng t ngoi), TiO2 li th hin tnh a nc.
Trong trng hp ny, electron v l trng vn c to ra nhng chng hot ng
theo cch khc. Trong qu trnh ny, electron s kh cation Ti 4+ thnh Ti 3+, l trng
s oxy ha anion O 2- to thnh oxy nguyn t v b a ra khi mng tinh th li
mt ch trng thiu oxy (hnh 1.21). Cc phn t nc c th chim nhng ch
trng oxy va c to ra ny v to nhm OH. Chnh nhm OH lm cho b mt
TiO2 tr nn siu a nc. B mt vt liu c khong 30 pht sau khi chiu sng
gc tip xc ca nc tin ti 0 , c ngha l nc s tri ra to thnh lp phim
mng trn b mt vt liu.
SVTH: Hunh Ch Cng
29
Hnh 1.21 C ch chuyn t tnh k nc sang tnh a nc ca TiO 2 khi

c chiu sng
Mc a nc ca vt liu c o bng gc tip xc ca nc vi b mt

vt liu, gc tip xc cng nh tnh a nc cng mnh. Hin nay c rt t vt liu
c gc tip xc ca nc nh hn 10 0, tr cc vt c bn cht ht nc hay cc b
mt c hot ha. Tuy nhin thi gian sng ca cc vt liu ny rt ngn hn
na gc tip xc nh cng khng duy tr c lu. Mng mng vi s c mt ca
cht xc tc quang TiO 2 c tnh cht siu a nc rt th v. u tin, gc tip xc
ca nc trn b mt TiO 2 khong vi chc , khi c chiu sng trong vng t
ngoi gc tip xc gim dn dn v cui cng t gi tr 00. Sau , khi ngng chiu
sng gc tip xc cng ch tng ln mt vi trong nhiu gi m khng cn phi
chiu sng. Nu mun gim gc tip xc, chng ta ch phi lm mt thao tc n
gin l chiu tia t ngoi ln b mt mu. Tnh siu a nc ca TiO2 l mt trong
nhng ng dng thc t d thy nht ca TiO2.
Sau y chng ta c th gii thch mt cch n gin c ch chuyn t k
nc sang siu a nc ca b mt vt liu khi c mt TiO2.
Bc 1: Nh chng ta bit TiO2 trong mi trng bnh thng rt d hp
th ha hc nhm OH (hydroxyl) c trong hi n c, tuy nhin cc nhm hydroxyl
SVTH: Hunh Ch Cng
30
ny khng n nh. Do chng s ht bm cc phn t k nc tn ti sn trn b

mt vt liu chuyn sang trng thi bn hn (hnh 1.21).
Hnh 1.22 B mt k nc ca TiO 2
Bc 2: Khi c chiu sng, cht xc tc quang TiO 2 s phn hy cc phn

t hu c k nc to thnh CO 2, H2O hay cc axit hu c lm cho cc nhm OH
l ra trn b mt (hnh 1.22).
Hnh 1.23 S phn hu cc cht hu c lm l nhm OH
Bc 3: Cc nhm OH l ra hp ph vt l, lin kt vi cc phn t nc

(hnh 1.23).
Hnh 1.24 Qu trnh hp ph vt l cc phn t nc

SVTH: Hunh Ch Cng
31
Bc 4: Nc b hp ph vt l s i vo trong cu trc bng cch khuch tn

qua b mt vt liu v c n nh ha (hnh 1.24)
Hnh 1.25 Nc khuch tn vo trong b mt vt liu
ng dng ca tnh siu a nc kt hp vi kh nng xc tc quang

Tnh siu a nc kt hp vi kh nng xc tc quang rt c ch trong nhiu
lnh vc c bit trong ngnh sn xut king (king xe, king ca s cng nh mt
king).
Nh chng ta bit hi nc rt d lm m gng v king do bi mi
trng khng kh m b lm lnh v to thnh nhng git nc ng trn b mt vt
liu thng thng. Cc git nc ny lm cho hnh nh truyn qua gng hay king
rt m nht. B mt k nc khng th lm ngng qu trnh lm m king tr phi
c s tc ng ca gi hay s rung ng mnh. Ngc li vt liu vi lp ph siu
a nc s ngn khng cho nc to thnh git m tri ra to thnh mt lp phim
nc mng trn b mt lm cho hnh nh truyn qua tt hn, r nt hn m khng
cn phi c gi hay s dao ng. iu ny c bit quan trng i vi cc loi
king dng trn cc phng ti n vn chuyn (king chiu hu, king chn gi ca
xe), gip ti x lun c mt ci nhn r rng, chnh xc khung c nh chung quanh.
Cc loi king ny s gip gim ng k cc tai nn giao thng trong nhng ngy
thi tit m t.
Hn na vi kh nng xc tc quang cc lo i king ny khng nhng c th
ngn cn tia UV c hi m cn c th phn hy t t cc cht bn hu c v ngn
SVTH: Hunh Ch Cng
32
cn chng bm trn b mt. Cc cht bn hu c ny s b ra tri khi tri ma hay

khi chng ta phun nc do c lp phim nc mng to ra trn b mt siu a nc.
Hnh 1.26 C ch t lm sch kt hp tnh cht siu thm t
1.3
Cc phng php phn tch m u trong kha lun:
1.3.1
Nguyn l v ng dng ca ph UV-VIS:
Ph UV Vis l loi ph electron, ng vi mi elctron chuyn mc nng

lng ta thu c mt vn ph rng. Phng php o ph UV Vis (phng php
trc quang) l mt phng php nh lng xc nh nng ca cc cht thng
qua hp thu ca dung dch.
Cho chm nh sng c di sng xc nh c th thy c (Vis) hay khng
thy c (UV - IR) i qua vt th hp thu (thng dng dung dch). Da vo
lng nh sng b hp thu bi dung dch m suy ra nng (hm lng) ca
dung dch .
SVTH: Hunh Ch Cng
33
C
Io
Hnh 1.27 Cng tia sng trong phng php o UV -VIS
I0 = I A + I r + I
(1.10)
Trong :
Io : Cng ban u ca ngun sng.
I : Cng nh sng sau khi i qua dung d ch.
IA: Cng nh sng b hp thu bi dung dch.
Ir : Cng nh sng phn x bi thnh cuvet v dung dch, gi tr ny c
loi b bng cch lp li 2 ln o.
C : Nng mol cht ban u.
l : Chiu dy lp dung dch m nh sng i qua.
Hnh 1.28 My UV-Vis Cary 100 Conc - Variant
1.3.2
Nguyn l v ng dng ca ph nhiu x tia X (XRD):
C th xem nhiu x l s thay i tnh cht nh sng hoc sng do s xuyn

su vo vt th, xem xt s nhiu x tia X xc nh cu trc tinh th.
SVTH: Hunh Ch Cng
34
Nu chiu mt chm tia X ti nguyn t, th cc electron trong nguyn t s

dao ng quanh v tr cn bng ca n. Ta nhn thy mt photon tia X b hp th
bi nguyn t th c mt photon khc pht ra vi cng mc nng lng. Khi khng
c s thay i nng lng gia photon ti v photon pht ra, ta ni b c x l tn x
n hi. Nu photon b mt nng lng th tn x khng n hi.
Hnh 1.29 S tn x tia X bi nguyn t
Hnh 1.30 S nhiu x tia X bi tinh th.
Hiu quang l xut pht t hai mt lin tip trong h mt biu din c tnh
theo cng thc :
2d.sin()=m
m= 1, 2, 3, ... ( nh lut Bragg ) l bc cc i cng ca phn x.
d: khong cch gia cc mt mng.
: l gc nhiu x tng ng.
SVTH: Hunh Ch Cng
(1.11)
35
Hnh 1.31 My chp ph XRD

1.3.3
Nguyn l v ng dng ca cc knh hin vi TEM, SEM, AFM:
1.3.3.1 Knh hin vi in t truyn qua (TEM) [13]:

Knh hin vi in t truyn qua ( transmission electron microscopy )l mt
thit b nghin cu vi cu trc vt rn, s dng chm in t c nng lng cao
chiu xuyn qua mu vt rn mng v s dng cc thu knh t to nh vi
phng i ln (c th ti hng triu ln), nh c th to ra trn mn hunh quang,
hay trn film quang hc, hay ghi nhn bng cc my chp k thut s.
Hnh 1.32 S cu to my TEM

SVTH: Hunh Ch Cng
36
Hnh 1.33 My JEM 1400

1.3.3.2 Knh hin vi in t qut (SEM) [13]:
Knh hin vi in t qut (Scanning Electron Microscope , l mt loi knh
hin vi in t c th to ra nh vi phn gii cao ca b mt mu vt bng cch
s dng mt chm in t (chm cc electron) hp qut trn b mt mu. Vic to
nh ca mu vt c thc hin thng qua vic ghi nhn v phn tch cc bc x
pht ra t tng tc ca chm in t vi b mt mu vt.
Nguyn l:
Vic pht cc chm in t trong SEM cng ging nh vic to ra chm in
t trong knh hin vi in t truyn qua, tc l in t c pht ra t sng phng
in t (c th l pht x nhit, hay pht x trng...), sau c tng tc. Tuy
nhin, th tng tc ca SEM thng ch t 10 kV n 50 kV v s hn ch ca thu
knh t, vic hi t cc chm in t c bc sng qu nh vo mt im kch
thc nh s rt kh khn. in t c pht ra, tng tc v hi t thnh mt chm
in t hp (c vi trm Angstrong n vi nanomet) nh h thng thu knh t, sau
qut trn b mt mu nh cc cun qut tnh in. phn gii ca SEM c
xc nh t kch thc chm in t hi t, m kch thc ca chm in t ny b
hn ch bi quang sai, chnh v th m SEM khng th t c phn gii tt
nh TEM. Ngoi ra, phn gii ca SEM cn ph thuc vo tng tc gia vt
liu ti b mt mu vt v in t. Khi in t tng tc vi b mt mu vt, s c
cc bc x pht ra, s to nh trong SEM v cc php phn tch c thc hin
thng qua vic phn tch cc bc x ny. Cc bc x ch yu gm:
SVTH: Hunh Ch Cng
37
in t th cp (Secondary electrons): y l ch ghi nh thng dng

nht ca knh hin vi in t qut, chm in t th cp c nng lng thp (thng
nh hn 50 eV) c ghi nhn bng ng nhn quang nhp nhy. V chng c nng
lng thp nn ch yu l cc in t pht ra t b mt mu vi su ch vi
nanomet, do vy chng to ra nh hai chiu ca b mt mu.
in t tn x ngc (Backscattered electrons): i n t tn x ngc l
chm in t ban u khi tng tc vi b mt mu b bt ngc tr li, do
chng thng c nng lng cao. S tn x ny ph thuc rt nhiu vo vo thnh
phn ha hc b mt mu, do nh in t tn x ngc rt hu ch cho phn
tch v tng phn thnh phn ha hc. Ngoi ra, in t tn x ngc c th
dng ghi nhn nh nhiu x in t tn x ngc, gip cho vic phn tch cu
trc tinh th (ch phn cc in t). Ngoi ra, in t tn x ngc ph thuc
vo cc lin kt in ti b mt mu nn c th em li thng tin v cc men st
in.
Hnh 1.34 S cu to my SEM
SVTH: Hunh Ch Cng
38
Hnh 1.35 My Jeol 6600

1.3.3.3 Knh hin vi lc nguyn t (AFM) [13]:
Knh hin vi lc nguyn t hay knh hin vi nguyn t lc (Atomic force
microscope) l mt thit b quan st cu trc vi m b mt ca vt rn da trn
nguyn tc xc nh lc tng tc nguyn t gia mt u mi d nhn vi b mt
ca mu, c th quan st phn gii nanometer. AFM thuc nhm knh hin vi
qut u d hot ng trn nguyn tc qut u d trn b mt.
Nguyn l:
B phn chnh ca AFM l mt mi nhn c gn trn mt cn rung
(cantilever). Mi nhn thng c lm bng Si hoc SiN v kch thc ca u
mi nhn l mt nguyn t. Khi mi nhn qut gn b mt mu vt, s xut hin lc
Van der Waals gia cc nguyn t ti b mt mu v nguyn t ti u mi nhn
(lc nguyn t) lm rung thanh cantilever. L c ny ph thuc vo khong cch gia
u mi d v b mt ca mu. Dao ng ca thanh rung do lc tng tc c ghi
li nh mt tia laser chiu qua b mt ca thanh rung, dao ng ca thanh rung lm
thay i gc lch ca tia lase v c detector ghi li. Vic ghi li lc tng tc
trong qu trnh thanh rung qut trn b mt s cho hnh nh cu trc b mt ca mu
vt.
Hnh 1.36 My Nanotec Electronica S.L

SVTH: Hunh Ch Cng
39
Hnh 1.37 S cu to my AFM
Hnh 1.38 th cc vng hot ng ca mi d
T nhng c s l thuyt trn, chng ti tin hnh tng hp vt liu TiO2 pha
tp SnO 2 v nghin cu cc tnh cht quang ca vt liu.
SVTH: Hunh Ch Cng
40
PHN 2
THC NGHIM
CHNG II:
TO V KHO ST TNH CHT VT LIU
2.1
To vt liu TiO2:
2.1.1
Qu trnh to sol:
2.1.1.1 Chun b:
Ha cht
Ethanol C 2H5OH ca Merk , M = 46,07 g/mol , d = 0,789
Tin(II) cloride SnCl 2.2H2O ca Merk, M=225,63 g/mol
Tetraisopropylorthotitanate
Ti(OC 3H7)4
ca
Merck,
M=284,25g/mol,
d=0,96g/ml.
Axit acetic CH 3COOH ca Merck, M = 60,05 g/mol , d = 1,049
Iso propanol (CH 3)2CHOH ca Merck, M=60,10 g/mol , d= 0,785
Methanol CH 3OH ca Merk, M = 32,04 g/mol , d = 0,791
Dng c th nghim
L trung tnh, pipet, a thy tinh, mung thy tinh, c t, bp khuy t c h
thng n nh nhit v tc khuy, cn, nhit k.
Chun b dng c trc v sau khi s dng:
u tin : Pipet, l, a thu tinh, mung thy tinh c ngm trong nc
sch khong 30 pht, l v a thy tinh ra vi x phng, sau ra sch vi
nc, trng qua nc ct v sy kh trong l nhit 100-120oC.
SVTH: Hunh Ch Cng
41
Sau khi s dng, pipet, a, mung dng ly ha cht phi c ngm

trong dung dch HCl pha long 0,5M kho ng na gi, sau mi tin hnh cc thao
tc lm sch khc. Cc pipet khc tin hnh lm sch tng t nh trn.
2.1.1.2 Thc hin:
To sol SnO 2:
Tnh t l mol t ti liu[10]. 16.74g SnCl 2 + 200ml C 2H5OH
SnCl2:
n SnCl 2
m SnCl 2
M SnCl 2
16,74
0.074(mol )
225,63
C2H5OH:
mC 2 H 5 OH VC 2 H 5 OH d C 2 H 5 OH 157,8( g )
nC 2 H 5 OH
mC 2 H 5 OH
M C 2 H 5 OH
157,8
3,379(mol )
46,7
C2H5OH:SnCl 2 = 46:1
Cc bc tin hnh:
Cn 8,37g SnCl 2.2H2O cho vo l, sau cho 100ml C 2H5OH vo, y np li.
Khuy u dung dch trong 5h vi nhit c gi n nh 80oC ta c sol
SnO2. em mt mu sol thu c o ph UV-VIS ta thy b hp thu ca sol thu
c c bc sng ~345 nm. Ta s dng sol ny pha tp vo TiO 2.
S to sol:
Hnh 2.1 S to sol SnO 2
SVTH: Hunh Ch Cng
42
To sol TiO 2 pha tp SnO2

H sol TiO 2 c pha theo t l t ti liu [20]:
6mlTiP + 6,92mlHac + 2,04 ml Iso +5,74 ml MeOH
Ti(OC3H7)4:
mTi(OC 3H 7 ) 4 VTi(OC 3H 7 ) 4 d Ti(OC 3H 7 ) 4 5,622( g )
mTi(OC 3H 7 ) 4
nTi(OC 3H 7 ) 4
0,0198( mol )
M Ti(OC 3H 7 ) 4
CH3COOH:
mCH 3COOH VCH 3COOH d CH 3COOH 7,259( g )
nCH 3COOH
mCH 3COOH
M CH 3COOH
0,1200( mol )
(CH3)2CHOH:
m(CH 3 ) 2 CHOH V(CH 3 ) 2 CHOH d (CH 3 ) 2 CHOH 1,603( g )
n(CH 3 ) 2 CHOH
m(CH 3 ) 2 CHOH
M (CH 3 ) 2 CHOH
0,0267 ( mol )
CH3OH:
mCH 3OH VCH 3OH d CH 3OH 4,545( g )
mCH 3OH
nCH 3OH
0,1419( mol )
M CH 3OH
Ta c t l mol:
Ti(OC3H7)4: CH3COOH: (CH 3)2CHOH: CH 3OH=1:6,06:1,34:7,17
Cc bc tin hnh:
Mt trong nhng kh khn ca cht TiP l rt nhy vi khng kh v nc v
vy nu ban u cho phn ng vi nc thi dung dch s nhanh chng kt ta v
nh th qu trnh sol-gel s khng xy ra. khc phc nhng nhc im trn,
u tin chng ti pha trn cht TiP vi axid acetic (Hac):
SVTH: Hunh Ch Cng
43
Ti-OiPr + HOAc <-> iPrOH + Ti-Oac
(2.1)
Hac s ng vai tr lm gim tnh kch hat ca TiP trong khng kh, v v y
cht TiP s khng b kt ta.
Vai tr th hai ca Hac l c th tham gia vo phn ng ester.
iPrOH + HOAC <-> iPrOAC + H 2O.
(2.2)
Ti-OiPr + HOH <-> TiOH + iPrOH.
(2.3)
V vy to thnh nc, gip cho qu trnh thy phn ca qu trnh sol-gel.

Qu trnh ngng t gip cho qu trnh hnh thnh m ng li Ti-O-Ti.
Ti-OiPr + TiOAc <-> iPrOAc + Ti-O-Ti.
(2.4)
Ti-OH + HO-Ti <-> Ti-O-Ti + H 2O
(2.5)
Cc bc tin hnh:
Cho 11,53 ml Axit acetic (CH 3COOH) vo l, sau cho 10 ml
Tetraisopropylorthotitanate Ti(OC 3H7)4 vo, y np kn li khuy trong 30 pht.
Sau cho thm 3,4 ml Iso propanol (CH 3)2CHOH vo khuy tip 30 pht na. Sau
cho thm 9,5 ml Methanol CH 3OH vo khuy 30 pht. Sau ly 1,17 ml sol
SnO2 pha trc thm vo dung dch thu c khuy thm 30 pht na ta c
sol TiO2 pha tp 5% SnO 2. y k np l li, 4 ngy th em to mng.
Lp li cc bc trn, gi nguyn cc cht ban u, thay i th tch sol SnO 2
pha thm vo thu c cc sol TiO 2 vi nng phn trm SnO 2 pha tp vo
khc nhau.
Thm vo 2,35ml sol SnO 2 thu c sol TiO 2 pha tp 10% SnO 2.
SVTH: Hunh Ch Cng
44
S to sol
Hnh 2.2
S to sol TiO 2:SnO2
Sau tin hnh thay i nng phn trm SnO 2 theo cc t l 5%, 10%,
20%, 30% khi lng.
2.1.2
Qu trnh to mng v bt:
Qu trnh to mng:
Mng c to trn thy tinh kch thc:7,5x2,5cm
Chng ti tin hnh to mng bng 2 phng php: Ph nhng v ph quay.
X l b mt :
cn c x l v bo qun tht k v c vai tr quan trng, nh hng
n bm, tinh khit v mt s tnh cht khc ca mng. Sau y l quy trnh
x l :
SVTH: Hunh Ch Cng
45
c ngm trong dung dch axt HCl long 0.5 M kho ng 2030
pht loi b tp cht.
Sau khi ngm axt, x nc, dng bn chi ch sch vi x phng.
Ra vi nc v tip tc ngm vo dung dch baz NaOH 10% trong
15 pht.
Sau khi ngm baz, x nc, dng bn chi ch sch li vi x phng.
Ngm trong nc ct.
nh siu m trong 15 pht b ng nc ct v acetone.
Sy kh b mt .
sau khi x l sch, c bo qun trong hp ng lam chuyn dng.
Ph quay:
Chng ti thc hin qu trnh to mng bng phng php ph quay trn thit
b quay ph ca PTN Cng ngh Nano.
Trnh t ph mng gm cc bc nh sau:
Bt ngun bin tn. nh trc vn tc quay ca motor bng bin tn.
t ln b g mu ca motor quay. Dng ng nh git nh mt
lng va dung dch ln.
Bt motor quay. Cho motor quay trong 1 pht dung mi bay hi.
Lp li t bc 2 n bc 3 cho qu trnh ph nhiu lp.
Gp mu ra khi b g. Lau sch dung dch d bm vo b g bng
aceton trnh lm bn mu tip theo.
dy mng c iu chnh bng cch iu chnh tc quay ca hoc
tng s ln ph. Trong trng hp ph nhiu lp, ui bt dung mi trc khi
ph ln mt lp khc, thi gian quay dnh cho mi lp ph l 1 pht. Sau mng
SVTH: Hunh Ch Cng
46
c t ln Hot Plate nhit 3000 trong 5 pht ri c lm ngui trc khi

ph lp tip theo.
Ph nhng:
Chng ti s dng phng php dip coating cho mc ch ph mng. My
dip coating t ti phng th nghim Quang Quang ph, b mn Vt l ng
dng, trng H KHTN TpHCM.
Hnh 2.3
My nhng mng (dipcoating)
Ph mng 1 lp:
M t: dng ph mng c a xung v c nhng hon ton trong
cht lng vi 1 vn tc nht nh. Ch khong 1 pht ri ko mng ln vi cng vn
tc .
Trong qu trnh thc nghim chng ti chn c tc nhng tt nht l
6cm/pht. Vi vn tc ny mng thu c l ng u nht.
SVTH: Hunh Ch Cng
47
Ph mng nhiu lp:

M t: Sau khi mng c ph 1 lp theo quy trnh nh trn, mng c a
vo l nung v nng nhit ln n 150oC. Vic nung mng ln n 150oC c tc
dng lm bay hi 1 phn cc hp cht hu c c trn mng. Sau l y mng ra v
tip tc nhng ln th 2. Qu trnh c lp i lp li ta s thu c mng c dy
thch hp.
Qua kho st c 2 cch to mng trn chng ti nhn thy: Do sol phn ng
vi khng kh kh nhanh nn mng thu c phng php ph nhng p v u
hn.
Qu trnh to bt
Sol to thnh trong 2 tun th gel ha. Sol khi gel ha c dng khi trong
sut, c sy 120 oC trong 5 gi cho bay hi ht cc cht hu c, sau nghin
nh thu c bt.
2.1.3
X l nhit:
Cc mu mng v bt c x l nhit trong cc l nung t ti: PTN Cng

ngh Nano HQG TpHCM v PTN Quang Quang ph H KHTN TpHCM.
i vi mng: Mng c nung t nhit phng ln n 500oC vi tc
gia nhit 10oC/pht, nung trong 2 gi.
i vi bt: Bt c nung t nhit phng n 500oC vi tc nng nhit
10oC/pht, nung trong 2 gi.
2.2
Kho st cc tnh cht:
Cc mu mng v bt sau khi thiu kt c em kho st cc tnh cht ha l

v tnh quang xc tc.
SVTH: Hunh Ch Cng
2.2.1
48
Kho st nng lng vng cm Eg:
Mng c chp ph UV-VIS bng my UV-Vis Cary 100 Conc ca hng

Variant - PTN Cng ngh Nano HQG TpHCM. T ph thu c ta c th xc
nh nng lng vng cm Eg ca vt liu to thnh.
2.2.2
Kho st cc thnh phn trong mu:
Sau em mu chp ph XRD xc nh cc thnh phn c trong mu (xc

nh s tn ti ca cc cht TiO2, SnO2 v ng thi bc u c lng kch thc
ht. Ph XRD c chp ti phng phn tch thch hc Vietnam Petroleum
Institute.
Bc sng s dng =1,5406 A 0, =0.04o.
2.2.3
Kho st cc tnh cht v kch thc v b mt mu:
Sau mu c o kch thc mt cch chnh xc hn bng cch chp nh

trn knh hin vi in t truyn qua (TEM). nh TEM c chp bng my JEM
1400 ti HBK TP.HCM.
Tip , chng ti tin hnh kho st cc tnh cht b mt ca mu. Mu c
chp nh trn knh hin vi in t qut (SEM) xc nh ng u trn b mt
mng. Mu c chp nh trn knh hin vi nguyn t lc (AFM) xc nh g
gh trn b mt.
nh AFM ca mng c chp bng my Nanotec Electronica S.L PTN
Cng ngh Nano HQG TpHCM.
2.2.4
Th tnh nng quang xc tc:
Tin hnh o tnh nng quang xuc tc c a mng bng cc phng php th
Metyl Blue (MB) v th tnh nng dit khun ca mng ti PTN Cng ngh Nano
HQG TpHCM. Sau o gc thm t ca mng bng my OCA-20 ca hng
Dataphysics ti Phng Th nghim trng im Quc gia v Vt liu Polymer v
Composite H BK HQG TpHCM .
SVTH: Hunh Ch Cng
Hnh 2.4
49
My OCA-20 Dataphysics
Cc bc th Metyl Blue (MB):

Chun b dung dch Metyl Blue (MB):
MB c cng thc phn t:C16H18N3SCl.3H2O .
Khi lng phn t: 375,5
MB c cn bng cn in t, ly khi lng l 2mg pha vi 400ml H 2O.
Nh vy, ta c dung dch MB c nng 1ppm. Dung dch pha xong c y
li k cho khi bi v bay hi dung dch (s lm thay i nng ).
Tin hnh o:
Dung dch MB c cho vo a thy tinh rng va lam v ngp va lam.
y k li. Chiu sng a bng n hunh quang vi nh sng trng.
Cch mi 30 pht em o ph hp thu ca dung dch trn bng my o UVVIS, xc nh hp thu ca nh hp thu chnh (ti bc sng hp thu cc i 662
nm) theo thi gian.
SVTH: Hunh Ch Cng
50
Theo nh lut Lambert-Beer

A log
I
lC
I0
(2.6)
Trong :
A : hp thu.
C : Nng (mol/l; mg/l).
l : Chiu dy lp dung dch (cm).
: H s hp thu phn t.
T cng thc trn ta suy ra:
C
A
C0 A0
(2.7)
Nng C ca dung dch s t l vi hp thu. T dng th biu din

s thay i nng
C
theo thi gian ng vi cc mu c nng phn trm SnO2
C0
pha tp khc nhau.

Th tnh nng dit khun:
Tnh nng dit khun ca mng c th bng cch m s khun lc trn a
petri. Nh mt lng vi khun ln mng, trong 4 gi. Sau ra mng bng
nc tit trng. Dng lng nc ny (c cha vi khun cn li trn mu) cy li
trn a thch vi khun pht trin trong 1 tun. Lng vi khun thy c t l
vi lng vi khun em cy lc u.
T nhng kt qu o c, chng ti nhn xt v nh gi cc tnh ch t ca

vt liu TiO2:SnO2 to thnh.
SVTH: Hunh Ch Cng
51
CHNG III
KT QU V BN LUN
3.1
Thay i mc nng lng hp thu:
Sol TiO2
Sol SnO2
Sol 5%
Sol 10%
Sol 20%
Sol 30%
3.0
2.5
Abs
2.0
1.5
1.0
0.5
0.0
380
400
420
440
460
480
500
(nm)
Hnh 3.1
Ph UV-VIS ca mng ng vi cc nng
Hnh 3.1 l ph hp thu UV-Viss ca dung dch SnO2, TiO2, v TiO 2: SnO 2 ti
cc nng khc nhau (5%, 10%, 20%, 30%). T ph hp thu trn cho thy khi pha
tp TiO2:SnO2 ph UV Viss c s dch chuyn v pha bc sng vi nng
pha tp SnO 2 cng cao th dch chuyn cng nhiu bc sng ln hn b hp
thu ca TiO2 (= 380 nm), v hp thu cng tng, trong khi b hp thu ca cc
dung dch trn u khng thay i, nguyn nhn ny c th l do di tc dng ca
nh sng, cc in t hnh thnh t TiO2 chuyn n SnO 2 v nguc li l trng t
SVTH: Hunh Ch Cng
52
SnO2 chuyn n TiO 2 do hnh thnh mi ni bn trong hai cht bn dn TiO 2:SnO2
[25] kt qu l lm chm qu trnh ti hp v hp thu tng khi nng pha tp
SnO2 cng nhiu. Mt khc nng pha tp cng nhiu th SnO 2 cng mun nhn
nhiu in t t TiO2 chuyn qua, v vy khi nng pha tp tng th hp thu
tng. y chng ti ch kho st nng pha tp n 30%, v trn 30% dung d ch
b kt ta nhanh.
Hnh 3.2 S dch chuyn in t trong TiO 2:SnO2
Tng t hnh 3.3 l ph hp thu ca mng TiO 2:SnO2 pha tp vi cc nng

khc nhau ti 500oC, so vi ph hp thu trong dung dch th hp thu tng v
dch chuyn v ph nh sng , s gia tng nh ca mng c th do 2 nguyn nhn:
do s gia tng nhit th kch thc ht tng ln v b tinh th ha dn n vic
cc ph hp thu dch v pha nh sng , mt khc SnO2 v TiO 2 l cc cht bn
dn c cc mc nng lng tng t nhau (nng lng vng cm Eg ca SnO2=3,8
eV, TiO 2=3,2 eV [11]). Mc d nng lng vng cm ca SnO 2 ln hn nhng
vng dn li c mc nng lng thp hn TiO 2 nh hnh v minh ha 3.2, SnO 2 dn
in tt hn TiO 2. Cc in t sinh ra khi TiO 2 hp th photon c th d dng
chuyn xung vng dn ca SnO 2 v ngc li, cc l trng chuyn t vng ha tr
ca SnO 2 sang TiO 2. Do c nhiu l trng n c b mt TiO2 thc hin phn
ng oxi ha, v nhiu in t tp trung vng dn ca SnO 2. Hn na, s phn t
SVTH: Hunh Ch Cng
53
SnO2 t hn TiO 2, mt phn t SnO2 c th c bao quanh bi nhiu phn t TiO2.

Cc electron hnh thnh t vng dn ca TiO 2 c th chuyn sang vng dn ca
SnO2 v in t t vng ha tr ca SnO2 c th c kch thch ln vng dn khi
c chiu nh sng.
TiO2
5%
10 %
20 %
30 %
0.3
Abs
0.2
0.1
0.0
390
400
410
420
430
440
450
460
470
480
(nm)
Hnh 3.3 Ph hp thu ca cc mng TiO 2:SnO2 pha tp vi cc nng

khc nhu ti 5000C
3.2
Hnh thnh tinh th TiO2:SnO2:
Hnh 3.4 l ph nhiu x tia X ca mu bt TiO2 theo cc nhit khc

nhau, hnh 3.5 l ph nhiu x tia X ca mu bt TiO2:SnO2 vi cc nng khc
nhau ti 5000C.
SVTH: Hunh Ch Cng
3000
2500
R
A
1500
3 0 0 0C
4 0 0 0C
9 0 0 0C
2000
I n te n s ity
54
A
R
A
A
1000
500
0
20
30
40
50
60
70
80
Hnh 3.4 Ph nhiu x tia X ca mu bt TiO2 ti cc nhit khc nhau

Hnh 3.4 cho thy s chuyn i pha ca tinh th TiO2 nhng nhit
khc nhau. pha anatase, cc peak tinh th TiO2 c quan st thy r hn khi c
s thay i nhit t 300-4000C. Mi peak c ch s mt mng ring. Khi nung
nhit ln 900 0C, ta thy xut hin cc peak c trng ca rutile, bn cnh vn
cn tn ti mt vi peak anatase ca TiO2. Nh vy c s chuyn i cu trc t
phase anatase sang rutile ti 9000C, nhng cha c s chuyn hn sang pha c cu
trc Rutile. Bt TiO2 khi nung ln n 700oC mi bt u xut hin pha rutile [1].
T hnh ph 3.5 cho thy c s chuyn pha hon ton sang dng rutil ch
nhit 5000C ti mu TiO2:SnO2 (30%), v dng hn hp anatase v rutil vi
mu pha tp TiO2:SnO2 (20%, 10%, 5%), ng thi ti nng pha tp 20% c s
xut hin ca cc peaks c trng cho tinh th SnO2, cng cc nh ny mnh
cc nng 20% v 30% SnO 2. iu ny chng t khi pha tp SnO 2 lm cho qu
trnh bin i pha ca TiO2 nhanh hn. Nh vy ti 5000C vi nng pha tp
SnO2 l 30%, tinh th TiO2 xy ra qu trnh chuyn pha han ton t anatase sang
rutil. iu ny ph hp vi cng trnh [22].
SVTH: Hunh Ch Cng
55
5 %
10 %
20 %
30 %
R (1 1 0 )
900
I n te n s ity
R (1 0 1 )
600
R (2 2 0 )
A (1 0 1 )
R (1 1 1 )
SnO 2
SnO 2
R
SnO 2
300
A (2 0 0 )
A (0 0 6 )
A (0 0 4 )
0
24
26
28
30
32
34
36
38
40
42
44
46
48
50
52
54
56
Hnh 3.5 Ph nhiu x tia X ca mu bt TiO2:SnO2 vi cc nng

pha tp khc nhau ti 5000C
T ph nhiu x tia X o c, ta c th tnh c kch thc ht ca tinh th

TiO2 t phng trnh Scherrers:
d hkl
0.9
(2 )Cos
(3.2)
: bc sng nhiu x, =1,5406 A 0

dhkl: kch thc ht
(2): rng peak ti na cng vch ph( bn rng).
Cos(): gi tr gc ng vi nh ph.
T cc mi peak o c, ta o bn rng v gc tng ng. Tnh tt c
cc gi tr d, sau tm gi tr trung bnh.
Kch thc trung bnh: d 14,37nm
SVTH: Hunh Ch Cng
56
Cc kt qu TEM, SEM, AFM sau y s cho ta cc s liu c th hn v kch

thc cc ht to thnh.
Hnh 3.6
nh TEM ca mu TiO2:SnO2
nh TEM (hnh 3.6) cho ta thy cc ht rn c dng khi a din vi kch

thc ht tng i ng nht trong khong 14nm-18nm. Kt qu ny kh ph hp
vi kt qu nhn c t kt qu phn tch X-Ray nh tnh ton trn.
Hnh thi b mt v kch thc ht ca mng TiO2:SnO2 ch to c nh
gi bng phng php hin vi in t qut (SEM). Qua ta c th nh gi c
hnh thi b mt v kch thc ht trn b mt mng ch to c.
SVTH: Hunh Ch Cng
57
Hnh 3.7 nh SEM ca mu TiO2:SnO2
T kt qu thu c ta thy cc hat TiO 2, SnO 2 phn tn kh ng u trn

mng. Nhn vo cc kt qu SEM (hnh 3.7) c chp phng i 100.000 ln
vi mu mng nano TiO2:SnO2 cho thy phn b khng gian, phn b kch thc
ht ca cc mu mng thiu kt cc nhit 5000C trong 2 gi l kh u, mng
khng b rn nt, c nhiu l xp gia cc ht.
Hnh 3.8
SVTH: Hunh Ch Cng
nh AFM ca mu mng TiO 2:SnO2 (30%) ti 5000C
58
T hnh 3.8 ta thy nh cng cho thy hnh thi b mt mng kh g gh. B
mt g gh gip lm tng hiu sut quang xc tc cho mng. Cc k t qu v tnh
nng quang xc tc sau s cho ta thy hiu qu ca b mt ny.
3.3
Tnh nng quang xc tc :
3.3.1
Kh nng phn hy MB:
Trn c s nghin cu ca cng trnh [2], vic o tnh nng quang xc tc

mng TiO 2 v mng TiO 2 pha tp SnO 2 ch ti nhit 5000C. S thay i v nng
ca dung dch theo thi gian c tnh ton da theo s st gim v hp thu
ca dung dch MB theo thi gian ti nh hp thu chnh ca dung dch MB 10 ppm
ti bc sng hp thu cc i 662 nm. Hnh 3.9 di y m t suy gim nng
ca cc mu mng TiO 2:SnO2 vi cc nng khc nhau c nung 5000C
trong 2 gi. Cc mu c chiu sng lin tc bng n compact sau mi khong
thi gian nht nh mu c mang i o ph hp th bng my hp thu Uv-Vis.
5%
10%
20%
30%
1 .1
1 .0
0 .9
0 .8
C / C0
0 .7
0 .6
0 .5
0 .4
0 .3
0 .2
0
50
100
150
200
250
T h i g ia n (p h u t )
Hnh 3.9
th biu din nng MB theo thi gian ng vi cc mu

pha tp SnO2 khc nhau
SVTH: Hunh Ch Cng
59
T hnh 3.19 ta thy vi nng SnO2 pha tp cng cao, MB cng nhanh b
phn hy, hot tnh quang xc tc ca mng cng mnh khi chiu nh sng bng
n compact.
Hnh 3.20 l th so snh hot tnh quang xc tc ca mng TiO 2:SnO2 vi
mng TiO 2.
TiO2:SnO2(30%)
TiO2
1.1
1.0
0.9
0.8
C/C0
0.7
0.6
0.5
0.4
0.3
0.2
0
50
100
150
200
250
Th
i gian (phut)
Hnh 3.10
th kho st nng MB theo thi gian xc tc mu TiO2

v TiO2:SnO2
T kt qu v kh nng phn hy MB, ta thy khi pha tp thm SnO 2 hiu ng

quang xc tc tng ln ng k . Nh gii thch phn 3.1, khi pha tp thm
SVTH: Hunh Ch Cng
60
SnO2 c s dch chuyn in t t vng dn ca TiO2 sang SnO 2 lm gim mt

in t vng ny dn n tng xc sut hp thu photon. ng thi, s dch chuyn
ny ngn cn qu trnh ti hp ca in t - l trng, tng s in t v l trng
tham gia vo qu trnh quang xc tc. iu ny lm tng hiu sut quang xc tc
ca TiO2, c th ng dng tt trong iu kin chiu sng bnh thng (nh sng mt
tri, nh sng n phn ln nng lng nh sng nm trong vng nh sng kh
kin). Kt qu ny ph hp vi suy on t kt qu ph UV-VIS cp phn
3.1.
Hnh 3.11 S mt mu ca dung dch MB trn lam knh theo thi gian
a) Mu lam knh ph mng
b) Mu lam knh cha ph mng.
Hnh 3.11 l hnh nh trc quan v kh nng phn hy hp cht hu c ca

mng TiO 2:SnO2 trn lam knh trong qu trnh chi u sng bng n compact v
c chp nh theo thi gian. Ta thy MB b phn hy rt nhanh. Ngoi kh nng
phn hy cht hu c, tnh siu a nc ca mng lm git MB tri rng ra trn lam
knh, tng din tch tip xc, dn n thi gian phn hy MB nhanh.
SVTH: Hunh Ch Cng
3.3.2
61
Tnh siu a nc ca mng:
Chng ti tin hnh o gc thm t 2 mu: 1 mu c chiu sng lin tc

bng n compact trong 2 gi ; 1 mu c gi trong iu kin bnh thng (t
di nh sng trong phng v sau ct li vo hp ti iu kin chiu sang bnh
thng). Theo kt qu nghin cu trc y [1], TiO 2 khi c chiu UV gc thm
t s gim, sau mt thi gian ngng chiu, gc thm t s tng chm. Sau y l
cc kt qu o c:
Hnh 3.12 Gc thm t trn lam knh cha ph mng
Hnh 3.13 Gc thm t trn mng TiO 2:SnO2 trong iu kin bnh thng
SVTH: Hunh Ch Cng
a)Mng TiO 2:SnO2
62
b)Mng TiO 2
Hnh 3.14 Gc thm t trn mng TiO 2:SnO2 chiu sng 2 gi (a) v mng
TiO2 chiu UV [2](b)
Bng 3.1
Bng kt qu gc thm t ca cc mu:

Mu
Gc thm t trung bnh
Lam trng
46,25o
TiO2:SnO2 cha chiu
12,19o
TiO2:SnO2 chiu sng 2 gi
<2o
T hnh 3.13 ta thy khi chiu sng t (tip xc vi nh sng hng ngy trong
thi gian ngn) gc thm t ca mng gim rt nhiu so vi lam knh trng. Kt
qu hnh 3.14 ta thy sau khi c chiu bng n compact (thnh ph n tia UV rt
t) mng (a) cng c tnh cht siu thm t nh mng TiO 2 (b) sau khi chiu t
ngoi.
SVTH: Hunh Ch Cng
3.3.3
63
Kh nng dit khun:
Tnh cht dit khun ca mng c kim nghim bng phng php m s
khun lc trn a petri (hnh 3.15 ). Mu lam kim nghim gm c mu lam khng
c ph mng lm mu i chng, v mu lam c ph mng TiO 2:SnO2. C hai
mu ny u c kch thch bng n compact trc khi th vi sinh. Sau cc
mu lam c nh 100 l dung dch vi khun nng 10-4 CFU ln trn v gi
trong khong thi gian 04 gi, tip sau c ra li bng 5ml nc tit trng, v ly
100 l dung dch sau ra ny cy li ln cc a thch vi khun pht trin (nhit
370C, trong 24 gi).
Hnh 3.15
Hnh nh khun lc trn a petri
a) Khun lc mc trn a petri ca mu i chng;

b) Khun lc mc trn a petri ca mu lam TiO 2:SnO2.
T hnh 3.15 ta thy khi pha tp thm SnO 2 hiu ng quang xc tc tng ln
ng k. iu ny ph hp vi suy on t kt qu ph UV-VIS ni trn.
SVTH: Hunh Ch Cng
64
KT LUN
Trong qu trnh nghin cu thc hin kha lun ny, chng ti tm hiu l
thuyt v sol-gel, c ch quang xc tc v dit khun ca TiO2. Nhm m rng b
hp thu ca vt liu nano bn dn TiO2 v vng kh kin, tng hiu sut quang xc
tc ca TiO2 chng ti thc hin pha tp SnO 2 vo TiO 2 bng phng php SolGel.
Chng ti thu c cc kt qu sau:
Tng hp thnh cng nano TiO2:SnO2 bng phng php Sol-Gel di
dng mng v bt.
Tng hp mu vi cc t l pha tp SnO 2 khc nhau nhm kho st hot
tnh quang xc tc. Kt qu cho thy TiO2:SnO2 to ra c hot tnh quang xc tc

tt hn TiO 2 di tc dng ca nh sng kh kin. Ngoi phng php th MB nh
cc ti liu trc, chng ti th kh nng dit khun bng phng php th vi
sinh. Kt qu cho thy TiO2:SnO2 chng ti to ra thc s c kh nng dit khun
tt.
Pht hin vai tr ca SnO 2 khi pha tp cn c tc dng gim nhit v
y mnh qu trnh chuyn pha ca TiO2, v tm ra nng SnO2 tt nht.
Pht hin vai tr ca SnO2 khi pha tp cn c tc dng lm gim kch
thc ht TiO 2 . Kch thc ht to thnh kh nh m khng cn s dng cc cht

chn no khc.
Kho st vt liu TiO2:SnO2 bng cc phng php UV -VIS, XRD, TEM,
SEM, AFM. Kt qu ch ra rng mng ch to c kh ng u, kch thc ht

kh nh (10-15nm). Mt ln na chng t ch to thnh cng nano TiO 2:SnO2..
Tuy nhin, do iu kin thi gian v thit b cn hn ch, chng ti cha tin
hnh kho st cc yu t nh hng n dy mng, c tc ng ln n cc tnh
cht ca mng.
SVTH: Hunh Ch Cng
65
Hng pht trin ca ti:

T cc kt qu t c nh trn, ti c th tip tc nghin cu:
Kho st vic kim sot dy mng v cc nh hng ca dy n
cc tnh cht ca mng.
To mng v kho st cc tnh cht TiO2:SnO2 trn nn gch men, bc
u a vt liu vo ng dng trong cuc sng.
SVTH: Hunh Ch Cng
66
Ti liu tham kho

Ting Vit:
[1]
ng Mu Chin (2008), Nghin cu ch to vt liu nano t lm sch v

dit khun trn gch men, Phng th nghim Cng ngh nano HQG.
Tp.HCM.
[2]
ng Th M Dung (2008), Tng hp v nghin cu tnh cht quang ca

mng nano CdS nhm ng dng to cm bin sinh hc v quang xc tc,
Lun vn thc s Trng i Hc Khoa Hc T Nhin.
[3]
Nguyn An H Qunh Giao (2008), Nghin cu s dch chuyn Sol-Gel

Silica bng phng php ph dao ng, Lun vn thc s Trng i Hc
Khoa Hc T Nhin.
[4]
L Th Hoi Nam, Bi Tin Dng, Trn Th c, Nguyn Th Dung, Nguyn

Xun Ngha (2004), Mt s yu t nh hng n hot tnh quang xc tc
phn hy phenol trn mng TiO2 trn knh, Vin Khoa hc v Cng ngh
Vit Nam.
[5]
Phm Hng Ngc (2007), Lun vn tt nghip, Trng i Hc Khoa Hc

T Nhin, TPHCM.
Ting Anh:
[6]
Arpac E, Saylkan F, Asilturk M, Tatar P, Nadir Kiraz, Saylkan H (2007),

Photocatalytic performance o f Sn-doped and undoped TiO 2 nanostructured
thin films under UV and vis -lights, Inonu University, Faculty of Arts and
Science, Department of Chemistry, 44280 Malatya, Turkey.
[7]
Arsen Z. Adamyan, Zaven N. Adamian, Vladimir M. Aroutiounian (2003),

Preparation of SnO 2 Films with Thermally Stable Nanoparticles,
Department of Physics of Semiconductors & Microelectronics, Yerevan State
University, 1, Alex Manoogian, Yerevan 375025, Armenia.
[8]
Arturo I. Martneza, Dwight R. Acostaa, Gerardo Cedillob (2005), Effect

of SnO 2 on the photocatalytical properties of TiO 2 films, Instituto de
Investigaciones en Materiales, Universidad Nacional Autonoma de Mexico,
Mexico, D.F. 01000, Mexico.
SVTH: Hunh Ch Cng
67
[9]
Chen Shifu, Chen Lei, Gao Shen, Cao Gengyu (2006), The preparation of
coupled SnO2/TiO2 photocatalyst by ball milling, Department of Chemistry,
Huaibei Coal Normal College, Anhui, Huaibei 235000, Peoples Republic of
China.
[10]
Dhere R.G, Moutinho H.R, Asher S, Li X, Ribelin R, and Gessert T, Young

D (1998), Characterization of SnO 2 Films Prepared Using Tin Tetrachloride
and Tetra Methyl Tin Precursors, National Renewable Energy Laboratory,
Golden, CO 80401.
[11]
El-Maghraby E.M, Nakamura Y, Rengakuji S (2008), Composite TiO 2

SnO2 nanostructured films prepared by spin -coating with high photocatalytic
performance, Center for Instrumental Analysis, Toyama University, 3190
Gofuku, Toyama 930-8555, Japan.
[12]
Funda Saylkana, Meltem Asiltrk, Nadir Kiraz, Esin Burunkaya, Ertu grul
Arpac, Hikmet Saylkana (2009), Photocatalytic antibacterial perf ormance
of Sn4+-doped TiO 2 thin films on glass substrate, Akdeniz University,
Faculty of Arts and Science, Department of Chemistry, 07100 Antalya,
Turkey.
[13]
Geraldine C. Schwartz Kris V. Srikrishnan (2006), Handbook of

Semiconductor Interconnection Technolo gy, Taylor & Francis Group,.
[14]
Giancarlo Espsito de Souza Brito, Celso Valentim Santilli, Sandra Helena

Pulcinelli (1994), Evolution of the fractal structure during sintering of SnO 2
compacted sol-gel powder, lnstituto de Quimica de Araraquara -UNESP,
P.O. Box 355, 14800-900, Araraquara, SP, Brazil.
[15]
Hikmet Saylkan (2004), Improved photocatalytic activity of Sn 4+-doped

and undoped TiO 2 thin film coated stainless steel under UV and VIS
irradiation, University, Faculty of Education, Department of Science, 44 289
Malatya, Turkey.
[16]
Hsiao-Ching Lee, Weng:Sing Hwang (2006), Substrate effects on the

oxygen gas sensing properties of SnO 2/TiO2 thin films, Department of
Materials Science and Engineering, National Cheng Kung University,
Tainan, Taiwan.
[17]
Jeffrey Brinker . C, George W. Scherer (1990) , Sol-gel science -The

Physics and Chemistry of Sol -Gel Processing, Boston San Diego New York
SVTH: Hunh Ch Cng
68
[18]
Jianwei Gong, Quanfang Chen (2004), Sol -Gel Prepared Single Wall
Carbon Nanotube SnO 2 Thin Film for Micromachined Gas Sensor,
Department of Mechanical, Materials & Aerospace Engineering, University
of Central Florida, Orlando.
[19]
Kwang Soo Yoo, Nam Woong Cho, Han Sang Song, Hyung Jin Jung (1995),
Surface morphology and gas -sensing characteristics of SnO 2-x thin films
oxidized from Sn films, Division of Ceramics, Korea Institute of Science
and Technology, P.O. Box 131, Cheongryang, Seoul 130 -650, South Korea.
[20]
Lm Quang Vinh (2006), Elaboration et caractrisation de couches minces

vitreuses dopes par des nano -particules semi-conductrices.
[21]
Lin-Rui Hou, Chang-Zhou Yuan, Yang Peng (2007), Synthesis and

photocatalytic property of SnO 2/TiO2 nanotubes composites, Institute of
Applied Chemistry, Xinjiang University, Urumqi 830046, PR China.
[22]
Lung-Chuan Chena, Fu-Ren Tsai , Shih-Hao Fang, Yi-Ching Hoa (2009),

Properties of solgel SnO 2/TiO2 electrodes and their photoelectrocatalytic
activities under UV and visible light illumination, Department of Polymer
Materials, Kun:Shan University, Yung Kang City, Tainan 710, Taiwan,
ROC.
[23]
Mahanty S, Roy S, Suchitra Sen (2004), Effect of Sn doping on the

structural and optical properties of sol gel TiO 2 thin films, SEM-ESCA
Section, Central Glass and Ceramic Research Institute, 196 Raja S.C.
Mullick Road, Kolkata 700032, India.
[24]
Masahisa Okada, Kazuki Tajima, Yasusei Yamada, Kazuki Yoshimura

(2009), Photocatalytic performance of very thin TiO 2:SnO2 stacked-film
prepared by magnetron sputtering, National Institute of Advanced Industrial
Science and Technology (AIST), 2266 -98 Anagahora, Shimoshidami,
Moriyama-ku, Nagoya 463-8560, Japan.
[25]
Minghua Zhou, Jiaguo Yu, Shengwei Liu, Pengcheng Zhai, Li Jiang (2008),
Effects of calcination temperatures on photocatalytic activity of SnO2/TiO2
composite films prepared by an EPD method, State Key Laboratory of
Advanced Technology for Material Synthesis and Processing, Wuhan
University of Technology, Wuhan 430070, PR China
SVTH: Hunh Ch Cng
69
[26]
Romana Khan, Tae-Jeong Kim (2009), Preparation and application of

visible-light-responsive Ni-doped and SnO 2-coupled TiO 2 nanocomposite
photocatalysts, Department of Applied Chemistry, Kyungpook National
University, Taegu 702-701, Republic of Korea.
[27]
Sasikala R, Shirole A, Sudarsan V, Sakuntala T, Sudakar C, Naik R,

Bharadwaj S.R (2009), Highly dispersed phase of SnO 2 on TiO 2
nanoparticles synthesized by polyol-mediated route: Photocatalytic activity
for hydrogen generation Chemistry Division, Bhabha Atomic Research
Centre, Trombay, Mumbai 400085, India.
[28]
Saylkan F, Asilt M, Tatar P, Kiraz N, Arpac E, Saylkan H (2008),

Photocatalytic performanc e of Sn-doped TiO 2 nanostructured mono and
double layer thin films for Malachite Green dye degradation under UV and
vis-lights, Akdeniz University, Faculty of Arts and Science, Department of
Chemistry, 07100 Antalya, Turkey.
[29]
Senguttuvan T. D and Malhotra l. K (1996), Electronic structure of sol -gel

derived SnO 2 thin films, Thin film Laboratory, Department of Physics,
Indian Institute of Technology Delhi, Hauz Khas, New Delhi 1 IO 016, India.
[30]
Seung-Chul Lee, Jae-Ho Lee, Tae:Sung Oh, Young-Hwan Kim (2003),

Fabrication of tin oxide film by sol gel method for photovoltaic solar cell
system, Department of Metallurgical Engineering and Materials Science,
Hong Ik University, 72-1 Sangsu-dong, Mapo-gu, Seoul 121-791, South
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[32]
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Terriera C, Chatelona J.P, Berjoanb R, Rogera J. A (1995),Sb-doped SnO,

transparent conducting oxide from the sol -gel dip-coating technique,
Dipartement de Physique des Matiriaur, Universitt Claude Bernard, Lyon 1,
France.
[34]
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photocatalysis and related surface phenomena, Kanagawa Academy of
SVTH: Hunh Ch Cng
70
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Kanagawa 213-0012, Japan.
[35]
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Fabrication and its characteristics of metal -loaded TiO2:SnO2 thick-film
gas sensor for detecting dichloromethane, Department of Chemistry,
Keimyung University, Daegu 704 -701, Republic of Korea.
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NH CHNH: TC GI CA TI LIU NY L TIN S LM QUANG

VINH V HUNH CH CNG. HTTP://WWW.MIENTAYVN.COM CH

CBHD: TS. Lm Quang Vinh

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

2.1.1.2 Thc hin ................................ ................................ .................... 41

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Tnh cht quang ca TiO2 ................................ ................................ .20

S liu v tnh cht v cu trc ca TiO2 ................................ ........... 21

Bng kt qu gc thm t ca cc mu ................................ ............ 62

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Phn ng thy phn ................................ ................................ ............ 10

Phn ng ngng t................................ ................................ .............. 11

S pht trin cu trc tinh th trong iu kin xc tc acid ................. 12

S pht trin cu trc tinh th trong iu kin xc tc base ................. 12

S pht trin cu trc mng trong qu trnh sol -gel............................. 13

Cc nhm sn phm ca phng php sol-gel ................................ .... 15

Phng php ph quay (spin coating) ................................ ................. 16

Cc giai on ca phng php ph quay................................ ........... 16

S pht trin dy mng ph ................................ ........................... 18

Hnh 1.10 Qu trnh ph nhng ................................ ................................ ........... 18

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

S to sol SnO 2 ................................ ................................ .............. 41

S to sol TiO 2:SnO2 ................................ ................................ ..... 44

My nhng mng (dipcoating) ................................ .......................... 46

My OCA-20 Dataphysics ................................ ............................... 49

Ph UV-VIS ca mng ng vi cc nng ................................ ...... 51

S dch chuyn in t trong TiO 2:SnO2................................ ........ 52

Ph hp thu ca cc mng TiO 2:SnO2 pha tp vi cc nng khc

Ph nhiu x tia X ca mu bt TiO2 ti cc nhit khc nhau......... 54

Ph nhiu x tia X ca mu bt TiO2:SnO2 vi cc nng pha tp

nh TEM ca mu TiO 2:SnO2................................ ............................ 56

nh SEM ca mu TiO 2:SnO2 ................................ ............................ 57

nh AFM ca mu mng TiO 2:SnO2 (30%) ti 5000C........................ 57

th biu din nng MB theo thi gian ng vi cc mu pha tp

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Hnh 3.10 th kho st nng MB theo thi gian xc tc mu TiO 2 v

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Phng php sol-gel:

Phng php sol gel l mt k thut tng hp ha keo to ra cc vt liu

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Mt h Gel l mt trng thi m cht lng v rn phn tn vo nhau, trong

Cc qu trnh chnh xy ra trong Sol-Gel:

Qu trnh sol-gel l mt phng php ha hc t tng hp cc phn t huyn

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Phn ng thy phn

M(OR)n + xHOH M(OR) n-x (OH)x + xROH

Phn ng ngng t [1]:

SVTH: Hunh Ch Cng

CBHD: TS. Lm Quang Vinh

Cc giai on chnh [17]:

To dung dch sol: alkoxide kim loi b thy phn v ngng t, to

Gel ha (gelation): gia cc ht sol hnh thnh lin kt. nht ca

Thiu kt (sintering): y l qu trnh kt cht khi mng, c iu

CBHD: TS. Lm Quang Vinh