I HC QUC GIA H NI

TRNG I HC CNG NGH

Nguyn Xun Vn

NGHIN CU CH TO MNG MNG TiO2

NHM CHO MC TIU
NG DNG QUANG XC TC

KHO LUN TT NGHIP I HC H CHNH QUY

Ngnh: Vt l k thut

H NI - 2011

I HC QUC GIA H NI
TRNG I HC CNG NGH

Nguyn Xun Vn

NGHIN CU CH TO MNG MNG TiO2

NHM CHO MC TIU
NG DNG QUANG XC TC

KHO LUN TT NGHIP I HC H CHNH QUY

Ngnh: Vt l k thut
Cn b hng dn: PGS.TS. L Vn Hng

H NI - 2011

LI CM N
Li u tin, em xin by t s knh trng v bit n su sc nht ti PGS.TS. L
Vn Hng ngi nh hng, gip v to iu kin thun li nht cho em
trong sut thi gian hon thnh kha lun tt nghip. Thy ch dy cho em nhng
kin thc v k nng c bn trong vic nghin cu khoa hc.
Em xin c bit cm n TS. Ng Th Hng L lun tn tnh hng dn, ch
bo cho em nhng kin thc l thuyt v thc nghim qu gi, cng s gip , ng
vin em hon thnh kha lun ny.
Em xin c gi li cm n ti CN. Hong Thanh Vn v TS. V nh Lm,
ThS. Hng Mnh, TS. Trn ng Thnh, CN. Nguyn Vn Chin, ThS. Nguyn
Vn Khin cng ton th cn b Phng Vt l Vt liu T v Siu dn, Vin Khoa hc
Vt liu, quan tm, gip em ngay t ngy u lm kha lun, gip em thc hin
cc php o v c nhiu kin ng gp vo kt qu ca kha lun.
Cng xin c cm n Phng Quang ha in t, TS. Nguyn Thanh Hng, TS.
Trn Thu Hng gip em rt nhiu trong vic hon thnh kha lun.
Em xin c cm n s quan tm, gip , n cn ch bo v nhit tnh ging dy
ca cc thy c ti trng i hc Cng Ngh, i hc Quc gia H Ni. Nhng kin
thc m cc thy c truyn t l nn tng vng chc cho chng em trong qu trnh
hc tp cng nh sau khi ra trng.
V cui cng, c c kt qu nh ngy hm nay, em xin c gi li cm n
v lng bit n n nhng ngi thn ca mnh.

TM TT NI DUNG
Mc tiu ca kha lun ny l thc hin cc nghin cu ch to mng mng nn
TiO2 anatase pha tp N c kch thc nm bng phng php nhit cao (500 oC)
v kho st cc tnh cht quang in ca vt liu ny, nhm ch to vt liu mng TiO 2
hp th nh sng vng nhn thy ng dng trong quang xc tc. T nhng nguyn liu
ban u chng ti tin hnh ch to cc mu mng mng TiO 2 vi cc t l % kh N 2
khc nhau. Trong kha lun ny, cu trc vt liu c nghin cu bng phng php
hin vi in t qut SEM v phng php phn tch ph nhiu x tia X (XRD); kho
st dy v b mt mng bng Profiler; cc c trng cho tnh cht quang (ph hp
th, truyn qua) c kho st bng my UV-VIS,... Cc php o thc hin trn cc
h my ca Vin Khoa hc Vt Liu, Vin Khoa hc v Cng Ngh Vit Nam. Kt qu
thc nghim c so snh rt ra kt lun v u v nhc im ca vt liu ch to
vi mong mun pht trin hng nghin cu v ng dng ca vt liu ny trong cng
ngh iu ch hydro.

LI CAM OAN
Em xin cam oan kha lun ny c hon thnh l kt qu nghin cu ca ring
mnh di s hng dn ca PGS.TS. L Vn Hng Vin Khoa hc Vt liu Vin
Khoa hc v Cng ngh Vit Nam. Cc s liu, kt qu trong kha lun l hon ton
trung thc cha tng c ai cng b trong bt k cng trnh no.

MC LC

M U.......................................................................................................1
Chng 1. TNG QUAN....................................................................................3
1.1. Vt liu TiO2...............................................................................................3
1.1.1. Gii thiu vt liu TiO2.......................................................................3
1.1.2. Cu trc ca vt liu TiO2...................................................................4
1.1.2. Tnh cht quang ca vt liu TiO2.......................................................7
1.2. Vt liu TiO2 nanomet................................................................................8
1.2.1. Tnh cht quang xc tc.......................................................................8
1.2.1.1. C ch phn ng xc tc quang d th.........................................9
1.2.1.2. C ch xc tc quang ca TiO2 anatase......................................12
1.2.2. Vt liu TiO2 pha tp.........................................................................14
1.2.2.1. Vt liu TiO2 pha tp cc nguyn t kim loi.............................14
1.2.2.2. Vt liu TiO2 pha tp cc nguyn t phi kim..............................17
1.3. ng dng ca vt liu TiO2......................................................................17
1.3.1. Tch H2 t H2O..................................................................................17
1.3.2. Cc ng dng khc ca vt liu TiO2................................................19
1.3.2.1. ng dng lm xc tc quang x l mi trng.........................19
1.3.2.2. ng dng lm cht n trong cc lnh vc sn t lm sch......19
1.3.2.3. X l cc ion kim loi nng trong nc ....................................20
1.3.2.4. Mt s ng dng khc................................................................21
Chng 2. THC NGHIM............................................................................22
2.1. Ch to vt liu mng TiO2......................................................................22
2.1.1. Ch to mu TiO2 dng sol................................................................22
2.1.1.1.Quy trnh thc nghim................................................................22
2.1.1.2.Cc phn ng ha hc xy ra trong quy trnh thc nghim........23
2.1.2. Ch to mu mng mng TiO2..........................................................25
2.1.3. Pha tp N vo mng mng TiO2........................................................27
2.2. Cc k thut o kho st tnh cht ca vt liu TiO2 pha tp N................27
2.2.1. Php o nhiu x tia X (XRD)..........................................................27
2.2.2. K thut hin vi in t qut (SEM).................................................28
2.2.3. o dy v b mt mng bng Profiler..........................................28
2.2.4. Ph hp th UV-VIS..........................................................................29
Chng 3. KT QU V THO LUN........................................................30
3.1. Ch to mu..............................................................................................30
3.2. Kt qu nhiu x tia X..............................................................................31
3.3. Kt qu chp FESEM...............................................................................34
3.4. Kt qu o dy v b mt mng bng Profiler....................................36
3.5. Kt qu o ph hp th.............................................................................37
3.6. Kt qu o truyn qua.........................................................................39
KT LUN........................................................................................................41

TI LIU THAM KHO................................................................................42

M U
Mt tri cung cp cho b mt tri t mt lng nng lng khng l vo khong
3.10 J/nm. Vic nghin cu chuyn ha c hiu qu ngun nng lng ny thnh
cc dng hu dng khc phc v i sng con ngi l mt trong nhng thch thc
i vi s pht trin nghin cu khoa hc v cng ngh trong tng lai. Mt trong
nhng hng nghin cu l s dng cc cht bn dn ng vai tr quang xc tc
chuyn ha nng lng nh sng mt tri thnh nng lng in hoc ha hc.
24

Titanium Dioxide (TiO2) l cht xc tc bn dn. Gn mt th k tr li y, bt

TiO2 vi kch thc c m c iu ch quy m cng nghip v c ng dng
rng ri trong nhiu lnh vc khc nhau: lm cht n trong cao su, nha, giy, si vi,
lm cht mu cho sn, men gm, s [3]. Gn y, TiO 2 tinh th kch thc nm
cc dng th hnh rutile, anatase, hoc hn hp rutile v anatase, v brookite c
nghin cu ng dng vo cc lnh vc pin mt tri, quang phn hy nc v lm vt
liu quang xc tc tng hp cc hp cht hu c, x l mi trng, ch to sn t lm
sch, ch to thit b in t, u cm bin v trong lnh vc dit khun [4,5]. Cc ng
dng mi ca vt liu TiO2 kch thc nm ch yu da vo tnh oxy ho kh mnh ca
n. Vi hot tnh quang xc tc cao, cu trc bn v khng c, vt liu TiO 2 c cho
l vt liu trin vng nht gii quyt rt nhiu vn mi trng nghim trng v
thch thc t s nhim. TiO 2 ng thi cng c hy vng s mang n nhng li
ch to ln trong vn khng hong nng lng qua s dng nng lng mt tri da
trn tnh quang in v kh nng phn tch nc.
Tuy nhin do rng vng cm ca Titanium Dioxide kh ln (3,25 eV i vi
anatase v 3,05 eV i vi rutile) nn ch nh sng t ngoi (UV) vi bc sng <
380 nm mi kch thch c in t t vng ha tr ln vng dn v gy ra hin tng
quang xc tc. iu ny, hn ch kh nng quang xc tc ca Titanium Dioxide, thu
hp phm vi ng dng ca vt liu ny. s dng c nh sng mt tri vo qu
trnh quang xc tc ca Titanium Dioxide, cn thu hp vng cm ca n. thc hin
mc ch ny nhiu ion kim loi v phi kim c s dng thay i cc th hnh
ca Titanium Dioxide. C th thc hin thay i cu trc ca Titanium Dioxide bng
cc phng php: sol gel, thy nhit, ng kt ta, hoc thay i b mt vi cc
phng php tm, nhng, phun, hp ph,
Pha tp TiO2 bng nhng ion phi kim khc nhau l cch thc hiu qu m
rng nh sng hp ph t vng UV sang vng nhn thy v gim s ti kt hp ca
nhng electron v l trng c pht quang ca TiO 2. c mt s bi bo v s tng

hp cht quang xc tc TiO2 pha tp N nh ca nhm tc gi R. Asahi, T. Morikawa,

T. Ohwaki, K. Aoki, Y. Taga, Visible-light photocatalysis in nitrogen-doped titanium
oxides [6]; T. Morikawa, R. Asahi, T. Ohwaki, K. Aoki, Y. Taga, Band-gap narrowing
of titanium dioxide by nitrogen doping [7]; H. Irie, Y. Watanabe, K. Hashimoto,
Nitrogen-concentration dependence on photocatalytic activity of TiO 2KxNx powders
[8],...
T nhng nghin cu nn tng , vi mong mun c ng gp mt phn nh
cho vic tm kim vt liu quang xc tc nn TiO 2 hot ng trong vng nh sng nhn
thy, chng ti tin hnh nghin cu ti: Nghin cu ch to mng mng TiO 2
nhm cho mc tiu ng dng quang xc tc.

Chng 1. TNG QUAN

1.1. Vt liu TiO2
1.1.1. Gii thiu vt liu TiO2
Mi trng nhim l h qu ca s pht trin trn th gii, y l mt vn
ht sc nghim trng khng th b qua. V d v nhim mi trng c th c lit
k rt nhiu nh: nhim ngun nc do cht thi cng nghip v h gia nh, cc
bnh v h hp do nhim khng kh nh SO x v NOx, khng kh trong phng b
nhim bi cc hp cht hu c pht ra t vt liu xy dng mi c pht trin, dioxin
thot ra t vt liu nha trong qu trnh t rc,... Thc t l vic s dng nng lng
loi b s nhim mi trng li lm tng lng kh thi CO 2 dn n s nng ln
ton cu nhiu hn, do dn n mt tnh trng kh x l khng th s dng nng
lng hon thnh mc tiu chng nhim mi trng.
Trong trng hp nh vy,
chng ta cn mt loi vt liu mi
c th nh nhng hi ha vi mi
trng b nhim khi phc li
nguyn trng bng cch s dng
nng lng t nhin, l mt
phn ca mi trng. Mt gii php
cho vn l cht xc tc
quang. Cht xc tc quang to ra
qu trnh oxy ha trn b mt
loi b cc cht c hi nh cc
hp cht hu c hay vi khun,... khi n c tip xc vi nh sng mt tri.
Cc phn ng quang ha trn b mt Titanium Dioxide (TiO 2) thu ht nhiu s
ch v vic ng dng thc t lm sch mi trng nh lm sch gch, knh,
TiO2 c nhng li th ca s n nh ha hc cao, khng gy c, gi thnh tng i
thp, nhng mt bt li ln l ch c nh sng t ngoi (chim khong 4% bc x mt
tri) c s dng cho cc phn ng quang ha. V vy n l s quan tm rt ln
nhm tm cch m rng vng bc sng hp th ca TiO 2 sang vng nhn thy m
khng lm gim hot tnh quang v s dng c hiu qu hn c tnh quang xc tc
ca loi vt liu ny. Vi nhng thnh cng bc u, nhng nghin cu v cu trc
vt liu TiO2 pha tp chng minh rng tnh cht v c im cu trc ca vt liu

TiO2 hon ton c th thay i c khi thay th mt phn cc ion titan bng cc ion
ca cc nguyn t khc. Hng nghin cu ny nhm mc ch m rng cc ng dng
ca loi vt liu ny trong lnh vc ch to vt liu x l mi trng, vt liu xy dng
thn thin mi trng, nng lng sch, trong iu kin chiu sng thng thng
m khng cn b sung ngun sng t ngoi (UV).
Hin nay, TiO2 c rt nhiu ng dng trong cuc sng nh ha m phm, cht
mu, sn, ch to cc loi thy tinh, men v gm chu nhit dng ht mn kch
thc nm, TiO2 c ng dng trong cc lnh vc ch to pin mt tri, sensor, lm
cht xc tc quang, c bit TiO2 c quan tm trong lnh vc lm xc tc quang
ha ng dng trong x l mi trng v cng ngh nng lng.
1.1.2. Cu trc ca vt liu TiO2
TiO2 trong t nhin tn ti ba dng th hnh khc nhau l rutile, anatase, v
brookite (hnh 1.1). C ba dng tinh th ny u c chung mt cng thc ha hc TiO 2,
tuy nhin cu trc tinh th ca chng l khc nhau. Hng s mng, di lin kt TiO, v gc lin kt ca ba pha tinh th c trnh by trong bng 1.1.
Titanium (IV) Oxide (II) c mt pha bn l pha rutile (tetragonal) v hai pha
gi bn l anatase (tetragonal) v brookite (orthorhombic). C hai pha gi bn chuyn
thnh pha rutile khi vt liu c nung nhit trn 700 oC [9] (915oC cho pha
anatase v 750oC cho pha brookite). Mt s tc gi cng thy rng nhit 500 oC
pha anatase bt u chuyn sang pha rutile trong cc qu trnh x l nhit [10].

Hnh 1.1. Cc dng th hnh khc nhau ca TiO2: (A) rutile, (B) anatase, (C) brookite.

Bng 1.1. Cc c tnh cu trc ca cc dng th hnh ca TiO2.

H tinh th
Hng s mng ()
Nhm khng gian
S n v cng thc
Th tch c s ()
Mt khi
di lin kt Ti-O ()
Gc lin kt Ti-O-Ti

Anatase
Tetragonal

Rutile
Tetragonal

a=4,59
c=2,96

a=3,78
c=9,52

P42/mnm
2
31,22
4,13
1,95 (4)
1,98 (2)
81,2o
90o

I41/amd
4
34,06
3,79
1,94 (4)
1,97 (2)
77,7o
92,6o

Brookite
Octhorhombic
a=9,18
b=5,45
c=5,15
Pbca
8
32,17
3,99
1,87~2,04
77,0o~105o

Cu trc mng li tinh th ca rutile, anatase v brookite u c xy dng t

cc a din phi tr tm mt (octahedra) TiO 6 ni vi nhau qua cnh hoc qua nh
oxy chung (hnh 1.2). Mi ion Ti+4 c bao quanh bi tm mt to bi su ion O2-.

Hnh 1.2. Khi bt din ca TiO2.

Cc mng li tinh th ca rutile, anatase v brookite khc nhau bi s bin dng
ca mi hnh tm mt v cch gn kt gia cc octahedra.
Pha rutile v anatase u c cu trc tetragonal ln lt cha 6 v 12 nguyn t
tng ng trn mt n v. Trong c hai cu trc, mi cation Ti +4 c phi tr vi
su anion O2-; v mi anion O2- c phi tr vi ba cation Ti+4. Trong mi trng hp
ni trn khi bt din TiO6 b bin dng nh, vi hai lin kt Ti-O ln hn mt cht so
vi bn lin kt cn li v mt vi gc lin kt lch khi 90 o. S bin dng ny th

hin trong pha anatase r hn trong pha rutile. Mt khc, khong cch Ti-Ti trong
anatase ln hn trong rutile nhng khong cch Ti-O trong anatase li ngn hn so vi
rutile. iu ny nh hng n cu trc in t ca hai dng tinh th, ko theo s khc
nhau v cc tnh cht vt l v ha hc.

Hnh 1.3. Cu trc tinh th ca TiO2: (A) rutile, (B) anatase.

S gn kt gia cc octahedra ca hai pha rutile v anatase c m t nh hnh
1.3. Pha rutile c xp cht cao nht so vi hai pha cn li, cc khi bt din xp tip
xc nhau cc nh, hai khi bt din ng cnh nhau chia s hai cnh chung v to
thnh chui, pha rutile c khi lng ring 4,2 g/cm3. Vi pha anatase, cc khi bt
din tip xc cnh vi nhau, trc c ca tinh th ko di ra v c khi lng ring l 3,9
g/cm3. TiO2 anatase khng pha tp l mt cht cch in d hng c cu trc
tetragonal (a=3,78 ; c=9.52 ) c hng s in mi tnh l 31.
Pha brookite c cu trc phc tp, brookite c cu trc orthorhombic vi i
xng 2/m 2/m 2/m v nhm khng gian Pbca. Ngoi ra, di ca lin kt Ti-O cng
khc nhiu so vi cc pha anatase v rutile, cng nh gc lin kt O-Ti-O [11]. C rt
t ti liu nghin cu v pha brookite.

Hnh 1.4. Cu trc tinh th ca TiO2: brookite.

Tt c cc dng tinh th ca TiO 2 tn ti trong t nhin nh l cc khong,

nhng ch c rutile v anatase dng n tinh th l c tng hp nhit thp.
Hai pha ny cng c s dng trong thc t lm cht mu, cht n, cht xc tc...
Cc mu TiO2 phn tch trong cc nghin cu hin nay bt u c tng hp t pha
anatase v tri qua mt chng trnh nung t c pha rutile bn [10]. Brookite
cng quan trng v mt ng dng, tuy vy b hn ch bi vic iu ch brookite sch
khng ln rutile hoc anatase l iu kh khn. Mt khc, do vt liu mng mng v
ht nano TiO2 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.
1.1.2. Tnh cht quang ca vt liu TiO2
Cu trc in t ca cht bn dn ng vai tr quan trng trong qu trnh quang
xc tc. Khng ging nh mt cht dn in, mt cht bn dn bao gm vng dn (CB
- Conduction Band) v vng ha tr (VB - Valence Band). Nng lng khc bit gia
hai mc ny c gi l nng lng vng cm (E g). Nu khng c s kch thch, in
t lp y vng ha tr, cn vng dn trng. Khi cht bn dn c kch thch bi cc
photon vi nng lng bng hoc cao hn mc nng lng vng cm, cc in t
nhn c nng lng t cc photon s chuyn di t vng VB ln CB. i vi cht
bn dn TiO2, qu trnh c th hin nh sau:

Nh chng ta bit nng lng vng cm ca anatase v rutile tng ng l

3,2 v 3,0 eV ti nhit phng. Chng c th c xc nh t nhiu kt qu
thc nghim khc nhau nh o c trng I/V hay C/V ca tip gip p/n hay tip
gip Schottky bn dn kim loi, hoc o ph hp th, o dn ph thuc nhit
hay quang dn ca vt liu. Hnh 1.5 trnh by ph quang dn ca mng anatase v
rutile. Kt qu trn hnh 1.5 cho thy nng lng ngng quang dn ca mng
anatase cao hn mng rutile. y l quang dn do kch thch vng vng v kt
qu l nng lng ngng gn nh ph hp vi nng lng vng cm quang
hc. Cu trc vng nng lng ca pha rutile c nghin cu rng ri. TiO2
rutile c vng cm thng (3,0 eV). Cn b hp th ca tinh th anatase c
xc nh l 3,2 eV ti nhit phng v m rng ti 3,3 eV ti 4 K.

Hnh 1.5. Ph quang dn ca mng anatase v rutile.

Bng 1.2. Cc c tnh cu trc ca cc dng th hnh ca TiO2.

Chit sut
Anatase
Rutile

2,49
2,903

Khi lng ring

(g/cm3)
3,84
4,26

rng vng cm
(eV)
3,25
3,05

Tnh cht quang hc ca tng pha l tng ng, tuy nhin c mt s khc bit
nh, v d nh b hp th ca chng khc nhau. Bng phng php thc nghim,
ngi ta quan st thy rng trong mng mng cu trc anatase c linh ng cao
hn so vi cu trc rutile [9]. Mc d c ba dng u th hin tnh cht quang nhng
anatase l cu trc c u tin hn trong qu trnh quang xc tc.
1.2. Vt liu TiO2 nanomet
1.2.1. Tnh cht quang xc tc
Nm 1930, khi nim quang xc tc ra i. Trong ho hc n dng ni n
nhng phn ng xy ra di tc dng ng thi ca nh sng v cht xc tc, hay ni
cch khc, nh sng chnh l nhn t kch hot cht xc tc, gip cho phn ng xy ra.
Khi c s kch thch ca nh sng, trong cht bn dn s to ra cp in t - l trng v
c s trao i electron gia cc cht b hp ph, thng qua cu ni l cht bn dn.

Bng cch nh vy, cht xc tc quang lm tng tc phn ng quang ha, c th l

to ra mt lot quy trnh ging nh phn ng oxy ho - kh v cc phn t dng
chuyn tip c kh nng oxy ho - kh mnh khi c chiu bng nh sng thch hp.
1.2.1.1. C ch phn ng xc tc quang d th
Qu trnh xc tc quang d th c th c tin hnh pha kh hoc pha lng.
Cng ging nh cc qu trnh xc tc d th khc, qu trnh xc tc quang d th c
chia thnh cc giai on nh sau:
(1). Khuch tn cc cht tham gia phn ng t pha lng hoc kh n b mt cht
xc tc.
(2). Hp ph cc cht tham gia phn ng ln b mt cht xc tc.
(3). Hp th photon nh sng, sinh ra cc cp in t - l trng trong cht xc
tc, v khuych tn n b mt vt liu.
(4). Phn ng quang ha, c chia lm hai giai on nh:
Phn ng quang ha s cp, trong cc phn t cht xc tc b kch
thch (cc phn t cht bn dn) tham gia trc tip vo phn ng vi cc
cht hp ph ln b mt.
Phn ng quang ha th cp, cn gi l giai on phn ng ti hay phn
ng nhit, l giai on phn ng ca cc sn phm thuc giai on s
cp.
(5). Nh hp ph cc sn phm.
(6). Khuch tn cc sn phm vo pha kh hoc lng.
Ti giai on (3), phn ng xc tc quang ho khc phn ng xc tc truyn
thng cch hot ho xc tc. Trong phn ng xc tc truyn thng, xc tc c hot
ho bi nhit cn trong phn ng xc tc quang ho, xc tc c hot ho bi s hp
th nh sng.
iu kin mt cht c kh nng xc tc quang:
C hot tnh quang ho.
C nng lng vng cm thch hp hp th nh sng t ngoi hoc
nh sng nhn thy.
Qu trnh ban u ca xc tc quang d th vi cht hu c v v c bng cht
bn dn (Semiconductor Catalyst) l s sinh ra ca cp in t - l trng trong cht

bn dn. C rt nhiu cht bn dn khc nhau c s dng lm cht xc tc quang

nh: TiO2, ZnO, ZnS, CdS Khi c chiu sng c nng lng photon (h) thch
hp, bng hoc ln hn nng lng vng cm E g (h Eg), th s to ra cc cp
electron (e-) v l trng (h+). Cc in t c chuyn ln vng dn (quang electron),
cn cc l trng li vng ho tr.
Cc phn t ca cht tham gia phn ng hp ph ln b mt cht xc tc gm hai
loi:
Cc phn t c kh nng nhn e- (Acceptor).
Cc phn t c kh nng cho e- (Donor).
Qu trnh chuyn in t c hiu qu hn nu cc phn t cht hu c v v c
b hp ph trc trn b mt cht xc tc bn dn (SC). Khi , cc quang electron
vng dn s chuyn n ni c cc phn t c kh nng nhn electron (A), v qu trnh
kh xy ra, cn cc l trng s chuyn n ni c cc phn t c kh nng cho
electron (D) thc hin phn ng oxy ho:
h + (SC) e- + h+
A(ads) + e- A-(ads)
D(ads) + h+

D+(ads)

Cc ion A-(ads) v D+(ads) sau khi c hnh thnh s phn ng vi nhau qua
mt chui cc phn ng trung gian v sau cho ra cc sn phm cui cng. Nh vy
qu trnh hp th photon ca cht xc tc l giai on khi u cho ton b chui phn
ng. Trong qu trnh quang xc tc, hiu sut lng t c th b gim bi s ti kt
hp ca cc electron v l trng.
e- + h+

(SC) + E

Trong :
(SC): tm bn dn trung ha.
E: l nng lng c gii phng ra di dng bc x in t (h h)

hoc nhit.
Hiu qu ca qu trnh quang xc tc c th c xc nh bng hiu sut lng
t, l t l gia s s kin xy ra trn s photon hp th. Vic o nh sng b hp th
thc t rt kh khn trong h d th v s tn x ca nh sng bi b mt cht bn

10

dn. xc nh hiu sut lng t chng ta phi tun theo nh lut quang ha ca
Einstein:
nh lut Einstein: Mt photon hay lng t nh sng b hp th th ch c kh
nng kch thch mt phn t ( mt in t).

Hnh 1.6. C ch xc tc quang ca cht bn dn.

Hiu sut lng t ca h l tng c xc nh bi h thc n gin:

Khi mt phn t cht bn dn b kch thch v phn ly ra mt electron km theo

mt l trng, mt s electron sinh ra ny c th chuyn ti cht phn ng, ta gi l N c,
s cn li kt hp vi l trng to li mt phn t trung ha N k. Theo nh lut
Einstein ta c tng s in t = s photon hp th , vy:

Gi s mi phn t (A) tham gia phn ng nhn mt electron, khi s phn t

phn ng s bng s electron c vn chuyn.

Vy hiu sut lng t c gi tr:

11

Nu ta xt qu trnh xy ra trong mt n v thi gian th c th thay s electron

bng tc vn chuyn electron kc v tc ti kt hp electron kk:

y ta tha nhn s khuych tn ca sn phm vo dung dch xy ra rt nhanh,

khng c phn ng ngc tch in t ca A-, v tch l trng ca D+. tng hiu
sut lng t ( ) th chng ta phi ngh cch tng tc chuyn in t k c v gim tc
ti kt hp electron vi l trng k k. By in tch c s dng thc y s
by in t v l trng b mt, tng thi gian tn ti ca electron v l trng trn b
mt cht xc tc bn dn. iu ny dn ti vic lm tng hiu qu ca qu trnh
chuyn in tch ti cht phn ng.
By in tch c th c to ra bng cch bin tnh b mt cht bn dn nh a
thm kim loi, cht bin tnh vo hoc s t hp vi cc cht bn dn khc dn ti s
gim tc ti kt hp in t - l trng v tng hiu sut lng t ca qu trnh
quang xc tc.
1.2.1.2. C ch xc tc quang ca TiO2 anatase
TiO2 dng anatase c hot tnh quang ha cao hn hn cc dng tinh th khc,
iu ny c gii thch da vo cu trc vng nng lng. Nh chng ta bit,
trong cu trc ca cht rn c ba vng nng lng l vng ha tr, vng cm v vng
dn. Tt c cc hin tng ha hc xy ra u l do s dch chuyn electron gia cc
vng vi nhau. Anatase c nng lng vng cm l 3,2 eV, tng ng vi mt
lng t nh sng c bc sng 388 nm. Rutile c nng lng vng cm l 3,0 eV
tng ng vi mt lng t nh sng c bc sng = 413 nm. Gin nng lng
ca anatase v rutile c ch ra nh hnh 1.7.
Vng ha tr ca anatase v rutile nh ch ra trn gin l xp x bng nhau v
cng rt dng, iu ny c ngha l chng c kh nng oxy ha mnh. Khi c kch
thch bi nh sng c bc sng thch hp, cc electron ha tr s tch ra khi lin kt,
chuyn ln vng dn, to ra mt l trng mang in tch dng vng ha tr. Cc
electron khc c th nhy vo v tr ny bo ha in tch ti , ng thi to ra
mt l trng mi ngay ti v tr m n va i khi. Nh vy l trng mang in tch
dng c th t do chuyn ng trong vng ha tr.

12

Hnh 1.7. Gin nng lng ca pha anatase v pha rutile.

Cc l trng ny mang tnh oxy ha mnh v c kh nng oxy ha nc thnh

nhm OH (OH*), cng nh mt s gc hu c khc:
TiO2(h+) + H2O

OH* + H+ + TiO2

Vng dn ca rutile c gi tr gn vi th kh nc thnh kh hidro (th chun l

0,00V), trong khi vi anatase th cao hn mc ny mt cht, ng ngha vi mt th
kh mnh hn. Theo nh gin th anatase c kh nng kh O 2 thnh O2- , nh vy l
anatase cc electron chuyn ln vng dn c kh nng kh O2 thnh O2-.
TiO2(e-) + O2

TiO2 + O2-

iu ny c minh ha bng hnh 1.8.

Hnh 1.8. S hnh thnh gc OH* v O2-.

13

Chnh cc gc OH* v O2- vi vai tr quan trng ngang nhau c kh nng phn
hy cc hp cht hu c thnh H2O v CO2.
Khi TiO2 dng tinh th anatase c hot ha bi nh sng c bc sng ()
thch hp th xy ra s chuyn in t t vng ha tr ln vng dn, ti vng ha tr c
s hnh thnh cc gc OH* v RX+.
TiO2(h+) + H2O

OH* + H+ + TiO2

TiO2(h+) + OH-

OH* + TiO2

TiO2(h+) + RX

RX+ + TiO2

Ti vng dn c s hnh thnh ca cc gc O2- v HO2*:

TiO2(e-) + O2
O2 - + H +
2HO2*

O2- + TiO2

HO2*
H2O2 + O2

TiO2(e-) + H2O2
H2 O2 + O 2

HO* + HO- + TiO2

O2 + HO* + HO-

Vy s khc bit l do dng anatase c kh nng kh O 2 thnh O2- cn rutile th

khng. Do anatase c kh nng nhn ng thi oxy v hi nc t khng kh cng
nh sng t ngoi phn hy cc hp cht hu c. Tinh th anatase di tc dng
ca nh sng t ngoi ng vai tr nh mt cu ni trung chuyn in t t H 2O sang
O2, chuyn hai cht ny thnh dng O 2- v OH* l hai dng c hot tnh oxy ha cao
c kh nng phn hy cht hu c thnh H2O v CO2.
Nh vy khi TiO2 anatase c chiu sng vi photon c nng lng ln hn
nng lng Eg s to ra cp in t - l trng linh ng. 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 v kh oxy ng vai tr l cht nhn to ra cc cht mi c
tnh oxy ho - kh mnh (OH* v O 2-) c th oxy ho hu ht cc cht hu c b ht
bm ln b mt vt liu.
1.2.2. Vt liu TiO2 pha tp
1.2.2.1. Vt liu TiO2 pha tp cc nguyn t kim loi
S pha tp cc ion kim loi chuyn tip hoc cc ion kim loi nhm t him
c kho st mt cch rng ri tng cng s hot ng xc tc quang ca TiO 2

14

[20-33]. Choi v cng s [20] tin hnh mt cuc kho st c h thng nghin
cu phn ng quang ha (photoreactivity) ca 21 loi ion kim loi c pha tp vo
TiO2. Kt qu cho thy, s pha tp ion kim loi c th m rng p ng quang ca
TiO2 vo vng ph kh kin. Khi ion kim loi c kt hp vo mng tinh th ca
TiO2, cc mc nng lng tp cht c hnh thnh trong vng cm ca TiO 2 theo qu
trnh nh sau :
Mn+ + h M(n+1)+ + echMn+ + h M(n-1)+ + hbTrong M v Mn+1 ln lt l kim loi v ion kim loi pha tp.
Hn na, s trao i in t (l trng) gia ion kim loi v TiO 2 c th lm thay
i s ti hp in t - l trng :
By in t : Mn+1 + ecb- M(n-1)+
By l trng : Mn-1 + hvb+ M(n-1)Mc nng lng ca Mn+/M(n-1)+ phi km m hn cnh vng dn ca TiO 2, cn
mc nng lng ca Mn+/M(n+1)+ phi dng hn cnh vng ha tr ca TiO 2. i vi
nhng phn ng quang xc tc, qu trnh dch chuyn ht ti cng quan trng nh qu
trnh by ht ti. Ch khi in t v l trng b by c dch chuyn ti b mt, phn
ng xc tc quang mi c th xy ra. Do , ion kim loi phi c pha tp gn b
mt ca ht TiO2 s dch chuyn ca in tch c tt hn. Trong trng hp pha
tp su, do s dch chuyn in t, l trng ti b mt kh khn hn, ion kim loi
thng c x nh nhng tm ti hp. Hn na, tn ti nng ti u ca ion kim
loi pha tp, trn mc , qu trnh quang xc tc b gim do s ti hp c tng
cng. Trong s 21 ion kim loi c nghin cu, ion Fe; Mo; Ru; Os; Re; V v Rh c
th lm tng qu trnh quang xc tc, trong khi , pha tp ion Co, Al, li to ra nhng
hiu ng khng tt [20]. S khc nhau v hiu ng ca cc ion kim loi l do kh nng
by v dch chuyn in t - l trng ca chng. V d, Cu v Fe, khng ch c th by
in t m c l trng v cc mc nng lng tp cht xut hin gn cnh vng dn
cng nh cnh vng ha tr ca TiO 2. Do vy, pha tp Cu v Fe c th tng cng qu
trnh quang xc tc [20,21,29,30].
S phn tch nh tnh trong vic kho st nh hng ca cc ion kim loi chuyn
tip (Cr, Mn, Fe, Co , Ni v Cu) ln qu trnh quang xc tc ca TiO 2 c tin hnh
bi Wu v cc cng s [26]. S oxy ha quang xc tc ca axit acetic c s dng
nh gi tc dng ca cc ion kim loi pha tp khc nhau. Do ion Cu, Mn v Fe c th

15

by c in t v l trng, vic pha tp cc ion kim loi ny c th cho kt qu tt hn

s pha tp cc ion Cr, Co, Ni, cc ion kim loi ch by mt loi ht ti. Xu v cc cng
s [24] so snh qu trnh xc tc quang ca cc kim loi khc nhau trong nhm t
him ( La, Ce, Er, Pr, Gd, Nd v Sm) khi c pha tp vo TiO 2. S tng cng qu
trnh xc tc quang v s dch ca p ng quang v pha nh sng c quan st
ti nng pha tp nht nh. Kt qu cho thy pha tp ion Gd l hiu qu nht trong
vic tng cng qu trnh xc tc quang do c kh nng dch chuyn ht ti ti b mt
TiO2 tt nht.
Hameed v cng s [23,35] nghin cu qu trnh phn tch nc sn xut
hydro, s dng WO3 pha tp ion kim loi chuyn tip (Fe, Co, Ni, Cu v Zn) di tc
dng ca bc x laser trong vng cc tm. Cnh vng dn ca WO 3 km m hn
EH 2 / H 2O . Do , WO3 khi b chiu x trong nc, khng th kh ion H + thnh phn t

H2. Tuy nhin, khi c ion kim loi chuyn tip trn b mt WO 3, oxit ca kim loi
chuyn tip c hnh thnh, hot ng nh nhng cht bn dn quang xc tc. Do
FeO, CoO, NiO v Cu2O c mc nng lng vng dn m hn EH

2 / H 2O

, cc in t

vng dn c th kh ion H+. Khng ging nh 4 oxit kim loi trn, ZnO khng th by
in t t vng dn ca WO 3 . Do vy ,pha tp Zn khng cho hiu qu nh cc ion
kim loi khc. Pha tp ion Ni vi nng 1% v 10% cho tc to thnh hydro cao
nht, c th mt phn do lm tng xc tc tch hydro t nc khi s dng my khuy
t [35]. Kt qu bo co cho thy khi NiO hoc Cu 2O c s dng vi my khuy t,
hydro c th c to thnh bi s phn tch nc ngay c trong bng ti, c bit
ti nh l phn ng c xc tc (mechano-catalytic reaction) [34]. Khng nh cc
nghin cu trn, Wu v cng s [26] bo co kt qu: pha tp ion Cu v Fe vo TiO 2
em li hiu qu cao hn l pha tp ion Ni. S sai khc ny c th c gii thch bi
cc dng pha tp khc bit. Trong nghin cu ca Wu v cng s, ion kim loi c
pha tp vo mng ht TiO 2, cn trong nghin c ca Hameed v cng s, ion kim loi
c lng ng trn b mt ca WO 3 di dng oxit kim li, hnh thnh nn cht bn
dn composite.
Peng v cng s [19] kho st hiu qu cu TiO 2 pha tp ion Be trong vic sn
xut hydro quang xc tc c mt cht cho in t (ethanol). Kt qu cho thy, s pha
tp ion kim loi gn b mt c li cho vic dch chuyn ht ti cn pha tp mnh (su)
dn n nhng biu hin km. Kt qu hon ton ging vi kt qu ca Choi [20].
Hn na, nng pha tp v phng php chun b cng c th nh hng ti vic

16

sn xut hydro quang xc tc. iu kin ti u ha ion Be pha tp trong TiO 2,

hydro sn xut c cao hn 75% so vi TiO2 khng pha tp.
Nhng nghin cu chuyn su v phng php tng cng quang xc tc ca
TiO2 bng cch pha tp ion kim loi c tin hnh c bit l trong ng dng lm
sch nc, khng kh. Nhng hp cht hu c hp ph bi cc cht xc tc quang,
c phn hy ch yu bi l trng trong vng ha tr v cc gc sinh ra (induced) bi
l trng. Do , c ch trong vic chuyn dch nhng l trng to bi bc x quang ti
b mt l iu v cng quan trng. Mt khc, i vi qu trnh quang xc tc sn xut
H2, s dch chuyn ca in t trong vng dn ti b mt v cc mc nng lng l
cc yu t quan trng nht nh hng ti tc hnh thnh H 2. Do , cc kt qu da
trn cc ng dng lm sch khng kh, nc khng th trc tip ng dng cho vic sn
sut H2. Bn cnh , hiu ng quang xc tc TiO 2 ph thuc nhiu vo phng php
pha tp, nng pha tp v nguyn t pha tp. Do , mt s kho st, so snh c h
thng, l cn thit c trng cho qu trnh quang xc tc sn xut H 2 tng cng
bi pha tp ion kim loi.
1.2.2.2. Vt liu TiO2 pha tp cc nguyn t phi kim
Vic pha tp cc anion (N, F, C, S, vv) trong tinh th TiO 2 c th lm chuyn
dch p ng quang ca TiO2 n vng kh kin [13,14-18]. Khng ging nh cc ion
kim loi (cation), cc anion t c kh nng hnh thnh cc trung tm ti hp v do
nng cao hiu qu hot tnh quang ho hn. Asahi et al. [13] xc nh hm lng
pha tp thay th ca C, N, F, P v S cho Oxy trong anatase TiO2. H cho rng vic trn
trng thi p ca N vi 2p ca O c th y b vng ha tr ln trn lm hp vng cm
ca TiO2. Mng mng TiO2 pha tp N2 bng phng php phn x trong mi trng
cha hn hp kh N2 (40%) trong Ar, tip theo c 550oC trong N2 khong 4 gi.
Bt TiO2 pha tp N2 cng c ch to bng cch x l TiO2 trong NH3 (67% ) trong
Ar 600oC trong 3 gi. Cc mu TiO2 pha tp N c bo co l c hiu qu cho
phn hy methylene xanh di nh sng nhn thy ( > 400 nm).
1.3. ng dng ca vt liu TiO2
1.3.1. Tch H2 t H2O
cung cp nhu cu v nng lng cho con ngi n nm 2050 t nng
lng mt tri, nhng d tnh s b xp x khong 10000 d n nng lng mt
tri (din tch 5km x 5km cho mi d n) chuyn ha nng lng mt tri vi
hiu sut l 10%. Tt c din tch cn thit l vo khong 250000 km 2, chim 1% din

17

tch hoang mc ca tri t, 570 tn kh H 2 c th c to ra trong mt ngy. Kh H 2

c th c s dng cho pin nhin liu, cc nguyn liu u cho qu trnh tng hp
cc cht ha hc nh CH3OH hay nhiu cht khc. Quang xc tc phn ly nc to H 2
v O2 thu ht c rt nhiu s quan tm ca cc nh khoa hc. Bi v y l qu trnh
ti sinh nng lng v hn ch c vic phi s dng nhin liu ha thch dn n s
pht thi kh CO2.

Hnh 1.9. C ch quang xc tc TiO2 tch nc cho sn xut hydro [12].

Vic sn xut H2 bng cht quang xc tc TiO 2 c th hin trong hnh 1.9. V
mt l thuyt, tt c cc loi cht bn dn p ng cc yu cu ni trn u c th
c s dng nh mt cht xc tc quang sn xut H 2. Tuy nhin, hu ht cc cht
bn dn, chng hn nh CdS v SiC to ra n mn quang in ha, khng ph hp
tch H2O. Vi hot tnh xc tc mnh, n nh ha hc cao v thi gian tn ti lu ca
cp in t - l trng, TiO 2 l mt cht xc tc quang c s dng rng ri. Hin
nay, hiu sut chuyn i t nng lng mt tri sn xut H 2 bng quang xc tc
TiO2 tch nc vn cn thp, ch yu l v cc l do sau:
Ti t hp ca cp in t - l trng kch thch quang: in t trong vng
CB c th ti t hp vi l trng trong vng VB v gii phng nng lng
di dng sinh ra nhit hay photon.

18

 Xy ra phn ng ngc: Phn tch nc thnh hydro v oxy l mt qu

trnh c nng lng ngy cng tng, do phn ng ngc (ti t hp ca
hydro v oxy vo trong nc) d dng xy ra.
Khng c kh nng s dng nh sng nhn thy: rng vng cm ca
TiO2 l khong 3,2 eV v ch c nh sng UV c th c s dng cho
sn xut hydro.
gii quyt nhng vn trn v mc tiu s dng nh sng mt tri trong cc
phn ng quang xc tc sn xut hydro c tnh kh thi, nhng l lc lin tc c thc
hin thay i trong cc cu trc ca vt liu TiO 2 nhm m rng kh nng quang
xc tc ca vt liu ny sang vng nh nhn thy. Nhiu tc gi th nghim bng
cch pha tp cc ion kim loi, ion phi kim,... h chng minh c iu c nh
hng hiu qu n vic sn xut hydro [12].
1.3.2. Cc ng dng khc ca vt liu TiO2
1.3.2.1. ng dng lm xc tc quang x l mi trng
TiO2 c nh gi l cht xc tc quang ha thn thin vi mi trng v hiu
qu nht, n c s dng rng ri nht cho qu trnh quang phn hy cc cht
nhim khc nhau [1]. Cht quang xc tc TiO 2 cn c th c s dng dit khun,
nh tin hnh tiu dit vi khun E.coli. Do c kh nng oxi ha mnh nn TiO 2
c chiu x, thng c dng loi b cc t bo u trong qu trnh cha tr ung
th. Bn cht phn ng quang xc tc ca cht bn dn khng phc tp. Nh vo s
hp th cc photon c nng lng ln hn nng lng vng cm ca TiO 2 m cc
electron b kch thch t VB ln CB, to cc cp electron - l trng. Cc phn t mang
in tch ny s di chuyn ra b mt thc hin phn ng oxi ha kh, cc l trng
c th tham gia trc tip vo phn ng oxi ha cc cht c hi, hoc c th tham gia
vo giai on trung gian to thnh cc gc t do hot ng tip tc oxi ha cc hp
cht hu c b hp ph trn b mt cht xc tc to thnh sn phm cui cng l CO 2
v nc t c hi nht. Qu trnh quang phn hy ny thng bao gm mt hoc
nhiu gc hoc cc phn t trung gian nh *OH, O2-, H2O2, hoc O2, cng ng vai tr
quan trng trong cc phn ng quang xc tc.
1.3.2.2. ng dng lm cht n trong cc lnh vc sn t lm sch
TiO2 cn c s dng trong sn xut sn t lm sch, tn chnh xc ca loi ny
l sn quang xc tc TiO2. Thc cht sn l mt dng dung dch cha v s cc tinh

19

th TiO2 c chng 8 25nm. Do tinh th TiO2 c th l lng trong dung dch m

khng lng ng nn cn c gi l sn huyn ph TiO 2. Khi c phun ln tng,
knh, gch, sn s t to ra mt lp mng mng bm chc vo b mt.
Nguyn l hot ng ca loi sn trn nh sau: Sau khi cc vt liu c a vo
s dng, di tc dng ca tia cc tm trong nh sng mt tri, oxi v nc trong
khng kh, TiO2 s hot ng nh mt cht xc tc phn hu bi, ru, mc, kh c
hi, hu ht cc cht hu c bm trn b mt vt liu thnh H 2O v CO2. TiO2 khng b
tiu hao trong thi gian s dng do n l cht xc tc khng tham gia vo qu trnh
phn hu.
C ch ca hin tng ny c lin quan n s quang - oxi ho cc cht gy
nhim trong nc bi TiO2. Cc cht hu c bo, ru, mc,... bm cht vo sn c th
b oxi ho bng cp in t - l trng c hnh thnh khi cc ht nano TiO 2 hp th
nh sng v nh vy chng c lm sch khi mng sn. iu gy ngc nhin l
chnh lp sn khng b tn cng bi cc cp oxi ho - kh mnh m ny. Ngi ta pht
hin ra rng, chng c tui th khng km g sn khng c bin tnh bng cc ht
nano TiO2.
1.3.2.3. X l cc ion kim loi nng trong nc [1][2]
Khi TiO2 b kch thch bi nh sng thch hp gii phng cc in t hot ng.
Cc ion kim loi nng s b kh bi in t v kt ta trn b mt vt liu. Vt liu bn
dn quang xc tc, cng ngh mi ha hn c p dng nhiu trong x l mi
trng. Cht bn dn kt hp vi nh sng UV c dng loi cc ion kim loi
nng v cc hp cht cha ion v c. Ion b kh n trng thi t c hn hoc kim
loi t d dng tch c. V d:
2h + TiO2 2e + 2h+
Hg2+(aq) Hg(ads) ( B hp ph ln b mt vt liu)
Hg2+(ads) + 2e Hg(ads)
2H2O 2H+ + 2OH2OH- + 2h+ H2O + 1/2 O2
...
Rt nhiu ion kim loi nhy vi s chuyn quang ha trn b mt cht bn dn
nh l Au, Pt, Pd, Ag, Ir, Rh... a s chng u kt ta trn b mt vt liu. Ngoi s
kh bng in t, cc ion cn b oxi ha bi l trng trn b mt to oxit. Nhng cht
kt ta hoc hp ph trn b mt c tch ra bng phng php c hc hoc ha hc.

20

1.3.2.4. Mt s ng dng khc

TiO2 cn c s dng trong nhiu lnh vc khc nh: Vt liu gm, cht to
mu, cht n, lm vt liu ch to pin mt tri, lm sensor nhn bit cc kh trong
mi trng nhim nng, trong sn xut bn ra t lm sch b mt trong nc (t x
l m khng cn ho cht), lm vt liu sn trng do kh nng tn x nh sng cao,
bo v b mt khi tc ng ca nh sng. S dng TiO 2 to mng lc quang xc tc
trong my lm sch khng kh, my iu ho, v.v...

21

Chng 2. THC NGHIM

Vi mc ch nghin cu cu trc tinh th v tnh cht quang ca vt liu TiO 2
pha tp N, chng ti tin hnh ch to mu, thc hin mt s php o kho st cu trc
tinh th v tnh cht quang ca mu nghin cu. Chi tit ni dung trn s c trnh
by di y.
2.1. Ch to vt liu mng TiO2
2.1.1. Ch to mu TiO2 dng sol
H vt liu TiO2 dng sol c ch c ch to bng phng php sol-gel to
phc. Phng php ny n gin, linh hot v r tin. Thit b ch to v cc ha cht
c s dng nh sau:
Thit b ha hc bao gm: Bp khuy t, con t, bnh cu hai c, sinh hn hi
lu, cc chu nhit, cc loi pipet, nhit k, t sy, l nung, bm chn khng v h
thng to chn khng
Ho cht:
Tetraisopropyl orthotitanate (TPOT): Ti(i-OC3H7)4,Aldrich
Axetylaxetone (ACT): C5H8O2,Aldrich

Isopropanol (IPA): 2-C3H7OH,Merck

Co(NO3)2.6H2O

Nitric axit : HNO3 69%,Merck

H2O kh ion

Vi thit b phn ng, ha cht v phng th nghim cha box sch, cc phn
ng ha hc c tin hnh c lp li kh cao.
2.1.1.1.Quy trnh thc nghim
Qui trnh ch to sol ca cc mu TiO2 c trnh by trong hnh 2.1. Trong
, IPA c s dng l dung mi tin hnh phn ng, HNO3 l cht xc tc v
ACT l l cht km hm qu trnh thy phn-ngng t. Cc cht TPOT, ACT c
trn v khuy u, tip pha IPA vo v tip tc khuy u trong 30 pht. Nh git
dung dch HNO3 2N vo hn hp trn cho n khi t t l mong mun. thu c
sol, hn hp ny c khuy u, tng nhit n 75C v duy tr phn ng trong

22

60 pht. Sol c bo qun trong t lnh khong 7C.

Hnh 2.1. Qui trnh ch to sol ca cc mu TiO2.

2.1.1.2.Cc phn ng ha hc xy ra trong quy trnh thc nghim
Khi TPOT c ha tan trong IPA v nc kh ion cc phn ng ha hc sau
s xy ra:
Phn ng thy phn:
Ti(i-OC3H7)4 + H2O HO-Ti(i-OC3H7)4 + i-OC3H7
Phn ng ngng t:
Loi nc:

Loi ancol:

Cc phn ng thy phn ngng t ca TPOT trong dung dch c xu hng dn

n s to thnh kt ta ca titan oxo polymer. V vy, phi iu khin tc cc

23

phn ng sao cho cc polyme ny tn ti di dng dung dch hoc gel. S iu

khin ny c th t c d dng bng cch thm cc cht axit v phi t phc nhm
c ch qu trnh ngng t tc l ngn cn s hnh thnh kt ta v s pht trin ca
kch thc ht.
nh hng ca xc tc n qu trnh thy phn v ngng t
Ti(i-OC3H7)4 c tc thy phn nhanh nn axit HNO3 v axetylaxetone (ACT)
ng vai tr l cht km hm trong cc phn ng thy phn- ngng t. Ngoi ra ACT
cn c kh nng to phc vi tin cht ca Ti. Phn ng xy ra nh sau:
Ti(i-OC3H7)4 + x acacH Ti(i-OC3H7)4-x(acac)x + x i- C3H7OH
Vi x = 0,12, tt c cc phi t ca axetylaxetone lin kt ht vi cc
nguyn t Ti trong tin cht. Kt qu ny ch ra rng c s chuyn i trong cu phi
v ca Ti. S chuyn i ny c th c m t nh sau:
2Ti(i-OC3H7)3(acac) Ti(i-OC3 H7)2(acac)2 + Ti(i-OC3H7)4
Cc phi t phc axetylaxetone c kch thc phn t ln lm gim tnh
hot ng ca Ti(i-OC3H7)4-x(acac)x (x = 1 v 2). Ngoi ra axetylaxetone cn c tc
dng ngn cn s keo t v lng ng ca cc ht sol hnh thnh trong qu trnh phn
ng. Cc phi t phc axetylaxetone cho vo hn hp phn ng c hai tc dng:
lm cho qu trnh phn ng din ra chm hn v trnh hin tng keo t ca h keo
khi ch to v bo qun.
nh hng ca t l nc / tin cht v ACT / tin cht n qu trnh thy phn
v ngng t
Cc phn ng thy phn ngng t ca cc tin cht Ti c cha ACT c
iu khin ch yu bi hai thng s: t s thy phn h = H2O/Ti v t s phc x =
acac/Ti. Axetylaxetone lm gim cc lin kt c thy phn ha Ti-acac dn n
ngn cn qu trnh ngng t v to thanh cc on mch ngn hn. S thy phn
ca Ti(i-OC3H7)4-x(acac)x c thc hin trong s c mt ca cc lng nc khc
nhau (1 < h < 10) cng vi t s phc hot ng v nng Ti quyt nh vic to
thnh cc m phn t, sol, gel hoc kt ta.
Vi t s thy phn cao h>1, v khong to phc x = 01, s thy phn ca tin
cht Ti bin th acac cho 3 vng chnh. Sol thu c khi 0,2 x 1. Sol ny c th
tr nn trong sut hoc b gel vn ph thuc v nng Ti. Ta quan st c kt ta

24

khi t s to phc x < 0,2 v t s thy phn h > 2.

Cc iu kin axit c th ph v cc cu oxo titan v hydoxo titan, v vy tng
cng cc phn ng o. i vi t s thy phn thp (h < 1,7), s thy phn ca tin
cht Ti ([Ti] = 1M) to ra sol trong sut.
Chng ta c th m t ton b qu trnh phn ng nh sau:
Ti(i-OC3H7)4-x(acac)x + (2-x/2)H2O TiO2-x/2(acac)x + (4-x) i- C3H7O
2.1.2. Ch to mu mng mng TiO2
Vi mc ch to c dung dch ng nht cao v ph c mng trn cc loi
vi cht lng quang hc cao, chng ti chn dung mi isopropanol lm dung
mi tin hnh phn ng tng hp. Dung dch sn phm c th a sang khu ph
mng theo k thut nhng ph. Tuy nhin, vic s dng dung dch trong mt thi
gian di ph mng l yu t rt cn thit trong pht trin cng ngh. Chnh v vy,
chng ti nghin cu cc bin php bn vng ha dung dch sol thu c. C mt
s k thut lm bn vng ha dung dch sol thu c nh: iu chnh pH, thay th
dung mi, hay h nhit xung thp. Mt s bin php c tin hnh,
trong cc dch sol c bo qun nhit 7oC, c th s dng ph
mng cht lng cao trong thi gian t 4 n 6 tun.
i vi cc dung dch sol sau khi ch to c rt nhiu phng php to
mng. Trong iu kin hin c phng th nghim, chng ti s dng phng
php to mng nhng ko.
u im ca phng php nhng ko rt n gin, c th ph cho din tch ln,
to c mng dy nhiu lp, iu chnh c chnh xc dy mng t 50 nm n
vi chc micro mt, tnh lp li cao Nhc im l cn lng dung dch ln to
mng v mng c ngn ngang do nht ca dung dch gy nn. Tuy nhin chng ti
c th iu chnh c nht.

25

Hnh 2.2. S m t phng php nhng ph to mng TiO2.

Chiu dy ca mng ch to bng phng php nhng ph c xc nh bi

cng thc [35] :
h = 0,944 (Nca)

1/6

(U/ g)

1/2

Trong :
h :Chiu dy mng
Nca = U/
: nht
U: Tc ko
: Sc cng b mt
: T trng
g : Gia tc trng trng
Nh vy i vi mt dung dch, tc ko tng, dy h tng bng cn bc
2/3.
Cc mng c to trn thy tinh. Cc thy tinh kch thc 1,25x3.75
cm c x l b mt bng cch ngm trong axit nitric c 100% v 65% trong
thi gian 10 pht, ngm vo axit flohyric 1% trong 2 pht, trng bng nc kh
ion v lm kh trong phng sch. Cc mng c ch to bng phng php nhng
ko s dng thit b nhng ko NK-097 ca Vin Khoa hc Vt liu, Vin Khoa
hc v Cng ngh Vit Nam, vi tc ko t 0,5 n 5 mm/s. H thit b tri mng
nhng ko NK-097 c lp rp ti phng th nghim bao gm cc cm chi tit c
kh chuyn ng, m t, h iu khin in t khng ch tc nhng ko nhp t

26

M. Ngoi ra mt s chi tit khc c gia cng ch to ti Vit nam gm: b phn c
kh g lp, chn , gi cp mu, bnh cha dch to mng. H thit b tri mng c
lp rp ch to thnh hai b c kt cu tng t, nhng khc nhau ch yu cc
thng s k thut nhm tho mn yu cu nhng ko 2 di tc khc nhau. Chng
ti s dng phn mm iu khin: ICL (Intelli Command Language).
Chiu di mu tri mng ti a: 30 cm
Tc tri mng: 0,2-5 mm/s (P261X); 2-120 mm/s (P51X).
Trong qu trnh to mng chng ti kho st cc tc nhng ko v chn
c tc ph hp vi vt liu l: 1,9 mm/s v 2,3 mm/s. Mng n lp v a lp
thu c nhit phng vi thi gian 60 pht, sau a mu vo sy trong 24h
70oC. Mng thu c c bo qun nhit phng v chun b pha tp N.
2.1.3. Pha tp N vo mu mng mng TiO2
Ch to vt liu mng TiO2 pha tp N vi mc ch kho st tnh cht quang ca
vt liu ny. Mng TiO2 sau khi ch to c pha tp vi N bng cch trong mi
trng N2 ti 500 oC trong thi gian 20 pht vi cc t l % ca N 2 v % ca O2 khc
nhau. Mu c nung bng l 1700 oC - Vin Khoa hc Vt Liu, Vin Khoa hc v
Cng ngh Vit Nam. Gin nung nh sau:

Hnh 2.3. Gin thi gian qu trnh nung mu TiO2.

Nhit nung c la chn l 500oC, ti nhit ny s hnh thnh pha

anatase l tt nht. y l kt qu c kho st bng thc nghim ca ti

27

Nghin cu ch to v tnh cht ca bn dn pha t long TiO 2 anatase pha tp Co

bng phng php sol-gel v phn x catot ca TS. Ng Th Hng L, Vin Khoa
hc Vt Liu, Vin Khoa hc v Cng ngh Vit Nam.
2.2. Cc k thut o kho st tnh cht ca vt liu TiO2 pha tp N
2.2.1. Php o nhiu x tia X (XRD)
Phng php ny cho php xc nh pha cu trc, phn tch nh tnh, nh
lng cc pha tinh th, tnh hng s mng, mc bin dng mng, so snh xc nh
tng i hm lng pha tp, t cho php iu chnh quy trnh cng ngh ch to
vt liu v gp phn l gii cc hin tng vt l.
Cc php o c thc hin trn h nhiu x k SIEMENS D5005 (CHLB c)
Thit b ny t ti Trng i hc Khoa hc v T nhin, i Hc Quc Gia H Ni.
2.2.2. K thut hin vi in t qut (SEM)
Knh hin vi in t qut (SEM) l mt loi knh hin vi c kh nng thu nhn
c cc nh b mt mu vi phn gii cao. Kiu nh chung nht c to bi cc
in t th cp c nng lng thp (E < 50 eV). Cc in t th cp ny thot ra t lp
mng c vi nm t b mt mu c thu nhn bi mt u d kiu Everhart-Thornley,
thc cht l ng nhn quang in nhp nhy hoc detector bn dn Si (Li). Hnh thi,
kch thc ht ca cc mu nghin cu trong lun n c kho st trn knh hin vi
in t qut pht x trng Hitachi S-4800 ti Vin Khoa hc Vt liu,Vin Khoa hc
v Cng ngh Vit Nam. Hnh 2.4 trnh by ton cnh h knh hin vi in t qut
pht x trng Hitachi S-4800.

Hnh 2.4. Hnh nh mt knh hin vi in t qut pht x trng Hitachi S-4800

28

2.2.3. o dy v b mt mng bng Profiler

Thit b Profiler, KLA-Techor (Alpha-Step IQ) l thit b o hnh thi hc b mt,
b dy mng c nhy cao, nhy bc trn b mt mu o theo nguyn tc qut t kim
trn b mt. Thit b c kh nng o vi nhm n c 1 , vng phm vi rt nh ca
b mt hoc trn khong cch n 10 mm, thit b c iu khin t ng bng my
tnh.
Thit b ny c t ti Phng Th nghim Trng im, Vin Khoa hc Vt liu,
Vin Khoa hc v cng ngh Vit nam.
2.2.4. Ph hp th UV-VIS
xc nh ph hp th ca mu (dung dch, khi, hay mng mng) ta tin
hnh theo s sau:

Tia sng t ngun sng n sc c tch lm hai tia 1 v 2 c cng I 0 nh

nhau nh gng bn m L1, tia 1 truyn thng ti vt nn ( trong trng hp mu dung
dch th l l dng ng dung dch, vi mu mng mng c ph trn thy tinh
th l ming thy tinh dng ph mng), tia th 2 sau khi phn x trn gng L 2 s
a ti mu cn xc nh hp th. Sau so snh cng sng sau khi truyn qua
mu IS v cng nh sng nn IG, ta s xc nh c hp th ca mu. Cng
sng b hp th bi mu c xc nh:
IS = I0 - IG
thu c ph hp th ca mu, bc sng nh sng ti s c qut t vng
hng ngoi gn ti vng t ngoi gn (UV-VIS-NIR). Bc sng m ti I S thu c
l nh nht chnh l bc sng m hp th ca mu l cc i, bc sng ny l c
trng i vi tng mu.

29

Hnh 2.5. Ton cnh my o ph hp th UV-VIS.

Chng 3. KT QU V THO LUN

H mu c ch to bao gm cc mu c trnh by trong bng 3.1.
Bng 3.1. Thng tin ca cc mu ch to.

% N2
TPT0

% O2
Khng kh

Tc nhng ko
(mm/s)
1,9

TPT1

100

1,9

TPT2

100

2,3

TPT3

90

10

1,9

TPT5

95

1,9

3.1. Ch to mu
Cc mng mng TiO2 pha tp N c ch to qua 3 giai oan: giai on u tin
l tng hp dung dch TiO 2 bng phng php sol-gel s dng k thut hi lu. Sau
, cc mng mng c ch to bng phng php nhng ko (dip coating). Cui
cng, mng mng sau khi ch to thnh cng c nung trong mi trng c t l %
N2 khc nhau pha tp N. Sau y, chng ti trnh by kt qu ch to v tho lun
v s nh hng ca cc iu kin cng ngh ln vi cu trc v hnh thi hc ca
mng.

30

Cc mu kho st u c ch to vi quy trnh nh nhau, tuy nhin c khc

nhau v tc tri mng v t l % ca N2 khi . u tin, mu sol TiO2 c iu ch
bi qu trnh hi lu sau y: Ti(i-OC3H7)4 v C5H8O2 c trn v khuy u trong 10
pht, tip pha 2-C3H7OH vo v tip tc khuy u trong 30 pht. Nh dung dch
HNO3 2N vo dung dch trn cho n khi t t l mong mun. Cc phn ng trn u
xy ra nhit phng. thu c sol, nhit phn ng c nng ln 75 oC v
duy tr phn ng trong thi gian 2 gi. Dung dch sol ny c d dng ch to ton
b cc mu mng. Tip n, mng mng c ph ln thy tinh bng phng php
nhng ko (dip coating). Mng mng thu c c sy s b vi ln nhit 60 oC
trong thi gian rt nhanh. Cc lp mng v qu trnh x l nhit c lp li 3 ln (to
mng 3 lp). Cui cng mng mng c pha tp N bng cch trong mi trng c
t l % ca N2 v % ca O2 khc nhau nhit 5000C trong thi gian 20 pht sau khi
tri qua mt qu trnh gia nhit. m bo t l % ca N 2 v % ca O2, mu c
t trong ng thch anh kn kh, trc ng c ht chn khng s cp t 10 -2
Torr.
Cc mu ch to bao gm: TPT0, TPT1, TPT2, TPT3, TPT5. Thng tin chi tit
v cc mu c th hin trong bng 3.1. Mu sau khi ch to c bo qun nhit
phng, chun b cho vic kho st bng cc php o.
3.2. Kt qu nhiu x tia X
T cc gin nhiu x tia X thu c chng ta thy trong gin nhiu x tia
X khng xut hin cc vch c trng ca cc pha rutile v brookite. Chng ta ch
quan st thy cc vch c trng cho pha anatase ti cc gc 2 = 25,3o. Quan st s
b chng ta thy rng vch ti gc 2 = 25,3o ca cc mu l khc nhau, ph thuc
vo nng kh N2 trong mi trng nhit.

31

VNU-HN-SIEMENS D5005 - Mau TiO2 - TPT0

200
190
180
170
160
150
140
130

d=3.532

Lin (Cps)

120
110
100
90
80
70

d=1.8923

60
50
40
30
20
10
0
10

20

30

40

50

60

70

2-Theta - Scale
File: Van-TiO2-TPT0.raw - Type: 2Th alone - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 05/18/11 18:54:40
21-1272 (*) - Anatase, syn - TiO2 - Y: 57.53 % - d x by: 1.000 - WL: 1.54056

Hnh 3.1. Gin nhiu x tia X ca mu TPT0.

VNU-HN-SIEMENS D5005 - Mau TiO2 - TPT3

200
190
180
170
160
150
140
130

110
100
90

d=3.512

80
70
60
50

d=1.8946

Lin (Cps)

120

40
30
20
10
0
10

20

30

40

50

60

2-Theta - Scale
File: Van-TiO2-TPT3.raw - Type: 2Th alone - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 05/18/11 19:20:05
21-1272 (*) - Anatase, syn - TiO2 - Y: 46.02 % - d x by: 1.000 - WL: 1.54056

32

70

Hnh 3.2. Gin nhiu x tia X ca mu TPT3.

VNU-HN-SIEMENS D5005 - Mau TiO2 - TPT5

200
190
180
170
160
150
140
130

110
d=3.520

Lin (Cps)

120

100
90
80
70
60

d=1.8900

50
40
30
20
10
0
10

20

30

40

50

60

70

2-Theta - Scale
File: Van-TiO2-TPT5.raw - Type: 2Th alone - Start: 10.000 - End: 70.000 - Step: 0.030 - Step time: 1.0 s - Temp.: 25.0 C (Room) - Anode: Cu - Creation: 05/18/11 19:44:05
21-1272 (*) - Anatase, syn - TiO2 - Y: 54.39 % - d x by: 1.000 - WL: 1.54056

Hnh 3.3. Gin nhiu x tia X ca mu TPT5.

Chng ta c th nh gi kch thc ht tinh th TiO 2 anatase t bn rng

vch nhiu x trn c s p dng cng thc Scherrer nh sau:
kchthuoc

0,9
D cos

Trong :
l di bc sng nhiu x tia X.
kch thc l bn rng vch ph nhiu x.
D l kch thc ht tinh th cn xc nh.
Trong trng hp ca chng ti :
-

= 1,54 = 0,154 nm.

Vch nhiu x tia X ti /2 12,65o/25,3o

Thay s liu vo cng thc trn ta tnh c kch thc ht:

Mu TPT0 v TPT3 vi bn rng l kch thc = 0,4 radians: D 20 nm.

33

Mu TPT5 vi bn rng l kch thc = 0,35 radians: D 23 nm.

T kt qu tnh c ta c th sau:

Hnh 3.4. bn rng ph ca TiO 2

pha tp N nung vi cc t l % kh N 2
khc nhau.

Hnh 3.5. Kch thc ht ca TiO2 pha

tp N nung vi cc t l % kh N2 khc
nhau.

T kt qu tnh chng ta thy

mu trong mi trng 90% N 2 v 10% O2 c cng kch thc ht 23 nm, bng kch
thc ht ca mu nung trong mi trng khng kh. Theo chng ti iu ny c th
gii thch c v trong khng kh c khong 15% O 2 cn li ch yu l N2. Cn mu
nung trong mi trng kh cha 95% N2 v 5% O2 c kch thc ht nh hn 23 nm.
iu ny chng t N c nh hng ln s kt tinh hnh thnh ht tinh th vt liu
TiO2. S gim kch thc ht c th do N thay th mt phn nh O trong cu trc ca
TiO2 lm tng ng sut gy bin dng mng ngn cn s pht trin ca tinh th. Nhn
xt ny tng ng vi kt qu thu c trn vt liu TiO 2 pha tp Co cng b
trong lun n tin s Ng Th Hng L. Qu trnh pha tp N vo TiO 2 c thc hin
thng qua nhit trong mi trng c tng cng nng N 2. C th lng thay th
cn qu nh nn cha quan st thy cc nh hng ca s th N cho O ln cu trc
tinh th ca vt liu. nng cao kh nng thay th N cho O c th phi to vt liu
TiO2 c cc nt khuyt oxy trc khi trong mi trng kh N 2, hoc gia tng thm
nhit v ko di thm thi gian nhit. kim chng li kt qu tnh kch thc
ht tinh th t bn rng vch nhiu x tia X chng ti tin hnh chp nh knh hin

34

vi qut pht x trng lnh FESEM. Kt qu trnh by trn cc hnh 3.6, hnh 3.7, hnh
3.8.
3.3. Kt qu chp FESEM

Hnh 3.6. nh FESEM ca mu TPT0.

35

Hnh 3.7. nh FESEM ca mu TPT3.

Hnh 3.8. nh FESEM ca mu TPT5.

36

Qua nh SEM ta thy kch thc ht tinh th ca cc mu ch to kh ng u,

mu TPT0 v TPT3 c kch thc ht l 20-30 nm. Khng phn bit c s khc
nhau kch thc ht ca cc mu. Kt qu nh gi t rng vch nhiu x tia X c
s khc nhau kh nh (3 nm) gia cc mu trong khng kh v mu trong hn hp
95% N2 v 5% O2. C th s chnh lch nh ny khng phn bit bng nh
FESEM do nh hng ca bin ht. Tuy nhin chng ti cho rng kt qu thu c t
gin nhiu x tia X l ng quan tm v cn nghin cu chi tit hn.
Kch thc ht tng i nh, khi s nguyn t phn b trn b mt tr nn
rt ng k so vi s nguyn t nm bn trong ht (ht tinh th c kch thc 1 nm ch
cha ~30 nguyn t vi hu ht cc nguyn t nm trn b mt; kch thc 4 nm cha
4000 nguyn t vi 40% s nguyn t nm trn b mt; kch thc 10 nm cha
khong 30000 nguyn t vi 20% nm trn b mt). Bn cnh , cu trc tinh th ca
ht v hiu ng lng t ca cc trng thi in t b nh hng ng k bi s
nguyn t trn b mt.
Mng TiO2 anatase c ch to nhm mc tiu ng dng cho cc nghin cu
quang xc tc nn cc kho st dy mng, truyn qua v b hp th l cc thng
tin cn quan tm. dy ca mng c xc nh bng k thut o Profiler Anpha
Step.
3.4. Kt qu o dy v b mt mng bng Profiler

Hnh 3.9. dy ca mng TiO2 c ko vi vn tc 1,9 mm/s.

37

Hnh 3.10. dy ca mng TiO2 c ko vi vn tc 2,3 mm/s.

Qua kt qu o dy mng bng Profiler ta thy cc mu mng mng ch to c

dy vo khong 300 nm.
Ta cng thy l ph kh bng phng, iu ny chng t mng c ch to c
nhn cao.
3.5. Kt qu o ph hp th
Vi mc ch kim tra nh hng ca nng pha tp N ln hot tnh quang ca
vt liu TiO2 chng ti ch to mng mng trong mi trng kh c nng kh N 2
khc nhau. Ph hp th ca cc mng c trnh by trn hnh 3.11.
Chng ta d dng nhn thy b hp th ca mng TPT0 ti bc sng 350 nm
(tng ng 3,54 eV) ln hn b hp th ca mng TPT3 (342 nm, 3,62 eV) v TPT5
(336 nm, 3,69eV). Chng ta nhn thy kt qu thu c khng ph hp vi mc tiu
ra ca th nghim l thay th mt phn N cho O gim gi tr khe nng lng
vng cm nh kt qu ca cc tc gi khc cng b [13]. T kt qu thu c ny
c th a ra nhn nh lng N thay th cho O cn qu nh, cha nh hng nhiu
ln cu trc vng nng lng ca vt liu. Ngc li trong mi trng c nng
kh N2 ln hn nh hng trc tip ln kch thc ht nh c nh gi t bn
rng vch ph nhiu x tia X phn trn.

38

Hnh 3.10. Ph hp th ca ba mu TPT0, TPT3, TPT5.

Chng ta bit rng khi kch thc ht gim n vng nanomet , hiu ng kch
thc lng t s ng vai tr v rng vng cm tnh cho vt liu c cu trc ht
gi cu s c m rng ra theo biu thc sau:

Trong :
R l bn knh ht tinh th.
l hng s in mi ca vt liu.
l khi lng rt gn .
T cng thc ny chng ta thy R cng gim th gi tr nng lng vng cm E
cng tng, ngha l b hp th s cng dch v pha nng lng cao hn (bc sng

39

ngn hn). iu ny c v cng ph hp vi kt qu nh gi kch thc ht tinh th

xc nh t bn rng vch nhiu x tia X.
3.6. Kt qu o truyn qua

Hnh 3.12. Ph truyn qua ca mu TPT3.

Hnh 3.13. Ph truyn qua ca mu TPT5.

Ph truyn qua c o trn thit b o ph hp th UV-VIS nhit phng.

Kt qu thu c trnh by trn cc hnh 3.12 v hnh 3.13. T kt qu o chng ta
nhn thy mu mng trong mi trng kh O 2/N2 cha 90% N2 c truyn qua
khong 90% trong ton di nng lng t 300 nm n 800 nm. Ngc li khi trong

40

mi trng kh O2/N2 cha 95 % N2 mng c truyn qua trong ton di khong

80%. Hai mng c dy tng ng nhau. Vy cu hi t ra l ti sao truyn
qua ca mng trong mi trng kh O 2/N2 cha nng kh N2 ln hn li gim?
Theo chng ti s st gim truyn qua c th khng lin quan ti s gia tng
hp th ca vt liu. Kt qu thu c c th c nhiu nguyn nhn nh hng ln s
st gim truyn qua m mt vi trong s l s gia tng nh hng ca bin ht
khi kch thc ca cc ht vt liu gim v hiu ng tng cng tn x b mt ht tinh
th gi cu khi bn knh ca qu cu tinh th gim.

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KT LUN
T cc kt qu nghin cu trnh by trn y, nhng kt qu chnh ca kha
lun c th c tng kt nh sau:
1.
ch to thnh cng mng TiO2 kch thc nano mt n pha
anatase bng phng php sol-gel.
2.
quan st thy nh hng ca N2 ln s hnh thnh tinh th, c
th l lm gim kch thc ht TiO 2. S gim kch thc ny c th do N 2 thay
th mt phn nh O2 trong cu trc ca TiO2 lm tng ng sut gy bin dng
mng ngn cn s pht trin ca tinh th.
3.
quan st thy s st gim truyn qua ca mng ph thuc
vo nng N2 trong mi trng nung vng bc sng t 300 nm n 800
nm. S st gim ny c th do s gia tng nh hng ca bin ht khi kch
thc ca cc ht vt liu gim v s tng cng ca hiu ng tn x b mt ht
tinh th gi cu khi bn knh ca qu cu tinh th gim.

42

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