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CHT XC TC QUANG HA

TITAN OXIT
I. Tng quan v TiO2
Titan ioxit l cht rn mu trng, khi nung nng c mu vng, khi lm lnh tr li
mu trng. TiO2 c cng cao, kh nng chy (Tnc = 1870
0
C).
Titan ioxit tn ti 3 dng tinh th (v mt dng v nh hnh) l anatase (tetragonal),
rutile (tetragonal) v brookite (orthorhombie)
Hnh 1: Cu trc tinh th cc dng th hnh ca TiO2
Rutile l dng bn ph bin nht ca TiO2, c mng li t phng trong mi ion
Ti
4+
c O
2-
bao quanh kiu bt din, y l kin trc in hnh ca hp cht c cng thc
MX2, anatase v brookite l dng gi bn v chuyn thnh rutile khi nung nng. Tt c cc
dng tinh th ca TiO2 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.
Cu trc mng li tinh th ca rutile, anatase v brookite u c xy dng t cc
a din phi tr tm mt (octahedral) TiO6 ni vi nhau qua cnh hoc qua nh Oxi chung,
Mi ion Ti
4+
c bao quanh bi tm mt to bi su ion O
2-

Anatase
Rutile
Brookite
Hnh 2: Hnh khi bt din ca TiO2
Cc dng tinh th rutile, anatase u thuc h tinh th tetragonal. Tuy nhin trong tinh
th Anatase khong cch Ti Ti ln hn v khong cch Ti O ngn hn so vi rutile.
Ngoi 3 th hnh ni trn th TiO2 cn tn ti dng v nh hnh nhng khng bn do
lu trong khng kh nhit phng hoc khi c nung nng th chuyn sang dng
anatase, dng v nh hnh c iu ch bng cch thy phn mui c c Ti
4+
hoc
cc dng hp cht hu c titan trong nc nhit thp thu c kt ta TiO2 v nh
hnh.
Trong cc dng th hnh TiO2 th dng anatase th hin hot tnh quang xc tc cao
hn cc dng cn li
II. Tnh xc tc quang ha ca TiO2 dng anatase
1. nh ngha
Xc tc quang ha l xc tc nu c kch hot bi nhn t nh sang thch hp th
s gip phn ng xy ra
2
,
3 2 2 2
2
5
2
2
( 0.0001 )
. .
TiO hv
CH CHO O CO H O
mmol
v
l h cm
+ +
=

2. C ch xc tc quang d th: c tin hnh pha kh hoc pha lng
Titan Oxit c lm cht xc tc quang v tha mn 2 iu kin:
- C hot tnh quang ha
- C nng lng vng cm thch hp hp th nh sang cc tm hoc nhn thy
im khc:
- Phn ng xc tc d th truyn thng: xc tc c hot ha bi nhit, 5 giai
on
- Phn ng xc tc quang ha: xc tc c hot ha s hp th nh sang, 6 giai
on
+ C th giai on hp th proton nh sang phn t chuyn t trng thi c bn
sang trng thi kch thch electron
+ Giai on oharn ng quang ha chia lm 2 giai on nh:
- Phn ng quang ha s cp: cc phn t cht bn dn b kch thch tham
gia trc tip vo phn ng vi cc cht b hp ph
- Phn ng quang ha th cp (giai on phn ng ti hay phn ng
nhit): phn ng ca giai on s cp.
C ch xc tc quang ca cht bn dn

iu kin: Nng lng photon nh sng(hv) > Nng lng vng cm (Eg)
Vi SC: b mt xc tc bn dn (TiO2)
Ni dung c ch:
- Khi chiu sng nh sang c nng lng photon (hv) thch hp >nng lng vng
cm (Eg) ln b mt xc tc bn dn (SC) th s to ra cc cp in t (e-) l
trng (h+) Cc e- chuyn ln vng dn (quang electron), cn cc l trng
li vng ha tr: hv + SC e- + h+
- Cc phn t cht tham gia phn ng hp th ln b mt xc tc gm 2 loi:
+ Cc phn t c kh nng nhn e (Acceptor)
+ Cc phn t c kh nng cho e (Donor)
- Quang electron vng dn s chuyn n ni c cc phn t c kh nng nhn
electron (A), qu trnh kh xy ra: A(ads) + e
-
A
-
(ads)
- L trng chuyn n ni c cc phn t c kh nng cho electron(D), thc hin
phn ng oxh:
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 sn phm cui cng
- Trong qu trnh xc tc quang electron v l trng c th ti kt hp lm hiu
sut lng t gim v gii phng nng lng di dng bc x in t hoc
nhit.
( ) e h SC E
+
+ +

- Thng thng Ag l kim loi c la chn to nn by in tch lm gim
tc ti kt hp in t v l trng, tng hiu sut lng t ca qu trnh quang
xc tc TiO2
C ch xc tc quang ca TiO2 dng Anatase:
- Khi xc tc c hot ha bi nh sang thch hp 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
+
:
2 2 2
2 2
2 2
( )
( )
( )
TiO h H O OH H TiO
TiO h OH OH TiO
TiO h RX RX TiO
+ - +
+ -
+ +
+ + +
+ +
+ +

- Ti vng dn c s hnh thnh cc gc
2
O

v
2
HO
-

2 2 2 2
2 2
2 2 2 2
2 2 2 2
2 2 2 2
( )
2
( )
TiO e O O TiO
O H HO
HO H O O
TiO e H O HO HO TiO
H O O O HO HO

+ -
-
-
-
+ +
+
+
+ + +
+ + +

So snh hot tnh xc tc ca Anatase v Rutile:
- TiO2 dng Anatase c hot tnh quang ha cao hn hn cc dng tinh th khc
- Mc d Rutile c th hp th c tia t ngoi v nhng tia gn vi nh sng nhn
thy, cn Anatase ch hp th c tia t ngoi nhng kh nng xc tc ca
Anatase ni chung cao hn Rutile

- Vng ha tr ca Anatase v Rutile trn gin xp x nhau v cng rt dng
chng u c kh nng oxi ha mnh (cc l trng vng ha tr oxi ha
H2O thnh OH
*
, hay mt s gc hu c thnh RX
+
)
2 2 2
2 2
2 2
( )
( )
( )
TiO h H O OH H TiO
TiO h OH OH TiO
TiO h RX RX TiO
+ - +
+ -
+ +
+ + +
+ +
+ +

- Vng dn ca Rutilecos gi tr gn vi th kh nc thnh kh Hidro (th kh
chun 0V), trong khi vi Anatase th mc ny m hn mt cht, ng ngha vi
tnh kh mnh hn Anatase c kh nng kh O2 thnh
2
O

, (cn Rutile th
khng) Vng dn ca Anatase c s hnh thnh cc gc
2
O

,
2
HO
-

2 2 2 2
2 2
2 2 2 2
2 2 2 2
2 2 2 2
( )
2
( )
TiO e O O TiO
O H HO
HO H O O
TiO e H O HO HO TiO
H O O O HO HO

+ -
-
-
-
+ +
+
+
+ + +
+ + +

So snh hot tnh xc tc ca Anatase v Rutile:
- Anatase c kh nng nhn ng thi oxy v hi nc t khng kh, cng vi nh
sng t ngoi gip phn hy cc hp cht hu c: Tinh th Anatase duwosi tc
dng ca nh sng t ngoi ng vai tr nh mt cu ni trung chuyn in t
t H2O sang O2, chuyn 2 cht ny thnh dng
2
O

v OH
*
, l 2 dng c hot
tnh oxi ha cao c kh nng phn hy cc cht hu c thnh H2O v CO2
- Tuy nhin, s so snh ny khng tht chnh xc v 2 dng TiO2 trn c bandgap
khc nhau v c to thnh t cc iu kin cng khc nhau, nht l v nhit
. V th, ta phi xt trong tng phn ng c th mi c th nh gi c hot
tnh xc tc, trong thnh phn pha l yu t nh hng ln nht.

III. ng dng
1. ng dng ca xc tc quang ha TiO2 trong pin quang in phn bn dn:
- Phn ng tch H2 v O2 t H2O
H2O H2 + 1/2O2
- L thyt: Nc trong sut vi nh sng nhn thy khng th phn hy
nc nh cc bc x n sc m phi nh nh sng cc tm vi 190nm <
- Honda v Fujishima nghin cu s phn hy quang hc nc nh pin
quang in phn bn dn ch cn dng nh sng c 400nm <
- C ch xut:
TiO2 + hv (TiO2)2e
-
+ 2h
+
(kch thch TiO2 bng nh sng cc tm)
2h
+
+ H2O 1/2O2 + 2H
+
(ti in cc TiO2)
2e
-
+ 2H
+
H2 (ti in cc cht quang)
Phn ng tng ca qu trnh:
H2O + 2hv 1/2O2 + H2
- Khi s dng quang in cc ha hc kh khn trong vic xy dng oxit bn dn
quang in cc
- Khi phn hy quang hc nc s dng cht bn dn thay cho cc quang in
cc: chi ph xy dng thp, kh nng bn ha di nh sng, din tch b mt
ln.

2. S tng th ng dng ca cht xc tc quang ca TiO2:
3. Mt s ng dng khc ca cht xc tc quang TiO2
ng dng xc tc quang trong x l mi trng
- Khi titan thay i ha tr to ra cp in t l trng vng dn v vng ha tr
di tc dng ca nh sng cc tm ciu vo. Nhng cp 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 s phm cui cng l CO2 v nc
t c hi nht.
ng dng lm cht n trong cc lnh vc sn t lm sch, cht do
- TiO2 cn c s dng trong sn xut sn t lm sch, tn chnh xcca loi ny
l sn quang xc tc TiO2. Thc cht sn l mt dng dung dch cha v s cc
tinh th TiO2 c chng 8 25 nm. Do tinh th TiO2 c th l lng trong dung
dch m khng lng ng nn cn c gi l sn huyn ph TiO2. Khi c
phun ln tng, knh, gch, sn s to 1 lp mng bm chc vo cc b mt
- Nguyn l hot ng ca sn 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 hy bi, ru, mc, kh c
hi, hu ht cc cht hu c bm trn b mt vt liu thnh H2O v CO2. TiO2
khng b tiu hao trong thi gian sng dng do n l cht xc tc khng tham
gia vo qu trnh phn hy.
- C ch ca hin tng ny c lin quan n s quang oxi ha cc cht gy
nhim trong nc bi TiO2. Cc cht hu c bo, ru, mc, bm cht vo sn
c th b oxi ha bng cp in t l trng c hnh thnh khi cc ht nano
TiO2 hp th nh sng v nh vy chng c lm sch khi mng sn. iu
ny gy ngc nhin l chnh lp sn khng b tn cng bi cc cp oxi ha 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
Ngoi ra, TiO2 cn c s dng trong nhiu lnh vc khc nhau nh l x l cc ion
kim loi nng trong nc, 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, lm vt liu
sn trng do kh nng tn x nh sng cao, s dng to mng lc xc tc trong my lm
sch khng kh, my iu ha,..v..v
IV. Thc nghim
Cc phng php thc nghim:
1. Phng php thc nghim iu ch bt titan ioxit kch thc nano mt bin tnh
lu hunh bng phng php thy phn TiCl4 trong dung dch Na2SO4
Chu trnh iu ch bt titan oxit kch thc nano mt bin tnh S theo phng php
thy phn TiCl4 trong dung dch H2SO4
2. Phng php thc nghim iu ch bt titan ioxit kch thc nano mt bin tnh
lu hunh bng phng php thy phn TiCl4 trong dung dch H2SO4

Chu trnh iu ch bt titan oxit kch thc nano mt bin tnh S theo phng php
thy phn TiCl4 trong dung dch H2SO4
V. iu ch, sn xut:
C 2 phng php iu ch chnh:
- Phng php axit sulfuric
- Phng php clo ha
Ngoi 2 phng php trn cn c nhng qui trnh sn xut TiO2

bng axit HCl m
c v phng php dng florua flo ha qung ilmenite
1. Phng php axit sulfuric:
Gm 4 giai on:
- Phn hy
- Tch Fe ra khi dung dch
- Thy phn to ra axit mtatitanic
- Nung H2TiO3
Giai on phn hy: dng H2SO4 phn hy qung ilmenite(FeTiO3) s xy ra nhng
phn ng:
FeTiO3 + 3H2SO4 = Ti(SO4)2 + FeSO4 + 3H2O
FeTiO3 + 2H2SO4 = TiOSO4 + FeSO4 + 2H2O
Lc u ngi ta ch cn nung ln 125
0
C 135
0
C, sau nhit s t ng tng ln
nh nhit ca phn ng ln n 180
0
C 200
0
C
Giai on tch Fe ra khi dung dch: lm sch dung dch khi phn ln lp tp cht
st, ngi ta dng phi st hon nguyn Fe
3+
n Fe
2+
v sau kt tinh cuporos st
FeSO4.7H2O (li dng tnh gim ha tan ca n lm sch dung dch). Sau khi k tinh
ta c ung dch cha TiO2, H2SO4 hot tnh, dulfat v tp cht Al, Mg, Mn,
Giai on thy phn to ra axit mtatitanic
TiOSO4 + H2O = H2TiO3 + H2SO4
Thnh phn dung dch v phng php tin hnh thy phn nh hng n thnh
phn v cu trc ca kt ta
C 2 cch tin hnh thy phn:
- Pha long dung dch
- Cho them mm tinh th vo dung dch: mm tinh th c cho vo di dng
dung dch keo ca oxit titan ngm nc.
Nung H2TiO3: tch nc v SO3 khi tinh th TiO2 ngi ta nung t 200
0
C 300
0
C
(i vi nc) v t 500
0
C 950
0
C (i vi SO3). Khi nung nhit < 950
0
C d cho
ta TiO2 dng anatase, cn khi > 950
0
C cho ta TiO2 dng rutile
Xt v phng php ny ta c u v nhc im sau:
- u im:
+ Qui trnh sn xut ch dng 1 loi ha cht l H2SO4
+ C th dng nguyn liu c hn lng TiO2 thp, r tin.
- Nhc im:
+ Lu trnh phc tp
+ Thi ra mt lng ln cht sulfat st v axit long
+ Khu x l cht thi kh phc tp v tn km
+ Chi ph u t ln.
2. Phng php Clo ha
Phng php clo ha gm 3 giai on:
- Thy phn dung dch TiCl4
- Thy phn trong pha kh
- t TiCl4
Thy phn dung dch TiCl4:
- Chun b dung dch n TiCl4 bng cch rt TiCl4 vo nc lnh hoc axit HCl
long
TiCl4 + 3H2O = H2TiO2 + 4HCl
- Sau nung H2TiO3 850
0
C 900
0
C s thu c TiO2
Thy phn trong pha kh:
- TiCl4 tc dng vi hi nc 300
0
C 400
0
C
TiCl4 + 2H2O = TiO2 + 4HCl
- Cho dng khng kh no nc v dng khng kh vi hi TiCl4 un nng 300
0
C
400
0
C vo trong bnh. Bnh phn ng cng c nung nng ti 300
0
C
400
0
C. tch TiO2 khi HCl c th dng mng lc bng gm.
t TiCl4:
- Mun ti sinh Cl2 th tt nht l nhn TiO2 bng cch t TiCl4 vi O2 nhit
cao.
TiCl4 + O2 = TiO2 + 2Cl2
- Qu trnh ny c th tin hnh in tc cho 2 dng kh c un nng 1000
0
C
1100
0
C gp nhau trong bnh phn ng. Bnh phn ng c nung v gi 750
0
C.
Theo ng kh cc ht TiO2 (khi) s c li vo v phn lc bi
u v nhc im phng php ny:
- u im:
+ Lng cht thi t hn
+ Kh clo c thu hi dng li
+ Sn phm trung gian l TiCl4 c th bn dng cho nghnh sn xut titan bt
+ Thnh phn c s dng rt rng ri trong nghnh sn, giy, plastic, v.v
- Nh im:
+ Sn phm ph l clorua st t c s dng
+ Phn ng nhit cao, tn nhiu nng lng
+ Bnh phn ng phi chn vt liu c th chng c
+ Ph hoi ca HCl khi c mt ca hi nc

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