titan dioxit

Nghin cu iu ch, kho st cu trc, hot tnh quang xc tc ca bt titan ioxit khch

thc nano t cht u TiCl4 v amin

Trn Th Thu Trang

Trng i hc Khoa hc T Nhin; Khoa Ha hc Khoa Ha hc Chuyn ngnh: Ha v c; M s: 60 44 25

Ngi hng dn: PGS.TS Ng S Lng Nm bo v: 2011

Abstract. Tng quan v cng ngh nano ; vt liu titan ioxit kich thc nano; titan ioxit kich thc nano c bin tinh bng nan o; titan ioxit kich thc nano c bin tinh bng nito vi tin cht cung cp nito la hydrazine v hydroxylamine . Nghin cu nh hng ca nng TiCl4 n kh nng quang xc tc ca bt TiO2-N kch thc nm iu ch bng cch thy phn TiCl4 trong dung dch nc vi s c mt ca hydrzine v hydroxylammine. Nghin cu nh hng ca nng hydrazine v hydroxylammine n cu trc, tnh cht, kh nng quang xc tc ca bt TiO2-N kch thc nm iu ch bng cch thy phn TiCl4 trong dung dch nc vi s c mt ca hydrazine v hydroxylammine. Xc nh iu kin thch hp (nhit nung, thi gian nung, thi gian thy phn, iu kin ra...) cho qu trnh iu ch c bt titan ioxit bin tnh N c hot tnh quang xc tc cao theo phng php thy phn.

Keywords. Cng ngh Nano; Vt liu titan ioxit; Xc tc quang ha

Content:

Titan ioxit (TiO2) kch thc nano l mt trong nhng vt liu c bn

trong ngnh cng ngh nano v n c cc tnh cht l, ha, quang in t kh

c bit, c bn cao v thn thin vi mi trng. V vy, titan ioxit 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 nano,

TiO2 c nhiu ng dng hn trong cc lnh vc nh ch to pin mt tri,

sensor, ng dng lm cht quang xc tc x l mi trng, ch to vt liu t

lm sch,

Hin nay, TiO2 l xc tc quang ha c nghin cu rng ri nht vi

nhiu ng dng, c bit TiO2 c quan tm trong lnh vc lm xc tc

quang ha phn hy cc hp cht hu c v x l mi trng v n khng c

hi, bn vng v r tin. Xc tc quang TiO2 do c di trng rng (ca rutile

l 3.05 eV v ca anatase l 3.25 eV) nn ch c hot tnh trong vng UV.

Trong khi , phn bc x t ngoi trong quang ph mt tri n b mt tri

t ch chim ~ 4% khin cho vic s dng ngun bc x ny vo mc ch

x l mi trng vi xc tc quang TiO2 b hn ch. m rng kh nng s

dng nng lng bc x mt tri c vng nh sng nhn thy vo phn ng

quang xc tc, cn gim nng lng vng cm ca TiO2.

Vi mc ch trn, trong nhiu nghin cu gn y bin tnh b mt

hoc vo cu trc TiO2 bng nhiu phng php c tin hnh, bng cch

a cc ion kim loi nh Zn, Fe, Cr, Eu, Y, Ag, Ni, ... v cc ion khng kim

loi nh N, C, S, F, Cl, .... Trong s , c bit phi k n l bin tnh bng

nit. S d bin tnh TiO2 kch thc nano bng nit c nghin cu nhiu v

cc hp cht cha nit (NH3, ur, cc mui amoni, cc hp cht amin) c

s dng ph bin trong qu trnh iu ch TiO2 kch thc nano vi vai tr

iu chnh pH, lm cht nh hng cu trc ng thi nhiu cng trnh

nghin cu cho thy N3- c tham gia vo cu trc TiO2 lm thay i cu trc

v tnh cht quang xc tc ca vt liu.

V vy, trong cng trnh ny chng ti t vn : Nghin cu iu

ch, kho st cu trc, hot tnh quang xc tc ca bt titan ioxit kch

thc nano t cht u TiCl4 v amin.

CHNG 1: TNG QUAN

1.1 Gii thiu chung v cng ngh nano.

1.1.1 Cng ngh nano v vt liu nano

Cng ngh nano nghin cu v ng dng cc h bao gm cc cu t c

kch c nano (10-9 m) vi cu trc phn t hon chnh trong vic chuyn ha

vt cht, nng lng v thng tin.

1.1.2. ng dng ca cng ngh nano

a. Lnh vc in t, cng ngh thng tin v truyn thng.

Cng ngh nano c nh hng r rt n lnh vc in t, cng ngh

thng tin v truyn thng. iu ny c phn nh r nht s lng cc

transitor kin to nn vi mch my tnh, s lng cc transitor trn mt con

chip tng ln lm tng tc x l ca n, gim kch thc linh kin, dn ti

gim gi thnh, nng cao hiu qu kinh t.

b. Lnh vc sinh hc v y hc.

ng dng cng ngh nano trong lnh vc sinh hc to ra cc thit b

cc nh c th a vo mi ni trong c th con ngi tiu dit virut v

cc t bo ung th, to ra cc chip sinh hc v tin ti kh nng to ra cc

my tnh sinh hc vi tc truyn t thng tin nh b no

c. Lnh vc vt liu.

Vt liu composit gm cc vt liu khc nhau v cu trc v thnh

phn, s dng cc ht nano trong vt liu nano composit lm tng tnh cht

c l, gim khi lng, tng kh nng chu nhit v ha cht, thay i tng

tc vi nh sng nhn thy v cc bc x khc.

d. ng dng trong lnh vc x l mi trng.

Nhng nm gn y, th gii ni chung v Vit Nam ni ring ngy

cng coi trng vn x l nhim mi trng c bit l nhim ngun nc

do cht thi hu c gy ra.

e. Vn nng lng.

Nhu cu v nng lng l mt thch thc nghim trng i vi s tn

ti v pht trin ca th gii. Trc mt thc t l cc ngun nng lng

truyn thng ang ngy mt cn kit th vic tm ra cc ngun nng lng

khc thay th l nhim v cp bch c t ra.

1.2. Gii thiu v vt liu titan ioxit kch thc nano.

1.2.1. Cu trc ca TiO2

TiO2 [8, 22] l cht rn mu trng, khi un nng c mu vng, khi lm

lnh th tr li mu trng. Tinh th TiO2 c cng cao, kh nng chy (o

nct =

1870oC).

TiO2 c bn dng th hnh. Ngoi dng v nh hnh, n c ba dng tinh th l anatase (tetragonal), rutile (tetragonal) v brookite (orthorhombic)

1.2.2. Gin min nng lng ca anatase v rutile

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 3 min 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.

1.2.3. S chuyn pha trong TiO2

Hu ht cc ti liu tham kho u ch ra rng qu trnh thu phn cc

mui v c u to ra tin cht titan ioxit dng v nh hnh hoc dng cu

trc anatase hay rutile. Khi nung axit metatitanic H2TiO3, mt sn phm trung

gian ch yu ca qu trnh sn xut TiO2 nhn c khi thu phn cc dung

dch mui titan, th trc ht to thnh anatase. Khi nng nhit ln th

anatase chuyn thnh rutile.

1.2.4. Tnh cht ha hc ca titan ioxit

TiO2 bn v mt ho hc (nht l dng nung), khng phn ng vi

nc, dung dch axt v v long, kim, amoniac, cc axit hu c.

1.2.5. Cc ng dng ca vt liu TiO2 kch thc nano

Hin nay, sn lng titan ioxit trn th gii khng ngng tng ln.

Bng 1.2: Sn lng titan ioxit trn th gii qua mt s nm.

Nm 1958 1967 2003

Sn lng (tn) 800.000 1.200.000 4.200.000

Gn 58% titan ioxit sn xut c c dng lm cht mu trng

trong cng nghip sn xut sn. Cht mu trng titan ioxit cng c s

dng mt lng ln trong sn xut giy, cao su, vi sn, cht do, si tng

hp v mt lng nh trong cng nghip hng liu. Cc yu cu i hi i

vi sn phm l rt a dng ph thuc vo cng dng ca chng.

a. ng dng trong xc tc quang ha x l mi trng

b. ng dng lm cht n trong cc lnh vc sn t lm sch, cht do.

c. X l cc ion kim loi nng trong nc.

d. Dit vi khun, vi rt, nm, t bo ung th

e. B mt siu thm t ca vt liu TiO2 [9].

g. Cc ng dng khc ca bt titan ioxit kch thc nano.

1.3. Gii thiu v titan ioxit kch thc nano c bin tnh bng nit.

1.3.1. Cc kiu TiO2 bin tnh

Ngoi titan ioxit tinh khit, ngi ta c cc kiu titan ioxit bin tnh nh

sau:

- TiO2 c bin tnh bi nguyn t kim loi (Fe, Zn, Cu, ...)

- TiO2 c bin tnh bi nguyn t khng kim loi [17, 19] (N, B, C,

F, S, ...)

- TiO2 c bin tnh bi hn hp (vt liu nano ng bin tnh bi Cl

hoc Br ...)

Trong bi bo co ny, chng ti quan tm ch yu n vt liu TiO2

c bin tnh nit.

1.3.2. Tnh cht ca TiO2 kch thc nano bin tnh bng nit.

a. Cc tnh cht in ca cc vt liu nano TiO2 c bin tnh

Cc nghin cu l thuyt v thc nghim gn y [14] cho thy rng

s thu hp di trng ca TiO2 cng c th thu c khi s dng cc cht thm

l khng kim loi. Ngi ta tnh ton cu trc di chuyn in t ca TiO2

dng anatase vi cc cht thay th khc nhau, gm C, N, F, P hoc S. Trong

nghin cu ny, cht thm C to nn cc trng thi v tr thp trong di

trng. b. Cc tnh cht quang hc ca vt liu nano TiO2 c bin tnh.

TiO2 c bin tnh bi phi kim [10, 11, 12] c mt mu sc t trng

ti vng hoc thm ch l mu xm sng, v bt u ca ph hp th, nh sng

dch chuyn v cc bc sng di hn. cc vt liu nano TiO2 c

bin tnh bi N, di trng hp th bt u dch chuyn t 380 nano ti 600

nano, i vi TiO2 khng c bin tnh, s hp th m rng n 600 nano.

S hp th quang ca TiO2 c bin tnh bi N trong vng nh

sng nhn thy c. Cc tnh cht quang in ca vt liu nano TiO2 c bin tnh.

1.3.3. Cc phng php iu ch TiO2 kch thc nano c bin

tnh bng nit

a. Mt s phng php vt l

- Phng php bc bay hi nhit: - Phng php bn ph ion (sputtering): - Phng php n mn quang in

b. Mt s phng php ha hc in hnh

* Phng php sol-gel

Quy trnh chung ca phng php sol - gel thc hin theo s trong

hnh 1.5.

* Phng php s dng sng siu m

Sng siu m c s dng trong lnh vc khoa hc vt liu trong vi

nm gn y, tc gi cng trnh [2] a ra phng php dng sng siu m

iu ch TiO2 kch c nano t cht u TiCl4.

* Phng php thy nhit

Tin cht

Peptit hoa

Thiu kt

Sol Gel hoa

gel Gi ha

Xerogel

Vt liu rn mang ban

cht oxit

Phng php thy nhit [20] c bit n t lu v ngy nay n

vn chim mt v tr rt quan trng trong nhiu ngnh khoa hc v cng ngh

mi, c bit l trong cng ngh sn xut cc vt liu kch thc nano.

* Phng php kt ta ng th

Cc tc gi [21] s dng dung dch TiCl4 lm cht u iu ch

bt TiO2 bng phng php kt ta ng th. Dung dch TiCl4 c lm lnh

0oC, sau thm tng mu nh vo thc hin phn ng thu phn to

thnh dung dch mu vng nht TiOCl2. Thm nc ct vo dung dch TiOCl2

thu c dung dch trong sut c nng Ti4+ l 0.5M, dng cho qu trnh

kt ta ng th.

* Phng php thu phn dung dch.

Trong s cc mui v c ca titan c s dng iu ch titan oxit

dng anatase th TiCl4 [24] c s dng nhiu nht v cng cho kt qu kh

tt.

Chun b dung dch nc TiCl4 bng cch rt TiCl4 vo nc hoc hn

hp ru-nc c lm lnh bng hn hp nc -mui thu c

dung dch ng nht. Sau dung dch c un nng qu trnh thu phn

xy ra.

1.4. Gii thiu v titan ioxit kch thc nano c bin tnh bng

nit vi tin cht cung cp N l hydrazine v hydroxylammine.

Qua tng quan ti liu chng ti thy:

- Vt liu TiO2 kch thc nano c hot tnh quang xc tc cao, c th

ng dng tt trong cc lnh vc x l mi trng phn hy cc hp cht

hu c bn trong mi trng nc v kh.

- Vt liu TiO2 bin tnh nit c hot tnh quang xc tc cao hn so vi

vt liu khng bin tnh, cho hiu sut quang xc tc cao trong c vng nh

sng nhn thy.

- C th iu ch TiO2 dng bt kch thc nano bng nhiu phng

php khc nhau, nhng phng php thy phn c nhiu u vit: iu kin

tng hp n gin, d tin hnh, sn phm c kt tinh cao v ng nht,

din tch b mt ring ln.

- Chn hydrazine v hydroxylammine lm tc nhn tng pH trong qu

trnh thy phn v cung cp nit.

Do , trong kha lun ny, chng ti chn phng php thy phn

trong dung dch, t cht u l TiCl4 trong dung mi nc vi s c mt ca

hydrazine v hydroxylammine.

CHNG 2: THC NGHIM

2.1. Mc tiu v ni dung nghin cu

2.1.1. Mc tiu

Nghin cu iu ch bt titan ioxit kch thc nano bin tnh bng

nit c hot tnh quang xc tc cao t cht u TiCl4.

2.1.2. Cc ni dung nghin cu

thc hin c mc ch trn, cn trin khai cc ni dung nghin cu

sau:

- Nghin cu nh hng ca nng TiCl4 n kh nng quang xc

tc, kch thc v tnh cht ca bt N-TiO2 kch thc nano iu ch bng

cch thy phn TiCl4 trong dung dch nc vi s c mt ca hydrzine hoc

hydroxylammine.

- Nghin cu nh hng ca nng hydrazine v hydroxylammine

n kh nng quang xc tc, kch thc v tnh cht ca bt N-TiO2 kch

thc nano iu ch bng cch thy phn TiCl4 trong dung dch nc vi s

c mt ca hydrazine hoc hydroxylammine.

- Xc nh iu kin thch hp (nhit nung, thi gian nung, nhit

thy phn, thi gian thy phn, thi gian lu mu trc li tm, iu kin ra

...) cho qu trnh iu ch c bt titan ioxit bin tnh N c hot tnh quang

xc tc cao theo phng php thy phn TiCl4 trong dung dch nc vi s

c mt ca hydrazine hoc hydroxylammine..

2.2. Ha cht v thit b

2.2.1. Ha cht

+ TiCl4 99% (Trung Quc) loi P

+ Etanol tuyt i (Trung Quc) loi P

+ Xanh metylen (C16H18ClN3S.3H2O) (Trung Quc) loi P

+ Hydrazine (Trung Quc) loi P

+ Hydroxylammine (Trung Quc) loi P

+ Nc ct hai ln.

2.2.2. Dng c v thit b

+ Cc thy tinh 100ml, 150ml, 250ml

+ a thy tinh

+ Pipet 0,5ml, 1ml, 5ml, 10ml, 25ml

+ Buret 25 ml

+ Nhit k

+ Bnh tia nc ct

+ ng li tm V=50ml

+ Chn nung

+ My khuy t gia nhit Bibby Sterilin HC 502 (Anh)

+ My ly tm Hettich Zentrifugen D78532 Tuttlingen (c)

+ T sy chn khng SheLab 1425-2 (M)

+ Bm lc ht chn khng Neuberger (c)

+ L nung Lenton (Anh).

2.3. Phng php thc nghim iu ch bt titan ioxit kch thc

nano bin tnh nit theo phng php thu phn t cht u l TiCl4 vi

s c mt ca hydrazine hoc hydroxylammine.

Qa trnh iu ch TiO2 bin tnh nit c tin hnh theo hnh 2.1.

Pha ch dung dch u (TiCl4 3M):

+ Lm lnh nc ct v chai TiCl4 bng hn hp nc mui n gn

0oC, t l th tch H2O/TiCl4 l 2/1.

+ Dng pypet tht kh ly mt lng chnh xc TiCl4 sau nh t t

tng git vo cc nc lnh ang khuy trn hn ch thu phn v thu

c dch trong sut. Qu trnh khuy v lm lnh c thc hin tip tc cho

n khi thu c dung dch trong sut. Ta thu c dung dch TiCl4 3M l

cht u trong qu trnh iu ch N-TiO2.

2.4. Phng php nghin cu

2.4.1. Phng php XRD

Phng php nhiu x tia X (XRD) c s dng xc nh thnh

phn pha v kch thc ht trung bnh ca cc ht s cp trong sn phm iu

ch c.

2.4.2. Ph tn x tia X (EDX hoc EDS)

S c mt ca nit trong mu sn phm TiO2 bin tnh xc nh theo

pic c trng trn ph EDX

2.4.3. Knh hin vi in t truyn qua (TEM)

2.4.4. Phng php kho st kh nng quang xc tc ca titan ioxit

Th hot tnh quang xc tc ca bt N-TiO2 kch thc nano vi tin

cht cung cp N l hydrazine v hydroxylammine

Hiu sut phn ng quang xc tc c tnh theo cng thc:

d c

d

C -CH(%)= .100

C (2.5)

Trong Cd v Cc ln lt l nng xanh metylen trc v sau phn

ng.

2.4.5. Phng php tnh hiu sut qu trnh iu ch.

CHNG 3: KT QU V THO LUN

3.1. Kho st nh hng ca nhit nung

3.1.1. Kho st nh hng ca nhit nung n mu N -TiO2 khi

s dng cht u cung cp N l hydrazine

V vy, chng ti chn 600C l nhit nung thch hp cho qu trnh

iu ch.

3.1.2. Kho st nh hng ca nhit nung n mu N -TiO2 khi

s dng cht u cung cp N l hydroxylammine

V vy, chng ti chn 600C l nhit nung thch hp cho qu trnh

iu ch.

3.2. Kho st nh hng ca nng TiCl4

3.2.1. Kho st nh hng ca nng TiCl4 n mu N-TiO2 khi

s dng cht u cung cp N l hydrazine.

Nh vy, ti nng TiCl4 l 0,19 M th sn phm thu c c hiu

sut phn hy quang xc tc tt nht nn chng ti chn.

3.2.2. Kho st nh hng ca nng TiCl4 n mu N-TiO2 khi

s dng cht u cung cp N l hydroxylammine

Nh vy, ti nng TiCl4 l 0,31 M th hiu sut phn hy quang l

tt nht nn chng ti chn.

3.3. Kho st nh hng ca nng hydrazine v

hydroxylammine.

3.3.1. Kho st nh hng ca nng hydrazine.

Nh vy, ti nng hydrazine l 7,5.10-3 M th sn phm thu c c

hiu sut quang xc tc tt nht nn chng ti chn.

3.3.2. Kho st nh hng ca nng hydroxylammine.

Nh vy, ti nng hydroxylammine l 0.125M th sn phm thu

c c hiu sut quang xc tc tt nht nn chng ti chn.

3.4. Kho st nh hng ca thi gian nung.

3.4.1. Kho st nh hng ca thi gian nung vi mu N-TiO2 khi

dng cht u cung cp N l hydrazine.

. Nh vy, ti thi gian nung l 1.5h th sn phm thu c c hiu sut

quang xc tc tt nht nn chng ti chn.

3.4.2. Kho st nh hng ca thi gian nung vi mu N-TiO2 khi

dng cht u cung cp N l hydroxylammine.

Nh vy, ti thi gian nung l 2h th sn phm thu c c hiu sut

quang xc tc tt nht nn chng ti chn.

3.5. Kho st nh hng ca thi gian thy phn.

3.5.1. Kho st nh hng ca thi gian thy phn vi mu N-TiO2

khi dng cht u cung cp N l hydrazine.

Nh vy, ti thi gian thy phn l 2h th sn phm thu c c hiu

sut quang xc tc tt nht nn chng ti chn.

3.5.2. Kho st nh hng ca thi gian thy phn vi mu N-TiO2

khi dng cht u cung cp N l hydroxylammine.

Nh vy, ti thi gian thy phn l 2h th sn phm thu c c hiu

sut quang xc tc tt nht nn chng ti chn.

3.6. Kho st nh hng ca nhit thuy phn.

3.6.1. Kho st nh hng ca nhit thy phn vi mu N -TiO2

khi dng cht u cung cp N l hydrazine.

Ti nhit 50oC va 90oC thi hiu sut phn huy quang la tt n ht,

nhng tai nhit 50oC hiu sut qua trinh iu ch thp hn nn chung ti

chn nhit thy phn l 90oC.

3.6.2. Kho st nh hng ca nhit thy phn vi mu N -TiO2

khi dng cht u cung cp N l hydroxylammine.

Ti nhit 60oC va 90oC thi hiu sut phn huy quang la tt nht ,

nhng tai nhit 60oC hiu sut qua trinh iu ch thp hn nn chung ti

chn nhit thy phn l 90oC.

3.7. Kho st nh hng ca thi gian lu mu trc li tm.

3.7.1. Kho st nh hng ca thi gian lu mu trc li tm vi

mu N-TiO2 khi dng cht u cung cp N l hydrazine.

T kt qua o quang cho thy khi tng thi gian lu mu trc li tm

khng anh hng nhiu n hiu sut phn huy quang ca sn phm.

3.7.2. Kho st nh hng ca thi gian lu mu trc li tm vi

mu N-TiO2 khi dng cht u cung cp N l hydroxylammine.

T kt qua o quang cho thy khi tng thi gian lu mu trc li tm

khng anh hng nhiu n hiu sut phn huy quang cua san phm.

3.8. Kho st nh hng ca iu kin ra.

3.8.1. Kho st nh hng ca iu kin ra vi mu N -TiO2 khi

dng cht u cung cp N l hydrazine.

V th chng ti ra bng 2 ln nc va 2 ln cn.

3.8.2. Kho st nh hng ca iu kin ra vi mu N -TiO2 khi

dng cht u cung cp N l hydroxylammine.

V th chng ti ra bng 2 ln nc va 2 ln cn (xen k nhau).

3.9. iu ch bt N -TiO2 kch thc nano vi tin cht cung cp N

l hydrazine v hydroxylammin.

3.9.1. S iu ch.

3.9.2. Thuyt minh quy trinh:

+ Tin hnh pha long dung dch TiCl4 3M n nng xc nh, thm

vo hn hp dung dch mt lng nh xc nh hydrazine hoc

hydroxylammine trong iu kin khuy trn. Qu trnh khuy trn tip tc

cho n khi thu c dung dch trong sut.

+ Nng nhit ca dung dch n 90oC qu trnh thy phn xy ra.

Qu trnh thy phn c thc hin iu kin khuy trn mnh trong 2h,

lng dung dich trong 24h. Sau o li tm tach pha rn ra khoi pha long , ra

cht rn thu c bng 2 ln nc va 2 ln cn (xen ke nhau), ly tm. Sau

em sy kh trong t sy nhit v thi gian xc nh, sau em nung

trong l nung 600oC trong 1.5h (vi mu N-TiO2 khi dung tin cht cung

cp N la hydrazine ), 2h (vi mu N-TiO2 khi dung tin cht cung cp N la

Nc ct 0C

Khuy, trn mnh

TiCl4 nh tng git

Hn hp cha TiCl4 3M

Lm lnh

Dung dch trong sut

Khuy Hydrazin hoc hydroxylammine

Thy phn 90oC trong 2h

Huyn ph TiO2.nH2O sau bin tnh

TiO2 bin tnh Nit

Khuy

Nung 600oC trong 1.5h (vi tin cht hydrazine) hoc 2h (vi tin cht hydroxylammine )

hydroxylammine) thu sn phm . Sn phm c mang i chp XRD

xc nh thnh phn pha v kch thc ht trung bnh, th quang xc tc

xc nh hiu sut phn hy xanh metylen.

3.9.3. Kt qua iu ch theo quy trinh.

a. Kt qua iu ch N-TiO2 khi dung tin cht cung cp N la hydrazine.

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau a11

01-078-2486 (C) - Anatase, syn - TiO2 - Y: 62.78 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 3.78450 - b 3.78450 - c 9.51430 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) -

00-004-0551 (D) - Rutile - TiO2 - Y: 96.40 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 4.59400 - b 4.59400 - c 2.95800 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - P42/mnm (136) - 62.4281 - F

2)

1)

File: Mau a11.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 20.000 - Theta: 10.000 - Chi: 0.00 - Phi:

Left Angle: 26.930 - Right Angle: 28.250 - Left Int.: 2.00 Cps - Right Int.: 2.00 Cps - Obs. Max: 27.449 - d (Obs. Max): 3.247 - Max Int.: 322 Cps - Net Height: 320 Cps - FWHM: 0.226 - Chord Mid.: 2


Lin

(C

ps)

0

100

200

300

400

2-Theta - Scale

20 30 40 50 60 70

d=

3.5

13

d=

3.2

45

d=

2.4

85

d=

2.4

28

d=

2.3

78

d=

2.3

32

d=

2.2

96

d=

2.1

86

d=

2.0

53

d=

1.8

91

d=

1.6

87

d=

1.6

66

d=

1.6

24

d=

1.4

80

d=

1.4

52

d=

1.3

60

d=

1.6

99

d=

1.3

46

b. Kt qua iu ch N-TiO2 khi dung tin cht cung cp N la

hydroxylammine.

Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - Mau Ndo nung M2-600C

01-089-4921 (C) - Anatase, syn - TiO2 - Y: 20.09 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 3.77700 - b 3.77700 - c 9.50100 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) -

01-089-4920 (C) - Rutile, syn - TiO2 - Y: 85.59 % - d x by: 1. - WL: 1.5406 - Tetragonal - a 4.58400 - b 4.58400 - c 2.95300 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - P42/mnm (136) - 2 - 62.

2)

1)

File: Mau Ndo nung M2-600.raw - Type: Locked Coupled - Start: 20.000 - End: 70.010 - Step: 0.030 - Step time: 1. s - Temp.: 25 C (Room) - Time Started: 11 s - 2-Theta: 20.000 - Theta: 10.000 - Ch



Lin

(C

ps)

0

100

200

300

400

500

2-Theta - Scale

20 30 40 50 60 70

d=3.4

93

d=3.2

27

d=2.4

75

d=2.3

68

d=2.2

87

d=2.1

78

d=2.0

48

d=1.8

85

d=1.6

82

d=1.6

61

d=1.6

20

d=1.4

76

d=1.4

49

d=1.3

57

d=2.4

18

KT LUN

1. kho st qu trnh iu ch bt TiO2 c bin tnh bi nit bng

cch thu phn TiCl4 trong dung mi nc vi s c mt ca hydrazine hoc

hydroxylammine. Kt qu kho st cho thy, iu kin thch hp cho qu

trnh bin tnh l:

1.1. iu ch bt TiO2 c bin tnh bi nit bng cch thu phn

TiCl4 trong dung mi nc vi s c mt ca hydrazine.

+ Nng TiCl4 trong dung dch khi thy phn l 0.19M

+ Nng hydrazine l 0.0075M

+ Thi gian thy phn l 2h 90oC

+ Nung 600oC trong 1.5h.

Hiu sut phn huy quang: 97.39

1.2. iu ch bt TiO2 c bin tnh bi nit bng cch thu phn

TiCl4 trong dung mi nc vi s c mt ca hydroxylammine

+ Nng TiCl4 trong dung dch khi thy phn l 0.31M

+ Nng hydroxylammine l 0.125M

+ Thi gian thy phn l 2h 900C

+ Nung 600oC trong 2h.

Hiu sut phn huy quang: 97.73

2. Vi iu kin bin tnh trn, nit c mt trong thnh phn cu trc

ca bt TiO2, hot tnh quang xc tc ca sn phm dch chuyn v vng nh

sng nhn thy v c hiu sut phn hu xanh metylen cao. Bt TiO2 c

bin tnh bi nit bng cch thu phn TiCl4 trong dung mi nc vi s c

mt ca hydrazine v hydroxylammine, c hiu sut phn hu xanh metylen

(ln hn 95%) cao hn hn so vi mu sn phm khng bin tnh (ln hn

80%).

3. Phng php iu ch c u im l iu kin tng hp n gin, d

tin hnh, cho hiu sut cao v i t cc cht u c gi thnh r.

References :

Ting Vit

1. V ng (2004), Cc phng php vt l trong ha hc, NXB

HQGHN.

2. Nguyn Khoi, inh Quang Khiu, H S Thng (2008), "Tng hp anatat

kch thc nano bng phng php siu m ha hc", Tp ch Ha

Hc, 46(1), tr. 30 - 34.

3. Ng S Lng, ng Thanh L (2008), "iu ch bt anatase kch thc

nano mt bng cch thu phn titan isopropoxit trong dung mi

cloroform- nc", Tp ch ha hc, 46(2A), tr.177-181.

4. Ng S Lng, Nguyn Vn Tin, Nguyn Vn Hng, Thn Vn Lin,

Trn Minh Ngc (2009), "Nghin cu quy trnh iu ch titan ioxit

kch thc nanomet t tinh qung inanoenit H Tnh bng phng

php axit sunfuric. Kho st qu trnh thy phn ng th dung dch

titanyt sunfat c mt ur iu ch titan ioxit kch thc nanomet",

Tp ch ha hc, 47(2A), tr.150-154.

5. Nguyn Hong Ngh (2002), L thuyt nhiu x tia X, Nh xut bn Gio

dc, H Ni.

6. Nguyn Xun Nguyn, Phm Hng Hi (2002), "Kh amoni trong nc v

nc thi bng phng php quang ha vi xc tc TiO2", Tp ch

Khoa hc v cng ngh, 40(3), tr. 20-29.

7. Nguyn nh Triu (2000), Cc phng php phn tch vt l v ha l,

Tp 1, NXB Khoa hc v K thut, H Ni.

8. Titandioxide, http://en.wikipedia.org/wiki/Titanium_dioxide.

9. Tng quan v TiO2

http://congnghehoahoc.org/forum/search.php?searchid=39326.

Ting Anh

10. Danzhen Li, Hanjie Huang, Xu Chen, Zhixin Chen, Wenjuan Li, Dong ye,

Xianzhi Fu (2007), "New synthesis of excellent visible-light TiO2x-Nx

photocatalyst usinh avery simple method", Journal of Solid State

Chemistry, 180, pp. 2630 2634

11. Deyong Wu, Mingce Long, Weimin Cai, Chao Chen, Yahui Wu Low

(2010) Temperature hydrothermal synthesis of N-doped

TiO2photocatalyst with high visible-light activity, Journal of Alloys

and Compounds

12. Hao-Li Qin, Guo-Bang Gu, Song Liu (2008), "Preparation of nitrogen-

doped titania with visible-light activity and its application", Comptes

Rendus Chimie, 11(1-2), pp. 95-100.

13. Hao-Li Qin, Guo-Bang Gu, Song Liu (2008), "Preparation of nitrogen-

doped titania using solgel technique and its photocatalytic activity",

Materials Chemistry and Physics, 112 (2), pp. 346-352.

14. Hongqi Sun, Yuan Bai, Wanqin Jin, Nanping Xu (2008), "Visible-light-

driven TiO2 catalysts doped with low concentration nitrogen

species", Journal of Photochemistry and Photobiology A: Chemistry,

92, pp. 76-83

15. Hongqi Sun, Yuan Bai, Huijing liu, Wanqin Jin, Nanping Xu (2009),

"Photocatalytic decomposition of 4-clorophenol over an efficient N-

doped TiO2 under sunlight irradiation", Journal of Photochemistry

and Photobiology A: Chemistry, 201, pp. 15-22

16. Huqun Wang, Junping Yan, Wenfu Chang, Zhimin Zhang (2009),

"Practical synthesis of aromatic amines by photocatalytic reduction of

aromatic nitro compounds on nanoparticles N-doped TiO2", Catalysis

Communications, 10, pp. 989994

17. In-Cheol Kang, Qiwu Zhang, Junya Kano, Shu Yin, Tsugio Sato, Fumio

Saito (2007), "Synthesis of nitrogen doped TiO2 by grinding in

gaseous NH3", Journal of Photochemistry and Photobiology A:

Chemistry, 189 (2-3), pp. 232-238.

18. J. Senthilnathan, Ligy Philip (2010), Photocatalytic degradation of

lindane under UV and visible light using N-doped TiO2, Chemical

Engineering Journal, In Press, Corrected Proof.

19. Ju-Won Jeon, Jeong-Rang Kim, Son-Ki Ihm (2010), "Continuous one-step

synthesis of N-doped titania under supercritical and subcritical water

conditions for photocatalytic reaction under visible light", Journal of

Physics and Chemistry of Solids, 71(4), pp. 608-611.

20. K. Kobayakawa, Y. Murakami, Y. Sato (2005), "Visible-light active N-

doped TiO2 prepared by heating of titanium hydroxide and urea",

Journal of Photochemistry and Photobiology A: Chemistry, 170(2),

pp.177-179.

21. K.M. Parida (2009), "Brundabana Naik, Synthesis of mesoporous

TiO2 xNx spheres by template free homogeneous co-precipitation

method and their photo-catalytic activity under visible light

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Issue 1, pp. 269-276.

22. Massimiliano DArienzo, Roberto Scotti, Laura Wahba, Chiara

Battocchio, Edoardo Bemporad, Angeloclaudio Nale, Franca

Morazzoni (2009), "Hydrothermal N-doped TiO2: Explaining

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N active sites", Applied Catalysis B: Environanoental, 93(1-2), pp.

149-155.

23. Peilin Zhang, Bin Liu, Shu Yin, Yuhua Wang, Valery Petrykin, Masato

Kakihana, Tsugio Sato (2009), "Rapid synthesis of nitrogen doped

titania with mixed crystal lattice via microwave-assisted hydrothermal

method", Materials Chemistry and Physics, 116(1), pp. 269-272.

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titan dioxit

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