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Nghiên cứu xử lý một số hợp chất hữu cơ ô nhiễm bằng xúc tác quang hóa tio2 có cấu trúc nano

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 
MỞ ĐẦU
1. Lý do chọn đề tài
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<&I5+&,'4#'45>/J4&>@
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M
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M
$&KQ,
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,'&(O0UVW&,X&Y,Z[\]MK=)I
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M 
_\`X+&4
E5L
M
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M
)*KC


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KO$A2*$=%&/>++'&DE#.d?
#.d'K+Dj/>+YX+&4Dj#.27'j.*
5#1&O4,=1"0+$1'=Z#/
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M
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A+&,"$+D$0#2D4OEa/^Z
%&?KOK5&4?'/KHEL
M
8$&K57-:
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M
8$&,K5$D14+
-))*0+#7/<&L
M
,#.d$>e,"
9)*'/,"5D:1d&CeK5&k5/;Hd
K-DP<aD(D:,
lNghiên cứu xử lí một số hợp chất hữu cơ ô nhiễm bằng xúc tác quang
hoá TiO
2
có cấu trúc nano”

2. Mục đích nghiên cứu
mgE0+L
M
&>^/%+,-
)250+#7/<&L
M

mna2U&YL
M
,'=/2<&#7/%&7K
/=)I%E5H
f/a9'=/>&NO&4,E#7/4//'2
24-)D"(=)
mb//'=Z#.2$=+4$=4
0K$O</KB.*0+&L
M
&$/
/?KO
3. Đối tượng và phạm vi nghiên cứu

m-)/D?K5K77&0+)&L
M
DED:a
$>"
M
m-)>a2U&Y,0+&L
M
,25%&
0+&'>a2
m-)2<&#7/%&L

M
>a2K-2+#.2
/5H

mb9$-)/D?K5K7%&0+)&,
L
M
8>"4/9K-)>&N
o+2>:?K-
oXB/>:?
opI25K7j
ok/D/'j-'aK0+
oq=/D">:%&0+
mb9$</KB>a2L
M
&>8'=/r+&
mb9$</KB#.2 &&
oX+<=#.2 O&4EL
M
&4ED #.2
oNa/
mb9$</KB#.25=4'F+<=#.2 O&
4. Phương pháp nghiên cứu

mgEL
M
&>^/%+
mp&-9,L
M
>^/:K"4


mb?K0+
op/e#&kUksYpI25K7j,j
op/'2jD+.<3Ut!Y4'2jD+.K:
<&Ut!Y'=/B/4'2$4K/R#a%&&<=0+
op/D+2>:?K-UntY'=/D"#9,+
2>:?K-%&0+
op/<&gs&&k/D/'j-'aK0+
op/I2+UumfY'=/D">:+%&0+
mq=/=)<&#7/
S
op/g'22  KUvAmAYbE5K$,
&=)
ok/Dr9fL /bK&
op/Da'F
5. Ý nghĩa khoa học và thực tiễn của đề tài
 !
u1,7-//gE4>a2,'=
Z)*%&0+&L
M

"#
b:, $D=/</KBD:a0+&L
M
qa<%&
%&D:,8K&'=Z)*0+&L
M
>a2K#.d
KO$,"9)*'/U9K-94+'FY
6. Cấu trúc luận văn

w0Z>&NS
Chương 1 : Tổng Quan
 KB>,8da:25L
M
5K7&4>a25L
M
&,/)*L
M
&KCe4BB-)+&
Chương 2 : Thực nghiệm
KB>,/>$a,C+:
mxKBD:aL
M
>^/%+4gE0+&

mq=/2<&#7/%&0+ O&4,E#7
/4//'224-)D"(=)K &&
- q=/'=Z#.d%&0+L
M
&D9$"9N
$>e$$=+4$=4N$
e'F@$//?KO,"9)*'/
Chương 3: Kết quả và bàn luận
KB>,/5D::
y
b?K425%&0+z2<&#7/%&0+D9$
 &&z.+)*0+K#.2'F45=,9
K-9
,K&Q18D4'a0,'a4,+&'=
{

Chương 1 - TỔNG QUAN
1.1. Giới thiệu về vật liệu nano TiO
2
$$$%&'
&,-9g>a)2K-$iK/D54KC-1'a
E$-9'/#Dj,&D#UL
M
YO5
%&L
M
KC-,V L
S
&V LmL
M
U<?illmenitY,0+L
M
O|}DE=#5;HN,&D#,5>/J4
5K7jN>&&K 4&&& ,>K' 4KD1&|
BO?5,K ,&&& 
1.1.1.1. Rutile
s ,K/j>:%&L
M
s 8nK&&)$
/B>/+a#78Drs ,&1D"#a?&5$&
&Q
a) (b)
Hình 1.1.Tinh thể Rutile: (a) dạng trong tự nhiên; (b) cấu trúc tinh thể
b9$K ~-.LDE>&#<&>8S-.
,&/D:f/>/+L


1[( K*_€€[`,[
Dr$/>/+^':q=/mL,[4\{\zm,M4\•
,S4{]u1•,[M€



1.1.1.2. Anatase
12<&1&5KS&
‚&& 8nK&&)$/B>/+a#78$
&,K*%&j>'3,‚&& O1,IJ4D'1
j1,,?#&41D"/>1j'-K5
eK~>:?4/a#$1,KR
L
M
‚&& 1jj1&,s8/D:'++D"
=)2E
(a) (b)
Hình 1.2. Tinh thể anatat: (a) dạng trong tự nhiên; (b) cấu trúc tinh thể.
‚&& 15K7)P,$/>/+>>a
D",-'amL>^&:(2&4K>B,[4\[]ƒ
1.1.1.3. Brookite
f12<&1&K5a4OK52?-2DED:0K/
-),)*f5K7jnK' DE>je8B[S

Hình 1.3.Cấu trúc tinh thể Brookite
Oxy
Titan
]
$$()*+%,-.
(

 
Hình 1.4. Cấu trúc tinh thể anatase và rutile
f=&&&& ,K D:DE-;/D&+9K2L
•
U>/
+Yf/>/+,R#a'/&K'&
C'/&:5K7j=8Da0D"'9,5K7D+.
%&Mj'3 C'/&:250d,25/(
n=[[-"9250d%&L
M
8&&& ,K 
Bảng 1.1. Một số tính chất vật lý của TiO
2
ở dạng anatase và rutile
Tính chất Anatase Rutile
X+j  K&&  K&&
1'& „y
[
& py
M

9& S4]…


y4{…


9 \4y\



M4\{


q9EK- S4…\{
S
y4M{
S
b"'7# M4{M M4][
b")U&!#Y {4{m•4€ •4€m]4€
X^9D+ S[ [[y
+D"1=
+D"&j&
K
[…{…

f
!)ZE|5U AY S4M{ S4€{

L
M
81'2$K K5>::?1&(4'&K
/&#
L
M
8'2$& 41j&&"9=)$&#,':
L
M
1"925+2E|,5#7/<&
mX5*//K|.4//K|N
,'='aK:<&

mw,0+1D"#9&4B0ZO'=Z#7/>:?
mn:4'D"4/,5
m†C>:?L
M
D9$/I.K5&4D1e,%"$
L
M
-/Da$D">/2K59
mND"5>FPD>^/5*>:?%&L
M
4K&
92b:,K52E+#.d/5'2?|&/
a>Fe,''2K,
mf/5>FO>'/1&,,K-L
M
4?25B
ND"=F,5>FD%i1j50DE
-49D"</KB<&#7/>$>89D"/E%&~
K9mD+.4/'a0%&5K7,/8>-,D14K5
'1D:'j,aK+)*<&#7/,:C
q.*K+#.d$4>:?%&L
M
=DE>&%>8/
I.$Dj-1K#;/-'aKb:,aC
a#7%&5>F$>:?L
M
4D?>+D9$H5eQ&&
uDI/,'&(/+-"25+O%&L
M
,

>:?L
M
cK8--5$'DEa/vAAB04+&
L
M
DE.*K:C#.2KO4=#5'21'=
ZC,,9O49D(4=#5/a>D+.4@
$$/-0
1.1.3.1. Phương pháp cổ điển _\`
O&D:aL
M
'a>^/'a%&&#&'X
y
LX
/*-f
y
U?UL
y
Y
M
Y4K.&'a%&5'KN
\
f
y
oyX
y
LX ‡ULXY
y
oyX
y

f U[[Y
ULXY
y
 ‡L
M
oMX
M
L  U[MY
1.1.3.2. Phương pháp tổng hợp ngọn lửa _S…`
L
M
DE=#5$</KB#/f
y
#=K&K"Q'2(
.&f/L
M
a'a8&&& ,K p=)ODE
C+8+D"&[€€€

fDjDE=F15E&
f
y
oL
M
L
M
oMf
M



U[SY
L
M 
pM{U &Y,"=FDED:a>^
/+If
y
K(.&1+D"&[M€

f$C1?%&
DK,#L
M
&D1DE#.d>^QDj>iXf
1.1.3.3. Phân huỷ quặng illmenit _S`4_y`
bI,/D-DE.*Dj=#5L
M

x/KBD:aNS&D

pIT<?  >^X
M
L
y
L
M
oMX
M
L
y
‡UL
y

Y
M
oMX
M
L U[yY
V LoX
M
L
y
‡V L
y
oX
M
L  U[{Y
V
M
L
S
oSX
M
L
y
‡V
M
UL
y
Y
S
oSX
M

L U[•Y

TI9&
UL
y
Y
M
oSUm[YX
M
L‡_LULXY
M
`
m[
UL
y
Y
M
oMUm[YX
M
L
y
U[]Y
LUL
y
YoMUm[YX
M
L‡_LULXY
M
`
m[

LUL
y
YoUm[YX
M
L
y
U[…Y

=FTI
_LULXY
M
`
m[
UL
y
Y
M
‡L
M
oML
S
oUm[YX
M
L U[\Y
1.1.3.4. Phương pháp ngưng tụ hơi hoá học _\`
bI,/D:a>"L
M
1'2$& 8+D"5
$•€€


ff
y
DE,>&8/+D"'/&DjDE//5
'/&4&D1DEj,Q=)X$}DED&
,QXf
y
 ,$DEK"$&"/&1<&
+Q,,'2L
M
8/5''2ˆ~/%&+Q4=
FDEgE>^,(ET,>"'
[€
1.1.3.5. Sản xuất TiO
2
bằng phương pháp plasma _[S`
bEa,K">B'21j7I'KN5'2
UO,'2KYg<&$/55Dj1j1N<&
K>B1MD+C9$"D+a'=,*qN
1D+c#5+N<&H&MD+Cq2H&MD+Cc1
+D"&C5K</KB,4/-.>5D+.K8,
/,D+.C4D12,&&
-.&>D+.>R/,>9,>&-4K8,
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;&,}1"9>K#9K-DOjD"q(DE
aD"1D+N<&2Ec1DE/8&K#9
$?0K&
1.1.3.6. Phương pháp vi nhũ tương _M{`
bI,"KH/Kj(DjD:a/1'2
$&X+}N1"&4"&512>:
?,"&$X+,,+I/>:4D6$%&&$K

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bO'2/('={mM€f/=)/(#=K&'/
(5}a#7&,B,-/1'2$& 
1.1.3.7. Phương pháp sol-gel _S]`
m ,</KBa0+#';4<&/
=)TIm*9'?:5&'# '
x/KBm N{&D&
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♦ u&DMu /
♦ u&DSbB
♦ u&Dy5
♦ u&D{qa'9
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1.1.3.8. Phương pháp thuỷ nhiệt _Sy`
T+,Ca,/=)/($C1?%&
U1j,$YK"+'28D:'++D"Q,/5$[
&p/T+DE)*Dj
♦ gEH0+)
♦ fa0+15K7&
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n^/,4&1jDE/j&4I&4&
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'2$4B/,,&9
mZE-*242=8DaKO
1.1.3.9. Phương pháp siêu âm
-I,"C-)<&K($DE/KjDI4.
*/D"D?>+%&-I5&,+D:'j/=)
/(

-I5&1/*Da=)/(<&+
)~gKKOD,N$4'>-D"%&1I
&Z-B5i>P,IK&C>('2f/>('2&D"4
^#3H",JDaCgI-1#'2/K&;>(‹
q#=K&Cg/>('2+D"1jDDa{€€€q,/51j
D$[€€€&+D"&,=)e,#=K&,,Z9E
I.&4ZD"D"I.JDaZ9D"=)†5
%&5i,&BZEaDj>('2,&DN
OZE1#'2K&'/>('2>#3,$
1.1.3.10. Phương pháp vi sóng
A1,"'r05+>^+&D"I.89D"K5
&4'=Z5+&,DN549</KBT+8+
D"&bI,C'aE%&</KB1O CjDg
ZE1-I,+,C(#/%&/I.
ŒDj2%&+D&1,K+=),D"(
CgEC&p/,D=,e?
p/1DPDE/*K5,KgEH4
a4,&,a<?4D:a/9D?>+4b9
$</KBgE0+'2$&B/,Da&2
DE<&I-)
[S
$$12345-.
(
1.1.4.1. Pha tạp với các chất kim loại _[y`4_M€`4_MM`4_M]`
!"9'‚4p4w4‰4f4!4f 4fK4V 4‚4w44@DE'a
E$L
M
K&HDjH  K<&4OD1aDE</
KB/'aE,DN&$CI&2<&#7/%&L
M


O&+1j#=K&=)H&/K->:?
$X
M
L
M
K254D:,1jI-+EIKP;%&/
,KKOE,iED9$H-
'a?c>-Kj'K''2c2K|
//'='aND"/Z-K'={€mM€€;>:
?2,AB0/$-.I>-KJK&DE?D+.m~
K9'DE'22>^//'='a-I,1Cj
D+.;>-K$>:?,A,04'/jL
M
&
DE>&<&>8/jL
M
'&BJc1+E<&
#7/$//'='a,'=+#=K&=)H&
/K->:?$X
M
L
M
K25
1.1.4.2. Pha tạp phi kim _•`4_SS`4_S{`
q&,/-9'4f4p4V4@O&05
1Cj>$15*:|//'='a4DNO1C
&Dg5K7j
f/-)DIrK&K^'/&a'=M4M{•/
IKjL

M
B>$1'221cj:'=
y€€m{€€q&Bc1CB,-'amLm)'
=m-I,1C&/>&%&L,
A09ITE5HcZ5SaJL
M
&
DE'228>$1yS•
1.1.4.3. Kết hợp TiO
2
với một chất hấp thụ khác
bjI&-<=#7/O&Q'aEL
M
$"0+:
L
M
? K4A0+:|Dj'aE==PD:'+
[y
♦ qDE=1/,%&L
M
K</KB#7/
♦ q>=2K</KB#7/
♦ a/=,D:'+.*34/ K=DE%"
$5,‚4H5K$=)<&#7/
,HD:'+K-4+(0+:Q*"D:'+.
*4D?2(4/=4T41=494 4>-4
'4/ K45,/=4D:1j|,0+:
1.2. Ứng dụng quang xúc tác của vật liệu TiO
2
$($-%67',-.

(
*f/5>/J1ZE|5t

ŽS4{ AD:1j,<&
#7/AB'DE'22>8////  KK-|/
K%&5>/Jc>'22,=-|J$D:'+ZE
%&/=$ZE|5t

qa<=,K-|Jc
1/  K&D+2I</KB>)#K&4(,  K
<&,K-|/Kc1/~K9&D+2
o
4DE
(,/~K9<&UXB[{Yt K<&,~K9<&
2,-IJDa/</KB/(#=K&4>&N</KB
#/D9$~K9<&,</KB'.D9$  K<&
q=Z'.,'=Z#/%&/  K<&,~K9<&
,K5&$//I#/'.DP>aK/(f/  K
<&1'=Z'.;o€4{Dam[4{Az/~K9<&1'=
Z#/;o[4€DaoS4{A_[…`
f/  K<&,~K9<&1jjK&>:?
#7/,/*KCa&/a$/55*K->:?a
55*K->:?,5  KB/~K9<&c/*
KCa?/aDjK&C4a55*K->:?
,50  KB  K<&c/*KCa?/a
K&I
!?'/4Dj=)#/#=K&KCaK->:?>/J4>aZ
[{
E|/KAn%&#7/>/J=1a#/&a#/
%&5=)KD:'+'=/_[…`

Hình 1.5.Cơ chế quá trình xúc tác quang trên vật liệu bán dẫn
!"95>/J,#'D=,•&'1ZE
|5t

^$)S4{ AL
M
Ut

‡S4M AY4ŠL
S 
Ut

‡M4… AY4
KL
S
Ut

‡S4M AY4‰LUt

‡S4M AY4‰Ut

‡S4• AY4fUt

‡M4{ AYD:1
j,#7/<&K-da4K-Car1L
M
,2E
=wd,BL
M
12#7/&54K:?/(,(>:

H4'>ZQ$/*%&//,//5_{`
L
M
8&&& 12<&/&6K b:,DE
=2C&K-=DNZEu=DN|ZE%&&&& ,
K DErK&8XB[•
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,K+$,*r$/5#/JDE,5
K+#.d$h
*!"9D?2=8Da2<&#7/%&0+&L
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♦ ,&&&& ,K
K:-)O&5K^L
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8&&& 12
<&#7/K C'/&:2<&#7/%&M
1j:-IKD14-I2,9D"/'aE%&
~K9<&,  K<&%&K $&&& !?'/
CB,jK r#=K&8+D"&,</KBD:DK&
1&K->:?%&K #=K&K+Dj,'0K'D1$
&&& BCB,j8+D"5->:?DPDEDK&/
/1DK#K->:?L

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K 
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%&&&& ,S4M A4K'%&K ,S AAK2D/|J%&&&&
&K €4M AAK2D/|J%&K K5/$Dj'.%&$
,#b:,,='=Z>RD+.%&$,#02
<&#7/%&K '>^&&& 
2<&#7/&5'=8&&& 'a
,)$"r+5K7&&& K 2E_[[`4_MS`f/KB
-)DPrK&K^2<&#7/'|&&& 'a
U\\4\•Y5KKOEr+&&& K ‡]€S€L

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♦ q2$_{`
q2$,i45K7j'1~#9B2<&
#7/,bDOD%&
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LX),Z
2<&#7/bNO1'2$,>3Bg+2>:?
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Z,D:'++#7/<&/IT5H
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♦ 255*_M`
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)r+0$D"5*/5K->:?#7/b"5*&,&
ZCa#7%&5#7/$E5H4D:'+0E
</KB=)
b"5**",
m+2>:?5#7/f5#7/1+2>:?$4D"#9
&ce,5*/E5HK$

m25&#>&hf5#7/1>:?&2&#c5*9
/5H&2>&hA,E45#7/1>:?&2
>&hc5*9/5H&2&#-I,+)
D+
m25&$,'$%&E5Hf/5#7/L
M
4
‚
M
L
S
5*K5'3/E5H'$K 
♦ bjD6D+h
bjD6D+%&"#'DED&,/KX%&
,D1>:?K,'&D+2
f8%&/#/DDjD6D+C&K-=)K,
D+2>:?b+2>:?%&"#'KKO$,
'a<=%&</KBK/,/KK->:?I>^4DE>j
,!LX4KD1!,'
!LXoX
o
→!LX
M
o
U[[{Y
!LX→ !L
m
oX
o
U[[•Y

O=)K->:?eK&|$=)K,K

LX
m
oX
o
→X
M
L U[[]Y
M[
b9$DjD6D+%&L
M
>-/*D//D"K#7
/Q,"9<&K(^BK&/KX2E%&KO
Dj,Z'=Z5*%&5=)-5#7/4;D1,Z
9D"=)
mqX%&KOiDjD6D+%&L
M
4>:?%&L
M
2D+,Z'=Z5*/&K->:?5#7/
mqX%&KO$DjD6D+%&L
M
4>:?%&L
M
2D+I,='=Z5*/&K->:?5#7/
♦ f/D?2<&(
C5*,>$D-%&</KB<&#7/%&5>/
JD1/D?2<&(%&j&L
M

=8K5$Da
'=Z<&#7/,+.*//'22DE-)
F0
q/~#9Z1j,Z5*/I.>:
?>-K%&/~'DEa/DD%-E>
5*>-K}2$>:?>-,f/'r>
5*,Q>=#,/#>8/Kj|J8>"
&,5-'a54D"N:>:?,C'a*%&/=
8Dai,15*,B0}=8Da/
jDg/(%&</KB<&#7/-,D14C/#*
",r9=#K>B,B0}*",L
M
a#7
$''2&$
$((89:%67',-.
(
& 7;5<=
q=Z<&#7/%&&L
M
DE)*K"KPK#.d
KO4,''24+'F4-+/a>,4@b?
>+:KB-))*+#7/L
M
vAKIT/
5HIeKO$9"49K;I49
+i4E5 4@DPDEC+,1:+9#.dDPDE
/*KCa
MM
1.2.2.1 Cơ chế phân huỷ các hợp chất hữu cơ gây ô nhiễm_[`4_[M`
A0+&L

M
5*ZE//'22,B
,/94=FK&

LX4

L
M
m
4X
M
L
M
4L
M
4 aDE
KB>,8[M[
f/9,=FK&

LX4

L
M
m
4X
M
L
M
4L
M

4#//,
H
soXL

→ s


oX
M
L U[[…Y
s


→X
M
LofL
M
o&# U[[\Y
♦ qE5H)&4&h=)#/<&IT#=
K& a&
s

‡ms•oXL

→sm‡

os•mLXU[M€Y
sm‡ms•oX

→sm‡


os•mX U[M[Y
sm‡

→s


o
M
U[MMY
♦ q/E5H)&‘X4mL
S
4aI
T#=K&&
smL
S
oXL




smLXoL
S

m
U[MSY
L
S

m

oXL
m


L
y
Mm
oX


U[MyY
smLXoXL




fL
M
o5 U[M{Y
04=F%&</KBI%5HIeKO
$K-+#7/<&L
M

,X
M
L4fL
M
,/5f6/E
5H)&K$-c>#1&,/=FK&
& ,&#&>#49|,fL

M
4X
M
L,KE5
HO>#1&,K&?
M
4,L
y
Mm
_[€`
9D"</KB#1&/9XL


*",ND"9XL

4N
D"%&L
M
4,ND"5HKKO$f/a9=8
DaND"%&9XL

>&NX4+D"4,K
=),>=5%&=)4@
1'.*2EL
M
c1'=Z#.dK+Dj/5
MS
eH,,,H5'D"fL
M
4X

M
L4
M
4
X
M
L
y
4@p/#.d$>e>^#7/<&L
M
D&,
,DE)*K"KPOH25+
♦ q11&5D"DE.*L
M
,"5'D"
ODE.*Dj-,CF,EF
♦ u/,K’,1jgEDEE$|,:*D2
'/&
♦ ND"5>FPD>^/5*>:?%&L
M
K&
92b:,K52E+,''2K,
♦ qC&,+E5*D1=F%&7'
=K=<&">$#.d*H&K$'D&K&KO,>"5>F
D:DE'/1&,,4?25,ND"D%iDj1j50
DE
-/,}1"9a5D9D"
</KB<&#7/>$>89D"/E%&~K9mD+.,K&
9D",Q*",/'a0%&5K7,/8>-
,

1.2.2.2. Động học của quá trình quang xúc tác trên TiO
2
a. Động học trên quá trình quang xúc tác
C/</KB#7/jK:94:?D"(=)
</KB#7/<&1j&,{&DD"09a&&
♦ fj/5=)K&i->:?#7/
♦ X5*25"KH5=)->:?5#7/
♦ p=)K&5*UK->:?5#7/Y
♦ u=5*/=F=)
♦ fj/=F=)'i>:?I$H&&&
p=)#7/<&#=K&K&5*U&DSYx/KB
<&1&#7/r'/</KB#7/jK:98'j1&#7
/K<&1&#7/,<&1&Q#7/jK:9,
My
1&+
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X “D?K</KB#7/j9D"=)UKYr+$
>:?> %>85=)UθY KB
 r = kKC/(1+KC) U[M•Y
KD1
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♦ q,+95*%&5=)K->:?L
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♦ f,ND"%&5=)
r=O&}.*KBt ms &Dj=a
=)%&"5'>5*,"5>5*KKOE
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r = k
obs

KC/(1+KC+K
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♦ f,ND"5H
♦ ,K/K&
b. Các yếu tổ ảnh hưởng đến động học quang xúc tác
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K+=)<&1&#7/49D">&D%&5=)r+
0$,E%&5#7/f
LM
8</KB#7/j
O-4'E5#7/E-"/K$,D1BC
Z9D"=)c0,K8-'*",f
LM
u/K$
,*",>=5=)45B,D:'+,+%&+
=)u/K$,)$,ECD%&L
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q,E#7/$/K$4+)R//
#7/;&c %"g>:?<&%&5#7/AB
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