Nghiên cứu điều chế, khảo sát cấu trúc, hoạt tính quang xúc tác của bột titan đioxit khích thước nano từ chất đầu ticl4 và amin




4




Khoa 




Abstract.  ; 




nano; 







 o; 














 
-
TiCl

-
              



ph

Keywords. 

Content:


2


 


,
TiO
2
             



2

     TiO
2
        


2





2



2
.


2





2
nano 

3


2
nano 


3-

2





4



1.1 



-9




nano
a. Lĩnh vực điện tử, công nghệ thông tin và truyền thông.





b. Lĩnh vực sinh học và y học.

 


c. Lĩnh vực vật liệu.
             



d. Ứng dụng trong lĩnh vực xử lý môi trường.
 


e. Vấn đề năng lượng.
 
               
 


1.2.
1.2.1. Cấu trúc của TiO
2

TiO
2
[8, 22] 

2

o
nc
t
=
1870
o
C).
TiO
2


1.2.2. Giản đồ miền năng lượng của anatase và rutile
TiO
2






1.2.3. Sự chuyển pha trong TiO
2




2
TiO
3
 

2

              

1.2.4. Tính chất hóa học của titan đioxit
TiO
2


1.2.5. Các ứng dụng của vật liệu TiO
2
kích thước nano

Bảng 1.2: Sản lượng titan đioxit trên thế giới qua một số năm.

1958
1967
2003


800.000
1.200.000
4.200.000

            




a. Ứng dụng trong xúc tác quang hóa xử lý môi trường
b. Ứng dụng làm chất độn trong các lĩnh vực sơn tự làm sạch, chất dẻo.
c. Xử lý các ion kim loại nặng trong nước.
d. Diệt vi khuẩn, vi rút, nấm, tế bào ung thư
e. Bề mặt siêu thấm ướt của vật liệu TiO
2
[9].
g. Các ứng dụng khác của bột titan đioxit kích thước nano.
1.3. Gii thiu v c bi.
1.3.1. Các kiểu TiO
2
biến tính

sau:
- TiO
2
c bi kim loi (Fe, Zn, Cu, )
- TiO
2
c bi i [17, 19] (N, B, C,

F, S, )
- TiO
2
c bii hn hp (vt ling bii Cl

hoc Br

)

2


1.3.2. Tính chất của TiO
2
kích thước nano biến tính bằng nitơ.
a. Các tính chất điện của các vật liệu nano TiO
2
đã được biến tính
[14] 

2


2


 

b. Các tính chất quang học của vật liệu nano TiO
2

đã được biến tính.
TiO
2
[10, 11, 12] 


2

 nano 
nano
2
nano.

2
 

c. Các tính chất quang điện của vật liệu nano TiO
2
đã được biến tính.
1.3.3. Các phương pháp điều chế TiO
2
kích thước nano được biến
tính bằng nitơ
a. Một số phương pháp vật lý
- 
- 
- 
b. Một số phương pháp hóa học điển hình
-gel
- 






 


2

4
.







Sol



gel

Xerogel














4
 

2

4


o


2

2


4+






4



4

4

--


1.4.  


- 
2



- 
2



-  TiO
2





- 

Do đó, trong khóa luận này, chúng tôi chọn phương pháp thủy phân
trong dung dịch, từ chất đầu là TiCl
4
trong dung môi nước với sự có mặt của
hydrazine và hydroxylammine.

C2

2.1.1. Mục tiêu
      
 TiCl
4
.
2.1.2. Các nội dung nghiên cứu
 
sau:
- 
4

-TiO
2


4
 
hydroxylammine.
-        

            -TiO
2

nano 
4
 
 hydroxylammine.
- 


TiCl
4
 

2.2. 
2.2.1. Hóa chất
+ TiCl
4


+ Xanh metylen (C
16
H
18
ClN
3
S.3H
2
O) 




2.2.2. Dụng cụ và thiết bị


+ Pipet 0,5ml, 1ml, 5ml, 10ml, 25ml
+ Buret 25 ml

 


 
+ 
 -

 (Anh).

nano 
4
v


2

Pha chế dung dịch đầu (TiCl
4
3M):

4


0
o

2
O/TiCl
4


4

  


4

-TiO
2
.

2.4.1. Phương pháp XRD



2.4.2. Phổ tán xạ tia X (EDX hoă
̣
c EDS)

2
 


2.4.3. Kính hiển vi điện tử truyền qua (TEM)
2.4.4. Phương pháp khảo sát khả năng quang xúc tác của titan đioxit
-TiO
2



dc
d
C -C
H(%)= .100
C
(2.5)

d

c


2.4.5. Phương pháp tính hiệu suất quá trình điều chế.



C

3.1.1. 

 -TiO
2
khi




3.1.2. 

 -TiO
2
khi




4

 
4
-TiO
2
khi


4



4
N-TiO
2
khi



4


         
hydroxylammine.


-3



           


-TiO
2
khi

 

-TiO
2
khi


 


-TiO

2




-TiO
2




3.6. 





.
3.6.1. 



 -TiO
2


 50
o



 90
o








 ,






 50
o









90
o

C.



3.6.2. 



 -TiO
2


 

60
o


 90
o








 ,







 60
o









90
o
C.
3.7. 





.
3.7.1. 







-TiO
2




















.
3.7.2. 







-TiO
2



























.
3.8. 





.
3.8.1. 





 -TiO
2
khi

2 



2 .
3.8.2. 






 -TiO
2
khi

2 



2 
3.9. 





-TiO
2

l.
3.9.1. 





.


3.9.2. 




:

4

           
hydr        


o




 24h. 







 , 




 2 




2 (



trong l
o
C trong 1.5h (



 N-TiO
2





 ), 2h (



 N-TiO
2






  



TiCl
4
t


4
3M









o
C
trong 2h



2
.nH
2
O




TiO
2




600
o
C trong 1.5h (


) 

2h (


)

hydroxylammine)  . 




3.9.3. 










.
a. Kết qua
̉
điều chế N-TiO
2
khi du
̀
ng tiền chất cung cấp 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
Left Angle: 24.590 ° - Right Angle: 25.940 ° - Left Int.: 2.00 Cps - Right Int.: 2.00 Cps - Obs. Max: 25.326 ° - d (Obs. Max): 3.514 - Max Int.: 219 Cps - Net Height: 217 Cps - FWHM: 0.298 ° - Chord Mid.: 2
Lin (Cps)
0
100
200
300
400

2-Theta - Scale
20 30 40 50 60 70
d=3.513
d=3.245
d=2.485
d=2.428
d=2.378
d=2.332
d=2.296
d=2.186
d=2.053
d=1.891
d=1.687
d=1.666
d=1.624
d=1.480
d=1.452
d=1.360
d=1.699
d=1.346

b. Kết qua
̉
điều chế N-TiO
2
khi du
̀
ng tiền chất cung cấp 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
Left Angle: 26.950 ° - Right Angle: 28.330 ° - Left Int.: 2.00 Cps - Right Int.: 2.00 Cps - Obs. Max: 27.618 ° - d (Obs. Max): 3.227 - Max Int.: 484 Cps - Net Height: 482 Cps - FWHM: 0.235 ° - Chord Mid.: 2
Left Angle: 24.760 ° - Right Angle: 26.290 ° - Left Int.: 2.00 Cps - Right Int.: 2.00 Cps - Obs. Max: 25.495 ° - d (Obs. Max): 3.491 - Max Int.: 149 Cps - Net Height: 147 Cps - FWHM: 0.277 ° - Chord Mid.: 2
Lin (Cps)
0
100
200
300
400
500
2-Theta - Scale
20 30 40 50 60 70
d=3.493
d=3.227
d=2.475
d=2.368
d=2.287
d=2.178
d=2.048
d=1.885
d=1.682
d=1.661
d=1.620
d=1.476

d=1.449
d=1.357
d=2.418















1. 
2


4

            

1.1.   
2
      
TiCl

4


4


+ Th
o
C

o
C trong 1.5h.




: 97.39
1.2.   
2
      
TiCl
4


4



0
C


o
C trong 2h.




: 97.73
2. 

2
 

2


4

ylen

80%).
3. 


References :







     Các phương pháp vật lý trong hóa học, NXB

"
", Tạp chí Hóa
Học, 46(1), tr. 30 - 34.
2008), "
          
cloroform- ", Tạp chí hóa học, 46(2A), tr.177-181.
4.          
2009), "
     nano    

 ",
Tạp chí hóa học, 47(2A), tr.150-154.
Lý thuyết nhiễu xạ tia X, 

"

2
", Tạp chí
Khoa học và công nghệ, 40(3), tr. 20-29.
Các phương pháp phân tích vật lý và hóa lý,

8. Titandioxide,
9. 
2






10. Danzhen Li, Hanjie Huang, Xu Chen, Zhixin Chen, Wenjuan Li, Dong ye,
Xianzhi Fu (2007), "New synthesis of excellent visible-light TiO
2x
-N
x
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
TiO
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12. Hao-Li Qin, Guo-Bang Gu, Song Liu (2008), "Preparation of nitrogen-
doped titania with visible-light activity and its application", Comptes
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13. Hao-Li Qin, Guo-Bang Gu, Song Liu (2008), "Preparation of nitrogen-
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14. Hongqi Sun, Yuan Bai, Wanqin Jin, Nanping Xu (2008), "Visible-light-
driven TiO
2
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15. Hongqi Sun, Yuan Bai, Huijing liu, Wanqin Jin, Nanping Xu (2009),
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doped TiO

2
under sunlight irradiation", Journal of Photochemistry
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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 TiO
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", Catalysis
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17. In-Cheol Kang, Qiwu Zhang, Junya Kano, Shu Yin, Tsugio Sato, Fumio
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gaseous NH
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", Journal of Photochemistry and Photobiology A:
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synthesis of N-doped titania under supercritical and subcritical water
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2  x
N
x
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       
Battocchio, Edoardo Bemporad, Angeloclaudio Nale, Franca
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2
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