Titanium Dioxide, TiO2

1
???

• ??? ??? ??? ??? ??? ??? ??? ??? ??? ??? ??? ???
  ???

2
Introduction

• ???

3
???????????

• ???????

• ????????????????

• ????????????

• ?????????

• ????????????

4
????
???????? ?? 51.4 ??
30.8 ?? 9.0 ??? 6.7
???? 2.1
5
??????

• 2H2 O2 ? 2H2O

??? H2O,???
?H 286 kJ/mol
???????
???3? ,???3.9?,???4.5?
6
???????????

• 1.?????

???????????????
2.?????
Ex ????,???????????
7
?????

• Water splitting
• ??????
• ??????

8
Water splitting

• ???

9
Water splitting

• ??????? - ???
• H2O H2O2

10
Water splitting???

• ?????? - ????
• 1.??????
• 2.????
• ????????????
• ( 1 ) ???????????
• ( 2 ) ????????????
• ( 3 ) ?????????

11
????

• ????????????,????????????????EX.???????
• ??????????????,????????
• ?? ??? ??
• ?? ??? ??

12
???????? PEC

• PhotoElectroChemical

13
?????????

• Photocatalytic
• ?????

Step 3.
H H2
O2 H2O
Step 3.
Step 2.
e- h
Step 1.
Recombination
Hv gt Eg
Particulate photocatalyst
14
Principle
15
???????

• ????
• ???
• ???
• ???
• ??
• ????

16
Titanium Dioxide, TiO2

• ????
• ???

17
TiO2

• Occurs in nature as well known minerals Rutile,
  Anatase and Brookite.
• Most stable form is Rutile.
• All contained 6 coordinated
• titanium.
• Their band gaps are similar.
• (3.0 eV for Rutile and 3.15 eV for Anatase)

18
Honda-Fujishima Effect

• Discovered by AKIRA FUJIJSHIMA and KENICHI HONDA
  in 1972.
• Suggested that water can be decomposed by visible
  light without any external voltage.
• TiO2 2hv ? 2e- 2p
• 2p H2O ? ½ O2 2H
• 2e- H ? H2
• -----------------------------------
• Overall H2O 2hv ? ½ O2 H2

19

• This effect is very similar to the photosynthesis
  process.

20
Development of TiO2

• Efficiency is low when pure TiO2 is used.
• Over the years, different materials have been
  used to develop TiO2.
• Replacement of Pt with Rh as the cocatalyst.
• TiO2 combine with metal oxides (eg SrO) to form
  metal tanalates (SrTiO3).
• NiO deposition on the metal tanalates improves
  the Quantum Efficiencies (QEs).
• Rh gt Ru gt Re gt Pt gt Ir gt Pd gt Os gt Co

21

• The table below shows some of the photocatalysts
  that have been developed over the years.

22
??????

• ???

23
??

• ??????????? 96??????????
• ?????????????,????????????????

24
??????

• ???
• ????
• ???? (1) C(s) H2O(g) ? CO(g) H2(g)
• (2) CO(g) H2O(g) ? CO2(g)
  H2(g)
• ?????
• ?????????? CH4 (g) 2H2O(g) ? CO2(g) 4H2(g)
• ???????????????? CH4 (g) 0.5O2(g) ? CO(g)
  2H2(g)
• ?????? CH4 (g) ? C(s) 2H2(g)
• ????????
• ?????? CH3OH(l) H2O(g) ? CO2(g) 3H2(g)
• ?????
• ?????????

25
??????????
????75
(1) CH4 (g) H2O(g) ? CO(g) 3H2(g) (2) CO(g)
H2O(g) ? CO2(g) H2(g) ???CH4 (g) 2H2O(g) ?
CO2(g) 4H2(g)
http//blog.roodo.com/energytech/archives/3936257.
html
26
????????

• ???????
• ?????????????????
• ????????????????
• ????
• ?????????,??????? ,????????
• ??????
• ????????

27
???? Cu/Zn/Zr/?-Al2O3
??????????? incipient wetness
Taylor C. E. Ind. Eng. Chem. Res. 2007, 46,
8906-8909
28
????????
?????????????,????????????????????????????????????
???????????????????????
http//blog.roodo.com/energytech/archives/3936577.
html
29
??????

• ???

30
???????

• ????(photosynthesis)
• ???(light fermentation)
• ???(darkfermentation)

31
????(photosynthesis)

• hydrogenase
• 2H 2Fd- H2
  2Fd

• ??????,??????
• ??????
• ???????,???????

32
???(light fermentation)

• Glucose 6 H2O 6 CO2 12 H2

• ???????,??????
• ?????????
• ?????nitrogenase???????
• ????????
• ???????

33
???(darkfermentation)

• C6H12O62H2O 2CH3COOH4H22CO2
• C6H12O6 CH3COOH2H22CO2

H2

• ?????,???????(????? etc.)
• ???????(?????????????)
• ???????????

34
???????????
35
??

• ???

36
????????!?????????????!

• ????
• ???????????????????,????????????????2535MPa?
  ??
• ????
• ???????????,???????????????,??????????70MPa??
  ????1.9wt???3wt

37

• ????
• 1. ???
• ???T????P1?P2????????????
• WA T log(P2/P1) A??????????
• 
  ??1?70MPa?0.8
• 2. ????
• ?????????????,???????????????
• ???,??????????????????

38
???????

• ????????????????????????
• ????????
• ??????

39
?????

• ???
• Advantages
• Disadvantages
• Examples
  

40
Advantages

• ?????????????????????????????????845?

845
41
Disadvantages

• ?????????
• ???????
• ????????

42
BMW?????????????-Hydrogen 7
43

• ????????,???3mm?????,???????????????-250???BMW????
  ?,??????????,??????????,????17?????????

44
??????

• ???

45
?????????

• LiAlH4?NaBH4????????? ????????
• ?????
• ?????????

46
???????????
47
??????
48
??????
49
????

• ??? ???

50
????
??v.s????
??
1.?????? 2.???? 3.???? 4.?????
51
???
????
(?????? ???, ????B? ?26? ?5? 1996)
52
????
????????? ???????? ????????
Picture from paper published in Nanotechnology,
Vol. 17, No. 15, 14 August 2006, pp. 3920-3924
(2006)
53
????
??
1.????????????SP2?????? 2.???????? 3.?????,???????
??? 4.?????????? 5.??????????????
??
???????????????????
54
BN???
1. ???????????,????????????????????
2. BN???????????????,BN????????????,????????,?????
?????
3. Narita?Oku????BN????????,????????,?????70?????
??,30?????
Tang, C. C. Bando, Y. Ding, X. X. Qi, S. R.
Golberg, D., J. Am. Chem. Soc.
55
??????
1. MoS2?TiS2
2. ??????BN?????
3. ?????,??????????
4. MoS2????????????S???????Mo??
56
Metal Organic framework

• ???????? ??????

ClusterZn4O6 Linker O2C-C6H4-CO2
Cavity
MOF-5
Zn4O(BDC)3 (BDC 1,4-benzenedicarboxylate)
57
Metal Organic framework

• ????
• 1.?????(20003000m2/g)
• 2.???(0.210.41g/cm 3)
• ????
• ?77K?,????4.5wt
• ????,?20Bar??,????1.0wt
• ? P??,??????

298K
78K
58
MOF ??????

• ??????????????
• ????

????
????? ?? 16 Å ??
59
MOF ??????

• ??????
• ????????? ??????????
• ???????????
• ??????????Mg2?Al3
• ???????
• ????(????)???????????

60
MOF ??????
2?

• ?????(linker)

IRMOF-6
4?
MOF-5
IRMOF-8
61
MOF?????????

• ???????????
• ?????????????

???????????,?3W PEM??????,???iPod
Shuffle????????(?????)
62
??

• ???

63
(No Transcript)
64

• ??
• 1.??????
• 2.?????????
• 3.???????
• 4.?????
• TiO2?Tanalates?Zirconium Oxide
• ???

65

• ??
• 1.????
• 2.????
• 3.??????
• 4.???????
• 5.????
• ???????????????

66
(No Transcript)
67
(No Transcript)
68
????

• ???

69
??

• ?????????????????
• ???????????????
• (ex??? ?? ???)

70
??????
71
?????

• ?????????
• ?????????
• ???????
• ????????

??????????????
72
??

• ???? ??????
• ???? ????????????

73
??????????
The Journal of Physical Chemistry
74
Thanks for your attention!!