ナノ粒子のサイズ・形態制御と構造敏感型触媒プロセスへの応用

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れんかごちょう
5 years ago
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2 2

3 3

4 10 9 m = 1 nm m 4

5 5 100 m 1m 10cm 100 m 1cm 1mm 10 m 1 m 100nm 10nm 1nm 1 10 m 1 m 1nm 100nm 10nm

6 10 8 6

7 1 nm

9 9

10 10

11 11

12 12

13 13

14 14

15 15

17 17

18 18

19 19

20 20

21 21

22 nm

23 Ni-Zn 2- Ni-Zn Zn Ni Ni-Zn B 5 10 nm 23

24 Ni-Zn 24

25 25

26 26

27 nm 5 50nm 27

28 28

29 29

30 H, CO H, CO Pt 30

31 nm Pt 3~5% 31

32 32

36 (T. Sugimoto, Adv. Colloid Interface Sci. 28, 65 (1987).)

37 100 Fe(OH)3 3 hours β-feooh days α-fe2o3

38 2µm

39 Ni Well-defined as 2-

40 Ni Ni Ni N Ni Ni

41 Ni Ni(OH) 2 Ni

42 Ni / Ni(OH) 2 / Ni/ 42

43 Ni / Ni(OH) 2 Ni(OH) 2 / ph Ni(NO 3 ) 2 : Ni α-fe 2x10-3 mol dm -3 α-fe 2 O 3 : 1x10-2 mol dm - 2 O 3 : 1x10-2 mol dm -3 ph =8 ph 10, 3 100, 24 hrs 100, 24 hours 43

44 Ni / 1 1- BET Ni STY STY (m 2 g -1 ) ( µm) Ni/Fe mol h -1 kg-cat -1 (wt%) mol h -1 mol-ni -1 % c (0.45 x 0.13) (2.2) c 106 (0.40 x 0.08) (7.0) {012} (0.23) (1.9) {012} (0.21) (3.0) c ( 2.05) (0.73) wt% =1-propanol 100 ml, =83, 1-octene= 3.2x10-2 mol, H 2 =50 ml/min-stp, =Ni 5 mmol = 280 mg 1 44

45 Ni / 2 CO K CO (C-atom%) MeOH EtOH CH 4 C 2 + (%) CO 2 no K/Ni =0.1 K/Ni = , 1.1 MPa, W/F=12.4 g h/mol (H 2 /CO=2), Ni(7.0wt%)/ 45

46 ph Pt(OH) wt%, ~1nm 46

47 Selective Deposition [ ] = 2.0 mm (HAuCl 4 ; RuCl 3, RhCl 3, PdCl 2, H 2 IrCl 6, H 2 PtCl 6 ) (, 24 h) NaOH = 1.6 g dm -3 (30 min) 100, 48 h Au, Ru, Rh, Pd, Ir, Pt 47

48 α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 48

49 α-feooh β-feooh ZrO 2 (A) Rough surfaces ZrO 2 (B) TiO 2 Smooth surfaces 49

50 50

51 51

52 Effect of ph on yields of Pt precursor (100, 2days) 100 -Fe 2 O TiO

53 Effect of ph on adsorption of Pt ions (25, 2days) TiO 2 -Fe 2 O

54 Pt TiO 2 54

55 Pt 1- (m 2 g -1 ) (wt%) (H/M) (nm) (% TiO 2, ellipsoid (anatase) Fe 2 O 3, ellipsoid (A)* SiO2 (Stober ) ZrO2 (B)** Al2O3 156 ALO

56 Ni-Zn/TiO 2 2- [Ni(AA) 2 ] = mol/l Zn/Ni = 0.1 [NaBH 4 ] = mol/l = 2.5 g/l Ni 12wt% TiO Ni-Zn/TiO 2 56

57 TiO 2 TiO 2 Sugimoto : 43m 2 /g T. Sugimoto, M. Okada, and H. Itoh: J. Colloid Interface Sci. 193 (1997)

58 Ni-Zn/TiO 2 58

59 Zn Ni Ni-Zn 10 nm 59

60 ESCA Ni-Zn/TiO 2 Ni Zn B 60

61 Ni-Zn/TiO 2 Ni/TiO Ni-Zn

62 62

63 1 63

64 2 FeSbO 4 ) etc FeSbO 4 ) 64

65 ( ) 500 FeSbO : FeCl 3 +SbCl 5 65

66 4 The Gel-Sol Method The gel acts as a protective matrix against the coagulation of the growing particles as well as a reservoir of precursor ion. Gel network Monomer Growing particle 66

67 nm

68 ph ( ) nm 1.0 FeSbO 4 +Sb 2 O < < 6.0 (FeSbO 4 ) 6.0 FeSbO 4 Fe-Sb 68

69 nm 69

70 (TEOA) TEOA: N(C 2 H 4 OH) nm TEOA {100} TEOA TEOA 70

71 13 TEOA 2 71

72 g C 2 H 5 OH/O 2 /N 2 =5.8/18.8/ ( 2C 2 H 5 OH + O 2 2CH 3 CHO + 2H 2 O 72

73 15 2) 1) (%/m 2 ) (m 2 /g) 0.15(g= ) 2) FeSbO FeSbO 4 1) {100} 73

74 74

ナノハイブリッド材料の創製

ナノハイブリッド材料の創製 1 α-fe2o3 α-fe2o3 α-fe2o3 α-fe2o3 2µm 2µm 2µm 10µm CdS CdS Cu2O 0.5µm 1µm 0.5µm 2 Ni-Zn 3 4 5 Ni-Zn 6 7 1. 2. 3. (T. Sugimoto, Adv. Colloid Interface Sci. 28, 65 (1987).) 8 LaMer 9 10 11 O 12 13 α-fe2o3

ナノ粒子のサイズ・形態制御と 構造敏感型触媒プロセスへの応用

ナノ粒子のサイズ・形態制御と構造敏感型触媒プロセスへの応用