2
3
10 9 m = 1 nm m 4
5 100 m 1m 10cm 100 m 1cm 1mm 10 m 1 m 100nm 10nm 1nm 1 10 m 1 m 1nm 100nm 10nm
10 8 6
1 nm 10 8 7
9
10
11
12
13
14
15
17
18
19
20
21
nm
Ni-Zn 2- Ni-Zn Zn Ni Ni-Zn B 5 10 nm 23
Ni-Zn 24
25
26
nm 5 50nm 27
28
29
H, CO H, CO Pt 30
nm Pt 3~5% 31
32
1. 2. 3. (T. Sugimoto, Adv. Colloid Interface Sci. 28, 65 (1987).)
100 Fe(OH)3 3 hours β-feooh days α-fe2o3
2µm
Ni Well-defined as 2-
Ni Ni Ni N Ni Ni
Ni Ni(OH) 2 Ni
Ni / Ni(OH) 2 / Ni/ 42
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
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 % 19 0.030 1.03 9.79 1.53 c (0.45 x 0.13) (2.2) c 106 (0.40 x 0.08) 0.096 (7.0) 10.04 33.92 5.30 32 0.026 1.67 10.43 1.63 {012} (0.23) (1.9) 38 0.041 4.19 16.53 2.59 {012} (0.21) (3.0) 8.5 0.010 0.10 1.60 0.25 c ( 2.05) (0.73) 150 10 wt% 1.02 1.73 0.27 =1-propanol 100 ml, =83, 1-octene= 3.2x10-2 mol, H 2 =50 ml/min-stp, =Ni 5 mmol = 280 mg 1 44
Ni / 2 CO K CO (C-atom%) MeOH EtOH CH 4 C 2 + (%) CO 2 no 10.02 4.3 1.4 49.7 34.1 10.5 K/Ni 8.35 4.0 2.4 27.9 57.2 8.5 =0.1 K/Ni 1.95 41.7 26.9 10.7 12.3 8.4 =0.1 250 300, 1.1 MPa, W/F=12.4 g h/mol (H 2 /CO=2), Ni(7.0wt%)/ 45
ph Pt(OH) 4 100 2 20wt%, ~1nm 46
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
α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 48
α-feooh β-feooh ZrO 2 (A) Rough surfaces ZrO 2 (B) TiO 2 Smooth surfaces 49
50
51
Effect of ph on yields of Pt precursor (100, 2days) 100 -Fe 2 O 3 80 60 40 20 TiO 2 0 0 2 4 6 8 10 12 14 52
Effect of ph on adsorption of Pt ions (25, 2days) 100 80 60 40 20 TiO 2 -Fe 2 O 3 0 0 2 4 6 8 10 12 14 53
Pt TiO 2 54
Pt 1- (m 2 g -1 ) (wt%) (H/M) (nm) (% TiO 2, ellipsoid (anatase) 37.5 3.0 1.1 0.99 11.9 18.9 1.3 0.86 35.7 3.6 1.4 0.98 3.7 20.0 6.3 0.40 9.7 -Fe 2 O 3, ellipsoid (A)* 136 22.0 2.0 0.09 4.6 SiO2 (Stober ) 4.20 13.6 10-50 0.31 5.0 ZrO2 (B)** 118 18.0 2.4 0.86 19.4 Al2O3 156 ALO6 18.0 1.6 0.85 52.1 3.0 1.2 1.00 10.6 18.0 4.8 0.28 21.2 55
Ni-Zn/TiO 2 2- [Ni(AA) 2 ] = 0.005 mol/l Zn/Ni = 0.1 [NaBH 4 ] = 0.0075 mol/l = 2.5 g/l Ni 12wt% TiO 2 30 2- Ni-Zn/TiO 2 56
TiO 2 TiO 2 Sugimoto : 43m 2 /g T. Sugimoto, M. Okada, and H. Itoh: J. Colloid Interface Sci. 193 (1997) 140 57
Ni-Zn/TiO 2 58
Zn Ni Ni-Zn 10 nm 59
ESCA Ni-Zn/TiO 2 Ni Zn B 60
1-83 1-1- + Ni-Zn/TiO 2 Ni/TiO 2 4.0 Ni-Zn 2.9 61
62
1 63
2 FeSbO 4 ) etc FeSbO 4 ) 64
3 1000 ( ) 500 FeSbO 3 900 : FeCl 3 +SbCl 5 65
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
8 67 100 nm
ph 250 9 0.11 0.73 4.0 ( ) 10.5 100 nm 1.0 FeSbO 4 +Sb 2 O 5 1.0 < < 6.0 (FeSbO 4 ) 6.0 FeSbO 4 Fe-Sb 68
100 200 250 10 100 nm 69
(TEOA) 11 0.075 0.10 0.15 TEOA: N(C 2 H 4 OH) 3 100 nm TEOA {100} TEOA TEOA 70
13 TEOA 2 71
14 0.15g C 2 H 5 OH/O 2 /N 2 =5.8/18.8/75.3 210 ( 2C 2 H 5 OH + O 2 2CH 3 CHO + 2H 2 O 72
15 2) 1) (%/m 2 ) (m 2 /g) 0.15(g= ) 2) FeSbO 3 900 FeSbO 4 1) {100} 73
74