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 -FeOOH α-fe 2 O 3 14
1 mol/l 1/100 mol/l 15
16
17
100 Fe(OH)3 3 hours β-feooh 6 days α-fe2o3 18
2µm 19
Ni(OH)2 With PEG 50,, 12 hours NaH2PO2 0.1 M Ni(OH) 2 + 4 M NaH 2 PO 2 0.5 wt% PEG 400,000 20
2M - : 0.5 M : 1.0 M 21
Reservoir of M Cd(OH)2 or Metal chelates 2+ M(NH3)n 2+ 2+ 2- M + S Reservoir of S 2- TAA Gelatin 22
(TAA: CH3CSNH2) 23
0.30 M M(CH 3 COO) 2 0.66 M Chelating agent A or 0.33 M Chelating agent B (TMD, DMED, DETA, TETA, AA, NTA) (TAEA, EDTA) 2.6 M NH 3 NaOH or CH 3 COOH ph 9.5 0.1 at 25 1 wt% Gelatin Total = 20 ml 25 or 60 1.20 M TAA 1 wt% Gelatin Total =5 ml Product 24
Amines Trimethylenediamine (TMD) H2NCH2CH2CH2NH2 N,N-Dimethylethylenediamine (DMED) H2NCH2CH2N CH3 CH3 Diethylenetriamine (DETA) H2NCH2CH2NHCH2CH2NH2 Triethylenetetramine (TETA) H2NCH2CH2NHCH2CH2NHCH2CH2NH2 Tris (2-aminoethyl) amine (TAEA) Amino Acids L-Aspartic Acid (AA) Nitrilotriacetic Acid (NTA) Ethylenediamine-N,N,N,N - tertaacetic Acid (EDTA) N CH2CH2NH2 CH2CH2NH2 CH2CH2NH2 HOOCCH2CH(NH2)COOH N HOOCH2C HOOCH2C CH2COOH CH2COOH CH2COOH NCH2CH2N CH2COOH CH2COOH 25
logk1 or logk1k2 at 25 or 20 Cd 2+ Zn 2+ Pb 2+ Cu 2+ Ni 2+ TMD (K 1 K 2 ) 16.9 DMED (K 1 K 2 ) 16.0 DETA (K 1 K 2 ) 13.8 (14.4) -0.35 (21.3) (29.6) TETA 13.9 (K 1 K 2 ) 11.9 (K 1 ) 11.4 (K 1 ) 20.1 (K 1 ) 14.1 (K 1 ) TAEA (K 1 ) (12.3) (14.7) (18.8) (14.8) AA (K 1 K 2 ) 15.2 NTA (15.5) (K 1 K 2 ) 9.18 (K 1 ) (11.4) (K 1 ) 13.2 (K 1 ) 16.2 (K 1 K 2 ) EDTA (K 1 ) 16.4 16.4 17.9 18.5 18.1 *Stability constants bound by ( ) are those at 20. K [ ML] [ ML ] = ; K = 2 ; KK 1 2 = [M][L] [ML][L] 1 2 [ ML ] 2 [M][L] 2 26
100 80 T T N T A A N D D D A N E CdS ZnS PbS Yield (%) 60 40 20 T N N T N A T N D D E 0 T A 10 12 14 16 18 20 N N E E E E D: DETA T: TETA A: TAEA N: NTA E: EDTA 25, 2 min 25, 1 h 60, 8 h log K1 or log K1K2 27
Role of NH3 on the Nucleation and Growth Without Ammonia With Ammonia Cd 2+ Cd(NH3)n 2+ Cd-EDTA Cd-EDTA Nucleation Nucleation 2+ [Free Cd ] Renucleation Growth Dissociation Critical Supersaturation Level Dissociation CdS CdS Growth 28
29
A B,C B CeO 2 1.0x10-3 mol/l Ce(SO 4 ) 2 4.0x10-2 mol/l H 2 SO 4 90 30
31
32
2.0x10-2 mol dm -3 FeCl 3 and 4.5x10-4 KH 2 PO 4 at 100 o C M. Ocana, M. Morales, and C.J. Serna: J. Colloid Interface Sci. 171 (1995) 85. M. Ocana, R. Rodriguez-Clemente, C.J. Serna: Adv. Mater. 7 (1995) 212. 33
0 hour 8 hours 2 day 4 day 7 day β-feooh α-fe 2 O 3 34
35
Run 1 Run2 Run3 36
37
CuO 38
CuO LaMer Matijevic CuO Lee, S.H., Her, Y.S., and Matijevic E., J. Colloid Interface Sci. 186, 193 (1997) 39
Cu(NO 3 ) 2 :0.20 mol dm -3, NaOH: 0.40 mol dm 3, 40 40
Cu(NO 3 ) 2 :0.20 mol dm -3, NaOH: 0.40 mol dm 3, 40 41
Cu(NO 3 ) 2 :0.0143 mol dm -3, NaOH: 0.0286 mol dm 3, 40 42
Cu(NO 3 ) 2 :0.0143 mol dm -3, NaOH: 0.0286 mol dm 3, 40 43
Cu(NO 3 ) 2 0.20 mol dm -3 Cu(NO 3 ) 2 0.0143 mol dm -3 NaOH NaOH 0.40 mol dm 3 0.0286 mol dm 3 Aging (40, 6 ) Aging (40, 1 ) CuO 44
CuO Cu 2 O 0.5 mol dm -3 CuO 0.5 mol dm -3 hydrazine (N 2 H 4 ) at ph 9.3, 30 o Cfor 3 hours Cu 2 O 45
CuO Cu 2 O 46
47
[Cu 2+ ] ph 48
Dissolution 1. CuO = Cu 2+ Reduction 2. Cu 2+ + N2H4 = Cu + Hydrolysis 3. Cu + + H2O = Cu2O Dissolution 4. Cu2O = Cu + Reduction 5. Cu + + N2H4 = Cu Dissolution 1. CuO = Cu 2+ Reduction 2. Cu 2+ + N2H4 = Cu 49
Ni-Zn 50
Ni-Zn 51
Ni-Zn 2- Zn Ni Ni Ni 2+ BH 4 Ni Ni Ni only Ni Zn 2+ Zn Ni Ni-Zn Zn 2+ Ni BH 4 Ni Zn 2+ Ni Ni B Zn Ni Zn Ni B B 52
10 9 m = 1 nm m 53
54 1m 10cm 1cm 1mm 100 m 10 m 1 m 100nm 10nm 1nm 1 100 m 10 m 1 m 1nm 100nm 10nm
55
56
57
nm 58
Ni-Zn 2- Ni-Zn Zn Ni Ni-Zn B 5 10 nm 59
Ni Zn, 118, p.211-216 (2002) 60
61
62
63
64
65
Ni-Zn 66
67
68
H, CO H, CO Pt 69
nm Pt 3~5% 70
71
72
73
74
Pt Pt Cl Cl Cl OH OH Cl Pt 4+ Pt4+ Cl OH OH Cl H 2 O H 2 O 100, 2 Pt 0.5 1.0 nm 20 wt% 20 30% 75
ph Pt(OH) 4 100 2 20wt%, ~1nm 76
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 77
78
100 Au 80 Au hydroxides Yield (%) 60 40 20 Initial ph = 6.24; Final ph = 5.98 0 0 4 8 12 16 20 24 28 32 36 40 44 48 Time (h) Metallic Au 79
100 Au/ Metallic Au 80 Yield (%) 60 40 Supernatant Au 20 Au hydroxides Initial ph = 5.98; Final ph = 5.86 0 0 8 16 24 32 40 48 56 64 72 Time (h) 80
Au ph Au : 2.0 mm 81
ph>7 ph UV ph 82
ph 6 ph 6 ph 7 HAuCl 4 AuCl 4 - + 4H + HAuCl 4 + 4OH - Au(OH) 3 + 4Cl - + H 2 O HAuCl 4 + 4OH - Au(OH) 3 + 4Cl - + H 2 O HAuCl 4 + 5OH - Au(OH) 4- + 4Cl - + H 2 O 83
Au 4Au(OH) 3 4Au + 6H 2 O + 3O 2 Au(OH) 3 Au(OH) 3 OH - Au 3+ Au 84
Au Table 2. Produced metallic Au deposited on hematite particles and oxygen in various forms in a concentrated system Reduced product Oxidized products Au ClO ClO 3 ClO 4 - O 2 1.25 x 10 2 2.88 x 10 4 4.64 x 10 3 3.33 x 10 4 1.31 x 10 3 Initial conditions: [HAuCl 4 ] = 2.0 x 10 2 Μ, NaOH = 8.0 x 10 2 Μ, ph = 6.55 [α-fe 2 O 3 ] = 2.0 x 10 1 mol dm 3 (polycrystalline ellipsoids) 100, 72 h 2[O] 3[Au - - - total 3] + 2[O2] = = 0 ] 2 [ClO ] + 3[ClO3] + 4[ClO 0 3 [Au ] 0 3 3 Au(OH) Au + O2 + H2O 4 2 3 G = 318kJ/mol (mol dm 3 ) 0.969 =1 85
Au/ ESCA Arbitrary Unit (-) Au/ Au/ (0.02M HCl ) Au 0 96 94 92 90 88 86 Binding Energy (ev) 84 82 80 86
α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 α-fe 2 O 3 87
Support Particles Table 1 Used Support Particles Size (µm) Structure BET Surface Area (m 2 /g) α Fe 2 O 3, ellipsoids (A) 0.20 0.038 polycrystal 136 α Fe 2 O 3, ellipsoids (B) 0.46 0.10 single crystal 21.8 α Fe 2 O 3, cubes 0.09 single crystal 15.9 α Fe 2 O 3, platelets 13.3 1.5 single crystal 0.70 α FeOOH, needles 0.50 0.020 single crystal 41.0 β FeOOH, needles 0.25 0.012 single crystal 112 ZrO 2 (A), spheres (rough surfaces) 0.015 single crystal 153 ZrO 2 (B), spheres (smooth surfaces) 0.015 single crystal 118 TiO 2, ellipsoids 0.35 0.045 single crystal 88
89
90
α-feooh β-feooh ZrO 2 (A) Rough surfaces ZrO 2 (B) TiO 2 Smooth surfaces 91
-FeOOH -FeOOH ZrO 2 (A) ZrO 2 (B) TiO 2 92
Table 3. Deposited amounts of Au(OH)3 and Au 0 and the mean size of Au 0 particles Support Particles Size (µm) Structure Deposited amount (mol %) Particle size of Au (nm) Au(OH) 3 Au 0 α Fe 2 O 3, ellipsoids (A) 0.20 0.038 polycrystal 19.9 75.1 1 2 α Fe 2 O 3, ellipsoids (B) 0.46 0.10 single crystal 13.8 60.6 2 5 α Fe 2 O 3, cubes 0.09 single crystal 10.5 74.7 3 5 α Fe 2 O 3, platelets 13.3 1.5 single crystal 74.3 8.5 5 15 α FeOOH, needles 0.50 0.020 single crystal 18.8 67.6 5 15 β FeOOH, needles 0.25 0.012 single crystal 10.3 62.7 5 20 ZrO 2 (A), spheres (rough surfaces) 0.015 single crystal 0.6 99.0 0.2-1 ZrO 2 (B), spheres (smooth surfaces) 0.015 single crystal 2.8 95.1 1 3 TiO 2, ellipsoids 0.35 0.045 single crystal 15.8 54.8 2 5 93
94
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 95
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 96
Pt TiO 2 97
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 98
Ni-Zn 99
Ni 100
101
Ni Well-defined as 2-102
Ni-Zn Zn 103
Ni-Zn/TiO 2 2- [Ni(AA) 2 ] = 0.005 mol/l TiO 2 Zn/Ni = 0.1 [NaBH 4 ] = 0.0075 mol/l 30 = 2.5 g/l Ni 12wt% 2- Ni-Zn/TiO 2 104
- / [Ni(AA) 2 ] = 0.005 mol/l Zn/Ni TiO 2 [NaBH 4 ] = 0.0075 mol/l TiO 2 = 2.5 g/l (Ni 12wt% ) 3-way ball valve 2Ni 2 + 3 BH + 4 2Ni B 2H Ni 2 H Ni-Zn/TiO 2 gas gas H 2 2 N 2 heating mantle 105
TiO 2 TiO 2 Sugimoto : 43m 2 /g T. Sugimoto, M. Okada, and H. Itoh: J. Colloid Interface Sci. 193 (1997) 140 106
Zn 107
/ (ICP ) 97 108
Ni-Zn/TiO 2 (Zn/Ni=0.1) 109
Zn Ni Ni-Zn (Zn/Ni=0.1) 10 nm 110
2 - (2) 10nm 10n m Zn/Ni=0.2 Zn/Ni=1.0 111
/ 0.2 Ni(Metal) TiO 2 (Anatase) 112
ESCA (Zn/Ni=0.2) Ni Ni( ) Ni(Metal) Zn N(E)/E Binding Energy(eV) Ni 0 2 Ni/TiO 2 Zn B 26.7% B Ni 73.3% Zn Ni-Zn/TiO 2 39.4% 55.1% 5.6% 113
1 1-Octene C 8 H 16 H 2 cat n-octane C 8 H 18 H 2 5cm 3 5.0 10 2 mol/h 30 4 Ni-Zn/TiO 2 in 2-propanol(50ml) 1-Octene 114
1- (1) Ni-Zn/TiO 2 (Zn/Ni=0.2) Ni Ni-Zn Ni/TiO 2 (Zn/Ni=0.2) 115
1-83 1-1- + Ni-Zn/TiO 2 Ni/TiO 2 4.0 Ni-Zn 2.9 116
1- (2) 117
Ni/TiO 2 Zn Zn B.G. Zn/Ni 1.0 600nm 118
Ni-Zn 119
120
1 121
FeSbO 4 ) etc FeSbO 4 ) 122
1000 ( ) 500 FeSbO 3 900 : FeCl 3 +SbCl 5 123
124
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 125
FeCl 3 +SbCl 5 NaOH Fe,Sb Fe 3+ ] 0 =[Sb 5+ ] 0 = 0.5M : H=1.6 250 2 (FeSbO 4 ) 126
8 FeSbO 3 FeSbO 3 100 127 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 128
100 200 250 10 100 nm 129
(TEOA) 11 0.075 0.10 0.15 TEOA: N(C 2 H 4 OH) 3 100 nm TEOA {100} TEOA TEOA 130
13 TEOA 2 131
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 132
1) 2) 1) (%/m 2 ) (m 2 /g) 0.15(g= ) 2) FeSbO 3 900 FeSbO 4 {100} 133
134
TiO 2 135
CS 2 UV-visible TiO 2 TiS 2 CS 2 1000, 1 136
137