July/August 2004 2
(75%) (25%).
.
. 70% (H2O) 30% (SiO2) . . . 1 . ,
. , .
, .
. (Fe) .
.
(most abundant) (, a class of material) .
.
(Oxyanions, Oxoanions)
. 2 .
University of Houston (1989) , , ( ) . (2000-2001), (2001) ,
2005 .([email protected])
Nanoporous Materials
1. .
(weight%) (atom%)
O 49.4 55.1
Si 25.8 16.3
Al 7.5 5.0
Fe 4.7 1.5
Ca 3.4 1.5
Na 2.6 2.0
K 2.4 1.1
Mg 1.9 1.4
H 0.9 15.4
Ti 0.6 0.2
2. .
C CO32-, HCO3-, C2O42-, C3O32-, C4O42-, C5O52-, C6O62-
Si SiO44-, SiO72-, [SiO32-]n, [Si3O96-]n, [Si4O128-]n,
[Si6O1812-]nN NO2-, NO3-
P PO43-, HPO42-, H2PO4-, P2O74-, P3O105-, P3O93-,
[PnO3n+1](n+2)-, [PnO3n]n-
S SO32-, HSO3-, SO42-, HSO4-, S2O42-, S2O82-
Se SeO42-
Cl ClO3-, ClO4-
Br BrO3-, BrO4-
I IO3-, IO4-
July/August 2004 3
P Si . (polyphosphates) (polysilicates) . ( 1) (, hard water)
Ca2+, Mg2+ (, soft water) . 30~40% (surfactant) Ca2+, Mg2+
. (detergent builder)
(eutrophication)
. .
.
.
. (1)
. (1) .
(1)
, . 3 1 (chain) 2 (sheets) 3 (cage) . 1 (single strand) (double
strand) 1 (asbestos) . 3 ( 2 ). .
asbestosis .
(chrysotile), (kaolinite, china clay), (talc) .
. (mica)
KMg3(OH)2Si3AlO10 . (formal charge) +4 +3 (2)
K+ .
(2)
3. .
(1)
(2)(3)
(single strand) : [SiO32-]n(double strand) : (mica), (talc)
1. Na5P3O10 .
July/August 2004 4
(self assembly) (substrate) .
. (vermiculite) Mg2+ [Mg(H2O)6]2+ .
.
.
. 3 . 3
. 3
65% . 3
65% (fieldspars). (quarts), (mica), (fieldspar) . 2 3 .
3-10 (nanopore) (zeolite) . 1756 Cronsted ( 3) 35 .
. Cronsted , , (steam) zeo() lite(, ) (zeolite) , . () .
4 A, ZSM-5, Zeolite-X Y, -L . A
2. (poly silicate anion) : (A), (B), 2 (C).
520pm
Na2SiO3
730 pm
1740 pm
[Si6O18]12-
Ca3Si3O9 (Fe9Ca)7Si7O21
[Si2O5]2- [Si4O11]6- [Si6O17]10-
6-Membered sheet 4:8 Sheet
A
B
C
3. Cronsted .
July/August 2004 5
3-5 11 supercage, -cage . (Si/Al) X (Si/Al = 1~1.5) Y (Si/Al
= 1.6~3) 7.4 13 supercage . . ZSM-5 -L . ZSM-5 5.5 5.1 5.3 5.6
-L 7.1 .
. .
.
.
.
.
3 (ultramarine) .
. 5 (sodalite) 3 (sodalite unit) S3- S3- S2- . S3- , S3-
S2- .
6 .
4. .
Zeolite-A Zeolite X or Y ZSM-5 Zeolite L
5. () ().
July/August 2004 6
[SiO4]4- [AlO4]5- . [SiO4]4- Si +4 [AlO4]5- Al +3 Al .
. (mobility)
. .
(zeolitic water) .
. (lattice energy) .
.
. , .
(molecular sieve) .
= . .
100 30
130 .
. 3 20 Si P AlPO4 Si Al . 7 Ga P 13.2 30 .
. (zeotype) .
, .
.
(vugs) ( 8) , (cuff link), . ,
. 1930 R. M. Barrer
. Barrer , ,
6. 2 Na+ 1 Ca2+ .
Si
OO
Al
O
Si
O
Al
O
Si
ONa+ Na+
O O O O O OO O O O
- -
Si
OO
Al
O
Si
O
Al
O
Si
O
O O O O O OO O O O
- -Ca2+
7. 4 (A) (cloverite) (gallophosphate) (B-D). D cloverite
1,3,5-triisopropyl benzene .
July/August 2004 7
. (~300C) (autogeneous pressure) (salt) . R. M. Milton 1949
Barrer (~100C)
. Milton 1960
.
, , . 9
(shape-selective) .
. (Bolsena)
(Caldera) . 60% 10% .
.
9. .
+
10. (Bolsena) .
8. : Bikitaite - USA(A), Analcime(B), Stilbite(C),
Heulandite(D), Chabazite(E), Scolecite(F).
A
C
E
B
D
F
July/August 2004 8
. (quarry) 10 .
.
. 11 .
12 (micropore), (mesopore), (macropore) . , (microporous) .
. 2-10 (mesoporous)
. . . 13 , (supramolecular array) .
tetramethyl orthosilicate(TEOS) (precursor) ( 14). . 2-10 .
Mobil J.S. Beck alkylbenezene sulfonate MCM- University
California at Santa Babara G. Stucky poly (ethylene
glycol)-block-poly (propylene glycol)-block-poly (ethylene glycol),
(EOn-POm-EOn) SBA . MCM SBA
11. .
Zeolites
Catalysts,Catalyst Supports
Adsorbents,Dessicants IonExchangers
ConstructionMaterials
SoilCondition
AdvancedMaterials
Animal Food
Additives
MolecularSieves
Nanochannels, Nanopores Hosts for Q-Dots, Q-Wires, Molecular
Organizers,
Memory Devices, Photonic Band Gap Materials, Nonlinear Optical
Materials,
Microlaser Cavities, Display Devices, Solar Cells
ers
13. . Spherical micelle(A), cylindrical micelle(B), lamellar
phase(C), reversed micelle(D), bicontinuous structure(E),
vesicle(F).
A
B
C
D
E
F
12. .
July/August 2004 9
.
KAIST SBA
HF ( 15) (Nature 412, 169 (2001)). O. Terasaki
- ( 16) - (Nature 416, 304 (2002)).
, .
,
. (quantum dot), (quantum wire)
.
.
.
14. CTAC(cetyltrimethylammonium chloride) .
15. SBA TEM (a) (b) (Nature 412, 169 (2001)).
16. - (Nature 416, 304 (2002)).
July/August 2004 10
. .
TS-1, TS-2 wide bandgap TiO2 ( 17A, B) SiO2 TiO2 ETS-10 ( 17C)
wide bandgap .
.
,
(nonlinear optical) ( 18) 2 - (J. Am. Chem. Soc. 126, 673
(2004)).
1 m 1 m 1 m A 109 1 nm 2 m 1 m 0.5 m 0.54 nm 500 nm 2106 ( 19).
1 1 m 1 m 1 m A (substrate) 1 nm 10 2 m 1 m 0.5 m 0.54 nm 500 nm 2
.
17. () TiO2 () : TS-1(A), TS-2(B), and ETS-10(C).
BA
TS-1 TS-2
C
ETS-10
18. hemicyanine .
glassglass
N
N
Br-+
19. (5.3 5.6 ).
20.
.
O H OHO H
O HOH
OHO H O H
OHOH
OH
OH OHO HOH
O HOHO H
O OOS i
O OOSi
O OOS i
O OOS i
O OOSi
O OOS i
O
OO
OO
OO
O OO O
O
SiM e O OM eOM e
O
O
O H OHO HOH
OH
OHOH OHOHOH
O H
OH O OO O
O
OO OO O
O
O
Si
NH2
Si
NH2
Si
NH2
S i
N H2
Si
N H2
O H OHO H
O HOH
OHO H O H
OHOH
OH
OH OHO HOH
O HOHO H
O OOS i
O OOSi
O OOS i
O OOS i
O OOSi
O OOS i
O
OO
OO
OO
O OO O
O
O H OHO HOH
OH
OHOH OHOHOH
O H
OH O OO O
O
OO OO O
O
O
Si
NH2
Si
NH2
Si
NH2
S i
N H2
Si
N H2
z e o l i te z e o l i t e
toluene,1100C, 1 h
toluene,1100C, >1 h
toluene,1100C, 1 h
glass
toluene,1100C, 1 h
toluene,1100C, >1 h
toluene,1100C, 1 h
glass
z e o l i teE tO
OE tOE t
O H OHO H
O HOH
OHO H O H
OHOH
OH
OH OHO HOH
O HOHO H
O OOS i
O OOSi
O OOS i
O OOS i
O OOSi
O OOS i
O
OO
OO
OO
O OO O
O
SiM e O OM eOM e
O
O
O H OHO HOH
OH
OHOH OHOHOH
O H
OH O OO O
O
OO OO O
O
O
Si
NH2
Si
NH2
Si
NH2
S i
N H2
Si
N H2
O H OHO H
O HOH
OHO H O H
OHOH
OH
OH OHO HOH
O HOHO H
O OOS i
O OOSi
O OOS i
O OOS i
O OOSi
O OOS i
O
OO
OO
OO
O OO O
O
O H OHO HOH
OH
OHOH OHOHOH
O H
OH O OO O
O
OO OO O
O
O
Si
NH2
Si
NH2
Si
NH2
S i
N H2
Si
N H2
z e o l i te z e o l i t e
toluene,1100C, 1 h
toluene,1100C, >1 h
toluene,1100C, 1 h
glass
toluene,1100C, 1 h
toluene,1100C, >1 h
toluene,1100C, 1 h
glass
z e o l i teE tO
OE tOE t
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
ze o l i te
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
ze o l i te
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
ze o l i te
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
O OOSi
O OOSi
O OOSi
O OOS i
O OOS i
O OOSi
OOH
N H
O
OHN H
OO H
N H
O
OHN H
O
OHN H
O
O HNH
ze o l i te
July/August 2004 11
A 10 2
.
. 20
( )
. 21
.
( 22A), ( 22B). 3 () ( 22C, D). photonic bandgap .
( 23, Science 301, 818 (2003)).
3 .
21. 20 -A .
2m
22. 3 (A), (B), 3 (C & D) SEM .
A
B
2 m20 m
C
D
23. a, b, c .
a b c
