Porous Materials

Porous Materials
Bressanone Sept. 2006
Porous Materials
Introduction
Pore Sizes
Aerogels/ Foams
100 nm
Inverse
Opals
Zeolites
M41S
microporous
< 2 nm
mesoporous
2 50 nm
Porous Materials
macroporous
> 50 nm
Introductionthrough Pores
Transport Mechanisms
Porous Materials
Outline
Types
of Pores
g
c
a
f
Porous Materials
Outline
Microporous materials
Zeolites
Metal-organic frameworks (MOF)
Mesoporous materials
Aerogels
M41S-type materials
Macroporous materials
Inverse opals
Foams
Hybrid porous materials

Incorporation of organic compounds
PMOs
Porous Materials
MicroporousZeolites
Materials - Zeolites
Crystalline network
Periodically ordered pore system (micropores)
Narrow pore radii distribution
Variable chemical composition
Mx/n(AlxSiyO2(x+y)) z H2O
Zeolithe
Castello dellOvo at Napoli made from natural zeolite
Porous Materials
Zeolites
Catalysis
Ion exchange
Detergents
Special
(Cosmetics)
Gas separation
COOLKEG
Porous Materials
Zeolites
Al
O
Si
O
Si
Si
O
Si
ZMS-5
Al
O
Porous Materials
Zeolites
Zeolith A
Porous Materials
Zeolites
Porous Materials
10
Zeolites
Porous Materials
11
MicroporousZeolites
Materials - Zeolites
Porous Materials
12
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

PMOs
Porous Materials
13
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
COOLKEG
Porous Materials
14
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Connectors
Linkers
N
CN
NC
CN
O
O
N
NC
O
N
COOLKEG
O
O
Porous Materials
15
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Examples for networks

(different connectors,
only one type of
linker!)
COOLKEG
Porous Materials
16
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Self-Organisation
Zn2+
Zn2+
Zn2+
O2-
Zn2+
Linker
Cluster as connector
Framework
COOLKEG
Porous Materials
17
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
COOLKEG
Porous Materials
18
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Side view
MOF-5: Zn4O(p-BDC)3
top view
(2D)
COOLKEG
Porous Materials
19
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
COOH
Diameter of the
Inner sphere
12,8
COOH
24,5
21,4
COOH
COOH
COOH
COOH
COOH
24,5
28,8
COOH
COOH
COOLKEG
Porous Materials
COOH
20
10
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Zn4O(BTB)2: MOF-177
Sg = 4500 m2g-1
Pores are large enough for
C60 molecules
HOOC
COOH
COOLKEG
BTB
COOH
Chae et al., Nature 2004, 427, 523.
Porous Materials
21
Metal-Organic Frameworks
Cu2
B.Chen et al., 2005
two different pore sizes

(0.83 and 1.01 nm)
Porous Materials
22
11
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Interpenetration networks
COOLKEG
Porous Materials
23
Microporous
Materials
- MOFs
Metal-Organic
Frameworks
Hydrogen storage
Fuel cell
COOLKEG
Porous Materials
24
12
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

Incorportation of organic compounds
PMOs
Porous Materials
25
Mesoporous Aerogels
Materials - Aerogels
HO
HO
O
HO
Si
HO
HO
OH
Si
Si
Si
O
HO
Si
Si
Si
O
Si
OH
Porous Materials
Si
Si
OH
O
Si
Si
O
Si
Si
O
HO
HO
OH
Si
O HO
Si
OH
Si
HO
OH
26
13
Mesoporous Aerogels
Density
Porosity
Pore size
BET surface area
0.003-0.500 gcm-3
80-99.8%
20-150 nm
100-1600 m2g-1
100 nm
Porous Materials
27
Mesoporous Aerogels
OH
H
O
OH
SiO2
OH
H
O
OH
O
H
Drying of the wet gel (density ~ 100 kg m )
H
O
O
With surface
modification (silylated)
Drying of the wet gel (density ~ 1000 kg.m )
O
H
Without surface
modification (non-silylated)
O
SiO2 O
O
O
O
OH
Time of drying
Change in volume
(normed)
1.0
0.9
Silylated
0.8
Not silylated
0.7
0.6
0.5
0.4
0.3
1
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1
Weight reduction of solvent (normed)
Porous Materials
28
14
Mesoporous Aerogels
Structural characteristics of silica aerogel
high porosity (80-99%) with accessible mesopores (20 -150 nm)
low density (0.0030.5 g/m3; for comparison: air 0.0012 g/m3)
high spezific surface area (1001600 m2/g)
Resulting materials properties
1/100 of the thermal conductivity of silicate glass
lower sound velocities as in air
transparent/ translucent (Rayleigh scattering)
modification by organic groups is possible
Porous Materials
29
Mesoporous
Materials
- Aerogels
Aerogels:
Applications
Heat insulation (translucent)
Sound insulation
erenkov detektors
Extremly pure and homogeneous glasses
Storage, increase of viscosity and
after sintering
transport of liquids, e.g. rocket fuels
Collection of cosmic dust
Films with low dielectric constants
Porous Materials
30
15
Mesoporous Aerogels
Porous Materials
31
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

PMOs
Porous Materials
32
16
Mesoporous
Materials
- M41-S
MCM-type
Materials
1971: US Patent 3,556,725 (Sylvania Electric Products)
Synthesis of porous SiO2 from TEOS und surfactant.
However, no characaterization of the material!
1991 Patent: Mobil Oil Co. (J. S. Beck et al., WO 91/11390)
Kresge et al., Nature 1992, 359, 710.
Beck et. al., J. Am. Chem. Soc. 1992, 114, 10834.
Characterization via
X-ray, TEM, adsorption
700
600
500
400
Numbers of publications
(search string: MCM-41)
MCM 41, 48, 50 =

Mobil Composition
of Matter
300
200
100
0
1990
year
1992
1994
1996
1998
2000
2002
1994 the first non-silica based mesoporous materials

1999 the first mesoporous carbons
Porous Materials
33
Mesoporous
Materials
- M41-S
MCM-type
Materials
Porous Materials
34
17
Mesoporous
Materials
- M41-S
MCM-type
Materials
a
a
a
hexagonal H1
Periodicity in
two dimensions
micellar
hexagonal
Ia3d
Periodicity in
Three dimensions
cubic
Porous Materials
Lamellar L,
Periodicity in
one dimension
lamellar
35
Mesoporous
Materials
- M41-S
MCM-type
Materials
Porous Materials
36
18
Mesoporous
Materials
- M41-S
MCM-type
Materials
High specific surface area (> 800 m2/g)

Control of pore size (1.5-30 nm)
Narrow pore radii distribution
Amorphous network with many Si-OH
Flexible network chemistry
(oxides, sulfides, doping)
Control of pore dimension (1, 2, 3-D)
Various templates (neutral, ionic)
Beck et. al., J. Am. Chem. Soc. 1992, 114, 10834.
Porous Materials
37
Mesoporous
Materials
- M41-S
MCM-type
Materials
Charge-Matching is very important ! sol-gel processing conditions
Porous Materials
38
19
Mesoporous
Materials
- M41-S
MCM-type
Materials
N+
Br-
CTAB
Brij
O
Brij 92
OH
OH
Brij 56
Pluronics
HO
O
m
O
n
OH
P123
with n = 20 , m = 70
F127
with n = 106 , m = 70
Si
Si
Si
Om
OH
PDMS-PEO
Porous Materials
39
Mesoporous
Materials
- M41-S
MCM-type
Materials
a0
l0
lc
v
v
cone
g = <1/3
spherical
micelle
truncated cone, truncated

cone
wedge
1/3 - 1/2
cylindrical
micelle
1/2 - 1
vesicles,
flexible bilayers
Porous Materials
cylinder
inverted
truncated cone
planar
bilayers
>1
inverse
micelles
40
20
Mesoporous
Materials
- M41-S
MCM-type
Materials
SBA-15
d100 = 96
hkl
d[]
100
100
100
86.6
83.1
80.2
(100)
SBA-15 host
SA-1
SA-2
d100
a
a
hexagonal: p6mm
u n its )
(110)
(200)
SBA-15 host
ts)
0,9
0.9
1,4
1.4
1,9
1.9
2,4
2
d100
3
a=
2,9
2.4
2.9
a = 111
a = d(pore) + d(wall)
2 Theota
2/
111
47
64
Zhao et al., J. Am. Chem. Soc. 1998, 120, 6024.
Porous Materials
41
Mesoporous
Materials
- M41-S
MCM-type
Materials
Slows down hydrolysis
O
O
P OO-
Ti O
O
Sg = 200 m2g-1
Calc.
350C
TiO2H2O
TiO2
Porous Materials
Ti-TMS1
Ti-Transition Metal Oxide
Sieve No. 1
42
21
Mesoporous
Materials
- M41-S
MCM-type
Materials
Carbon Mesostructured by Kaist
Sacharose
(sugar) +
H2SO4
Pyrolysis
HF or NaOH
SiO2/carbon/carboncomposite
Mesoporous SiO2
(SBA(SBA-15)
Mesoporous carbon
(CMK(CMK-3)
Nanocasting
Porous Materials
43
Mesoporous
Materials
- M41-S
MCM-type
Materials
HO
HO
OH
OH
O Si O
O
HO
OH
O
Si
HO
OH
R.C. Mehrothra 1966

K. Sattler, H. Hoffmann 1999
HO
HO
HO
OH
O
O Si
O
O
HO
140C
OH
OH
HO
HO
O Si
O
O
OH
OH
O Si O
Ar
OH
HO
HO
2
OH
O Si
O
HO
EGMS
Advantages of the ethylene glycol route:

high water solubility of the precursor molecule (no alcohol required)
hydrolysis and condensation reactions do not require a catalyst
good compatibility with surfactant LC phases
Porous Materials
44
22
Mesoporous
Materials
- M41-S
MCM-type
Materials
25 wt% P123
TEM
nm
SEM
cm
Porous Materials
45
Mesoporous
Materials
- M41-S
MCM-type
Materials
HO
OH
O
O Si O
O
HO
OH
pH
0.7
2.5
EGMS
100 nm
Scale bars 1 m
Porous Materials
46
23
Mesoporous
Materials
- M41-S
MCM-type
Materials
OCH2CH3
Si
H3CH2CO
OCH2CH3
+ Ethanol, Wasser, HCl, Surfactant
OCH2CH3
EvaporationInduced
Self-Assembly
(EISA)
Block
Copolymer
EtOH
H2O
Porous Materials
47
Mesoporous
Materials
- M41-S
MCM-type
Materials
mesostructured thin
film (amorphous silica)
Thickness of single layer: 2.3+-0.1 nm

Film thickness: 130 nm
Porous Materials
48
24
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

PMOs
Porous Materials
49
Macroporous Materials Inverse Opals

Inverse
Opals
1. Suitable Template?
Spheres with a diameter above 50 nm,

e.g. organic latex spheres, but also inorganic spheres (Stber particles)
2. Regular packing of the template
Porous Materials
50
25
Porous Materials
51
F. Caruso, Chem. Mater. 2002, 14.
Porous Materials
52
26
Porous Materials
53
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

PMOs
Porous Materials
54
27
Macroporous
Materials
Foams
Porosity
by Controlled
Phase
Separation
Macropore control relies on inducing a phase separation into domains in the

micrometer regime with polymer-additives (PEO or PEOxPPOyPEOx) parallel to the
sol-gel transition
Porous Materials
55
Macroporous Materials Foams
K. Nakanishi, Sol-Gel Science and Technology, Vol 1, Ed. S. Sakka, Kluwer, 2004, pp. 527
Porous Materials
56
28
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

PMOs
Porous Materials
57
Inorganic-Organic
Hybrid
Modification of Pores
by Porous
OrganicMaterials
Groups
3) Addition of
non-reactive compounds
to the precursor solution
HO
OH
OH
M(OR)x
OH
HO
OH
HO
HO
HO
OH
OH
Network
Formation
Drying
4) Co-condensation
+ RM(OR)x
HO
OH
F
OH
OH
HO
OH
OH
HO
F
OH
HO
OH
OH
OH
OH
HO
HO
HO
HO
HO
OH
HO
OH
Drying
OH
HO
HO
OH
Drying
HO
OH
HO
OH
OH
HO
2) Post-synthesis
modification
of the wet gel
or inorganic-organic
nanocomposite material
F
F
F
F
F
F
FF
F F FF
FF
FFF FF
F
F
F
F
OH
Drying
1) Post-synthesis modification
via gas phase
or liquid phase
F
F
F
F
F
F
F
F
F FF F
F
FFF F F
F
F
F
F
Porous Materials
F = functional group
58
29
Inorganic-Organic
Hybrid Porous Materials
Co-Condensation
A
A
A
A
SiO2
SiO2
SiO2
SiO2
A
A
A
A
A
A
unmodified
organic
modification
coated by
carbonaceous
structures
Porous Materials
organofunctional
modification
59
Inorganic-Organic
Hybrid
Porous Materials
Postsynthetic
Modification
Porous Materials
60
30
Inorganic-Organic
Hybrid
Porous Materials
Postsynthetic
Modification
- + - - - + +
- ++
+
+
+
+
+
+
- - -
Me3SiCl
or Me3SiNHSiMe3
surfactant
bonded silyl group
Porous Materials
61
Inorganic-Organic
Hybrid
Porous Materials
Postsynthetic
Modification
Drying by silylation with trimethylchlorosilane

10-20% Me3SiCl in petroleum ether
tms
scf
Quantitative extraction of the surfactant !

Monolithic structure stays intact !
Porous Materials
62
31
Inorganic-Organic
Hybrid
Porous Materials
Postsynthetic
Modification
4.7 mmol g-1
1000
1000 nm
nm
Porous Materials
63
Outline
Zeolites
Aerogels
M41S-type materials
Inverse opals
Foams

Inclorporation of organic compounds
PMOs
Porous Materials
64
32
Inorganic-Organic
Hybrid Porous
Materials - PMO
Periodic Mesoporous
Organosilicas
Porous Materials
65
Inorganic-Organic
Hybrid
Porous Materials
- PMO
Periodic Mesoporous
Organosilicas:
Precursors
Porous Materials
66
33
Inorganic-Organic
Hybrid Porous
Materials - PMO
Periodic Mesoporous
Organosilicas
OR
RO
RO
Si
RO
Si
OR
OR
Porous Materials
67
Inorganic-Organic
Hybrid Porous
Materials - PMO
Periodic Mesoporous
Organosilicas
BET surface area = 500 m2g-1

Mesopores = 7 nm
Macropores = 400 nm
Porous Materials
68
34

Porous Materials

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Porous Materials

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Porous Materials

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Hybrid porous materials

Bressanone Sept. 2006

Castello dellOvo at Napoli made from natural zeolite

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Hybrid porous materials

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Examples for networks

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Chae et al., Nature 2004, 427, 523.

Bressanone Sept. 2006

B.Chen et al., 2005

Bressanone Sept. 2006

two different pore sizes

Bressanone Sept. 2006

Bressanone Sept. 2006

Hybrid porous materials

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Drying of the wet gel (density ~ 100 kg m )

Drying of the wet gel (density ~ 1000 kg.m )

0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

Weight reduction of solvent (normed)

Bressanone Sept. 2006

Bressanone Sept. 2006

Heat insulation (translucent)

Extremly pure and homogeneous glasses

Storage, increase of viscosity and

Collection of cosmic dust

Films with low dielectric constants

Bressanone Sept. 2006

Bressanone Sept. 2006

Hybrid porous materials

Bressanone Sept. 2006

MCM 41, 48, 50 =

1994 the first non-silica based mesoporous materials

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006

High specific surface area (> 800 m2/g)

Beck et. al., J. Am. Chem. Soc. 1992, 114, 10834.

Bressanone Sept. 2006

Charge-Matching is very important ! sol-gel processing conditions

Bressanone Sept. 2006

Bressanone Sept. 2006

Bressanone Sept. 2006