Mesoporous materials

Overview
Why mesoporous materials? Self assembled templates and the structures that can be formed using them Control of pore size Mechanism of formation Absorption properties

Why mesoporous materials?

Zeolites are limited to pore sizes of ~15 Materials characteristics similar to zeolites but with larger pores would be very useful
Separate larger molecules Perform catalysis on larger molecules
Crack higher MW hydrocarbons to form gasoline etc.

Self assembled templates offer a way to produce oxides with larger pores

Self assembled templates

In zeolitic materials the template is a single molecule or ion Self assembled aggregates of molecules or ions can also serve as templates
Surfactants aggregate into a variety of structures depending on conditions

Self assembled surfactant structures

In solution surfactants can self assemble to form micelles, rods, sheets and 3D structures
All of these can in principle be used as templates Rod like surfactant aggregates have provided some of the most interesting structures

A lot of work has been done exploring the formation of silicate structures using self assembled templates
Other inorganic oxides have also been examined

Materials containing rod like assemblies

MCM-41 silicate structures Material is highly ordered and gives a diffraction pattern but the silicate walls are not crystalline, they are glass like

A typical MCM-41 synthesis

MCM-41 contains rod like surfactant aggregates. MCM-41 materials can be made in many ways. Aluminosilicate materials have been prepared as follows
C16H33NMe3OH, catapal alumina, TMA silicate and amorphous silica stirred in water Heated in autoclave for 48 hours at 150 C Recover by filtration and remove template by heating in nitrogen to 540 C for 1 hour and then heating in air for 6 hours
Surfactant decomposes by Hoffman elimination reaction

Pore size distribution

The pore size distribution in MCM-41 is usually quite narrow as well ordered materials can be made, but it is not as tightly defined as that for a zeolite as MCM-41 is not a crystalline product

3D porous silicate structures

3D porous networks can also be prepared. Once again the silicate is glass like but the pores are ordered.

Lamella structures

A Variety of different layered structures can be formed. These data apply to MCM-50 a stabilized layered structure. Unstabilized structures contain surfactant bilayers and collapse when the surfactant is removed

Controlling the type of self assembled structure

Changing the composition of the synthesis mixture can change the type of self assemebled structure that is formed

Firouzi et al. Science 267, 1138 (1995)

Control of pore size

All the early work on mesorporous silicates was done using Me(CH2)n-1NMe3+ surfactants
Increasing the chain length produces materials with bigger pores Swelling the surfactant assembly by the use of an organic additive such as trimethylbenzene also gives bigger pores

After a material has been made the pore size can be reduced by modifying the interior surface

Influence of chain length

Increasing the surfactant chain length increase the pore to pore spacing and the total fraction of the material that is open space

Pore size and chain length

Surfactant chain length n CnH2n+1NMe3
+

Lattice constant ()

Ar pore size ( )

Maximum benzene uptake at 50 torr (wt%) 16 37 32 36 54 64

8 9 10 12 14 16

31 32 33 33 38 40

18 21 22 22 30 37

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

Swelling using auxiliary organics

Post synthesis modification

Silylation of hydroxyl groups in MCM-41 using reagents such as Me3SiCl can be used to reduce the effective pore size

Mechanism of formation for MCM-41

Quite some controversy
Does the surfactant self assemble and then get coated in silica or does the interaction between the silicate species and surfactant play an important role in self assembly?

Even layered intermediates have been proposed

Some layered silicates can be converted to MCM-41 like materials by treatment with a surfactant
Supports notion that there may be a layered intermediate in the formation of MCM-41

Role of silicate
Interactions between the silicate and the surfactant play an important role in the self assembly process
Ordered structures are formed in the presence of silicate that are not formed in pure surfactant solutions under similar conditions

Firouzi et al. Science 267, 1138 (1995)

Mechanism involving silicate surfactant interactions

Firouzi et al. Science 267, 1138 (1995)

NMR evidence for mechanism

Deuterium NMR tells us what phases are present in solution. If low synthesis temps are used You can reversibly transform layered and hexagonal structures. Heating polymerizes the silicate and locks in the structure

Firouzi et al. Science 267, 1138 (1995)

Absorption in MCM-41
Absorption in mesorporous materials is different from that in zeolites
uptake occurs at higher pressure and may show hysteresis

Benzene absorption

Oxygen absorption