What are Porous materials

Most generalized definition of porous materials is continuous and solid network material filled through voids. A material can be recognized as porous if its internal voids can be filled with gases. The history of porous materials began with the zeolites having aluminoisilicates framework which was synthesized by the use single template molecule with small pore.

Classification of porous materials

Depending on pore size

Depending on building framework

Macroporous

Micropoorus

Mesoporous

<2nm ZSM-5

2-50 nm MCM-41

>50nm Sponge Purely inorganic Silica Organic Inorganic hybrid MOF Purely organic

organic porous polymers

Mesoporus Materials
Meso a Greek prefix in between - micro and macro porous system Mesoporous materials may be ordered or disordered. They possess high Surface area -400 -1000 m2/g Large pore volume High stability -500 -600 C They are usually synthesized by the use of Soft template method. Ex: MCM-41,SBA-15,FDU-11,IITM-56 etc.

Difference between the zeolites and mesoporous materials

Zeolites
Highly crystalline TO4 networks

Mesoporous Materials
Periodic arrangement with amorphous in nature TO4,TO5 and TO6 networks

Si and Al are four connected by covalent Si and Al are 2 or three connected ,more bond, less surface hydroxyl groups surface hydroxyl groups Hydrophobic surface area Hydrophilic surface area High hydrothermal stability Crystalline walls and are thick Synthesis temp is high (80 300 C) Long crystallization time Aqueous media is required for crystallization Synthesis of zeolite is carried out in neutral /weakly acid media Less hydrothermal stability Amorphous walls and are thin Synthesis temp is low (-10 to 120C) Formation rates are fast Non aqueous solvents and non polar solvents can be used Synthesis pH rang is from 0 to 12

Synthesis of mesoporous materials

Soft template (endo template) Uses soft templates like organic molecules .
Hard template (exo template, nano casting) Uses inorganic materials like silica, carbon etc Tedious work up, hard to get good morphology and costly CMK-1

Good shape , Size and morphology. simple SBA-15 ,MCM-41 etc

Meso-silica

CMK-1

Synthesis of mesoporous materials using soft template strategy

1. 2. 3. 4. 5. 6. 7. 8.

Surfactants. Formation of Micelles. Inorganic precursor . Interaction of Micelles with inorganic precursor. Hydrothermal treatment followed by separation and drying Removal of template. Proposed mechanism Characterization of material.

1. Surfactant/ Template/Structure directing agent.

Large organic molecules(High molecular weight) with both hydrophilic and hydrophobic groups. Depending upon charge they can be classified as Cationic
Excellent solubility High critical Micelle con. acidic and basic media toxic and expensive

Anionic
Excellent solubility repulsion between the anionic surfactant is more.

Non ionic/neutral
Excellent solubility High critical micelle temp. Acidic / basic media non-toxic and cheap

2. Formation of micelle
At a Low surfactant concentration will favor arrangement on the surface. As the concentration increases surface being more crowded as result molecule arrange in to micelles.

At certain concentration the surface is completely loaded and any further addition leads to the Micelle arrengment.This conc. is known as CMC.
Beyond the CMC self assembly of micelle occurs to from 3D and 2D rod like arrays.

Different template have the different CMC.

To get ordered materials 0 to20 mg/L

Different type of surfactant arrangement

What Makes them to show different type of arrangements ?

1. Critical micelle concentration Low micelle conc. are good to get ordered materials. 2. Packing parameter (g) g = V / ao l V=Total volume of surfactant hydrophobic chains+ co-solvnet. ao= Effective hydrophilic head group area at the aq. micelle surface. l = kinetic surfactant tail length. g <1/3 = cubic and 3 D hexagonal, 1/3<g>1/2 = 2D hexagonal 1/2<g>2/3 = cubic g=1 = Lamellar 3. The hydrophilic and hydrophobic Volume ratio (VH/VL)

3.Inorganic precursor and pH

Inorganic Precursor silica depends upon pH Basic synthesis (pH =9.5 to 12.5) -Polymerization and cross Linkage of silicate species are reversible Silica gel, colloidal sol, Water glass , TEOS etc. Acidic synthesis(pH= 1 to 2 ) - Irreversible. - Slow hydrolysis TEOS is preferred.

4. Interaction of Micelles with inorganic precursor.

Direct interaction of Surfactant with inorganic precursor

Basic -Medium

Acidic-Medium

Interaction of Surfactant with inorganic precursor through intermediate ions

Acidic-Medium

Basic -Medium

Interaction of non ionic Surfactant with inorganic precursor through intermediate ions.

Hydrogen bonds favors most of times

5. Hydrothermal treatment followed by separation and drying.

Method to improve mesoscopic regularity's of products. Reorganization, growth and crystallization 80 -150 C is temperature is usually used. High temperature will lead to the disorder and decomposition of surfactants. Separation filtration or centrifugation. Washing alcohol or water. Basic media needs through washing. Drying at room temperature is good.

6. Removal of template.
Removal of template will give rise to mesoporosity
Different ways by which template can be removed

Calcination
Slow heating rate. N2 -1 hr O2- 4-6 hr 2 C/min O2-1 C/min No surfactant recover low Surface silanol groups Not good for low thermal stable materials P-123 -550 C CTAB -350 C

Light irradiation Solvent Extraction

Solvent ethanol /THF small HCl is added Surfactant can be reused

Microwave Ultraviolet rays O3 and O

p6mm SBA-15 MCM-48 Ia3d, Pm3n

SBA-1 and 6

Fd3m Im3m SBA-16 FDU-2 Fm3m. KIT-5

Proposed mechanisms for synthesis mesoporous materials 1. Silicate rod assembly

2 or 3 monolayer's of silicates species first deposits on isolated surfactant miceller rods

2. Cooperative self assembly

Low concentration Surfactant

3. True liquid crystal templating route

High concentration Surfactant

Complete synthesis summary

7. Characterization of mesoporous materials

1. Low angel XRD 0.5 -5 -2theta - orederness / disorder.

2. N2 sorption measurements BJH method Surface area/pore diameter /pore volume

3. TEM images Order ,Morphohology , Wall thickness

Applications

Application Chemical Catalysis

1. Mesoporous Materials as catalyst
Al-MCM-41 ,B-MCM-41, Sn-SBA-15 - Acidic K- AlMCM-41 , Cs-AlMCM-41 -basic TiMCM-41 ,V-MCM-41 -Redox

2.Mesoporous Materials as catalyst support

Noble metal supported catalyst supports Au-McM-41 , Pt- CMK-3 Metal oxide supported catalysis Fe2O3- MCM-41 ,RuO2-SBA-15 Metal complex supported catalysts Mn-Salen SBA-15

3. Application in environmental catalysis

Immobilization of enzyme on Mesoporous Materials as catalysts

Enzymes are excellent biocatalysts with high selectivity and efficiency in environment field, chemical and pharmaceutical industries are limited by their poor stability and chemical sensitivity

4. Good adsorbents

5.Applications in Biomedical field

1) Sustained Drug Release System

Virtually any drug within a size range compatible with the size of the mesochannels has potential to be encapsulated and further deliver intracellularly.

M. Vallet-Regi, et al. A New Property of MCM-41: Drug Delivery System, Chem. Mater. 2001, 13, 308-311.

2. Mesoporous Materials for Bone Tissue Engineering

Mesoporous Bioactive scaffolds

Scaffolds are needed that can act as temporary templates for bone regeneration and actively stimulate vascularized bone growth so that bone grafting is no longer necessary. Bioactive glass is an ideal material because it rapidly bonds to bone and degrades over time, releasing soluble silica and calcium ions that are thought to stimulate osteoprogenitor cells.

1 Day

3 Day

7 Day

6.Mesoporous Polymers