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Silica and Aluminosilicate-based Nanostructures and Metal-Organic Framework

Dr Montree Sawangphruk (DPhil) Chemical Engineering, Kasetsart University, Room #1248, email:fengmrs@ku.ac.th

Porous Materials
Zeolites MCMs (silica) Bio-foams

2 nm

50 nm

Microporous

Mesoporous

Macroporous

Molecule

Protein

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Silicon Dioxide or Silica

Silicon dioxide is the main component of the crust of the earth. Combined with the oxides of magnesium, aluminum, calcium, and iron, it forms the silicate minerals in our rocks and soil.

Functional Groups of a Silica Particle

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Mesoporous Silica

Mesoporous silica is a form of silica and a recent development in nanotechnology. The most common types of mesoporous nanoparticles are MCM-41 and SBA-15, 16. Research continues on the particles, which have applications in catalysis, drug delivery and imaging.

Synthesis of Mesoporous Silica (SBA-16)

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Santa Barbara Amorphous (SBA) type material SBA-16

Mobil Composition of Matter (MCM)

Mobil Composition of Matter (MCM) is the initial name given for a series of mesoporous materials that were first synthesized by Mobil's researchers in 1992. MCM-41 (Mobil Composition of Matter No. 41) and MCM-48 (Mobil Composition of Matter No. 48) are two of the most popular mesoporous molecular sieves that are keenly studied by researchers. The most striking fact about the MCM-41 and MCM-48 is that, although composed of amorphous silica wall, they possess long range ordered framework with uniform mesopores. These materials also possess large surface area, which can up to more than 1000 m2g-1. Moreover, the pore diameter of these materials can be nicely controlled within mesoporous range between 1.5 to 20 nm by adjusting the synthesis conditions and/or by employing surfactants with different chain lengths in their preparation.

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MCM-41 (Mobile Crystalline Material-41)

hexagonal pore arrangement

Applications of MCM

MCM-41 and MCM-48 have been applied as

catalysts for various chemical reactions a support for drug delivery system adsorbent in waste water treatment etc

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An MCM-41 type mesoporous silica nanospherebased (MSN) controlled-release delivery system

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Carbon Nanotube Synthesis Using Mesoporous Silica Templates

What are zeolites?

Natural or synthetic crystalline, microporous, aluminosilicate materials with well-defined structures and unique characteristics

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Zeolite types

Natural zeolites form where volcanic rocks and ash layers react with alkaline groundwater.

Synthetic zeolites are created through a slow crystallization process using a combination of silica and alumina and using a foundation of alkali and organic templates.

Synthetic Zeolite

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Porous Materials
Zeolites MCMs Bio-foams

2 nm

50 nm

Microporous

Mesoporous

Macroporous

Molecule

Protein

Structure

SiO44- and AlO45- tetrahedra linked in several ways, resulting in over 130 different 3D framework structures

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Structure

The presence of Al in the framework induces a negative charge that is balanced by an extraframework cation.

Classification

Depending on the pores dimension and on the framework structure, zeolites can be A, X, Y or L type

Zeolites A
10.1007/s00897990300a, 1999 Springer-Verlag New York, Inc.

Zeolite Y

A. H. Roy, R. R. Broudy, S. M. Auerbach and W. J. Vining, The Chemical Educator, Vol. 4, No. 3, S1430-4171(99)03300-2,

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Schematic structure of natural zeolite TETRAHEDRON

The cells: POLYHEDRONS inside of which there are voids of different sizes dependent on the zeolite type A- 0.4 nm i type X- 0.9 nm

sodalite

faujasite

The Faujasite Zeolite

O
Zeolite are aluminosilicates composed of [SiO4 For each Al, a negative charge is created. The negative charge is compensated by cation. ]4 and [AlO4 ]4 tetrahedra.

O Al O O

O Si O M+ O

Cations occupy different sites. Cations are exchangeable. The zeolite has cages. 2 types of Faujasite, X and Y. Si/Al = 1.2 (NaX), 2.4 (NaY). Salient chemical properties: NaY unreactive, no supercage Na+ Basicity of supercage O atoms Cations attract anions formed

Sodalite cage (0.67 nm) Supercage (1.3 nm)

Faujasite structure
4738 (2005)]

[J. Phys. Chem. B. 109,

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Classification

Zeolite A is a small-pore zeolite in which the Si:Al ratio is 1 and the cages are linked octahedrically. The pore diameter varies from about 3 to 5 .

Classification

Zeolites X and Y are large-pore zeolites (6-8 ) containing various Si:Al ratios and tetrahedrically linked cages

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Zeolites
Framework Structure

Pores of Zeolite Y 7.413

Crystalline, well-defined nano-pore structure Charged framework Spatial arrangement Extreme Thermal & Chemical Stability

Classification

Zeolite L - the crystals are very flat cylinders of "hockeypuck" or "coin" shape Linear channels in which one-dimensional diffusion takes place Hexagonal crystal system

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Introduction- Registered Zeolites

Character of Zeolite Elimination Reaction

(i) Titration using NaOH: Zeolite acidity increased dramatically after adsorption of 2chlorobutane.

a 1436 1492
1500 1300 Wavenumber (cm )
-1

(ii) IR assignments 1436 cm-1: Lewis (PyNa+) 1548 cm-1: Bronsted(PyH+) 1492 cm-1: superposition of 1436 cm-1 and 1548 cm-1

1548

1700 Elimination No HCl gas produced pointing to acid zeolite (HX).

Al O Si NaX zeolite Na Al

1100

900

+ RCHXCH3

O Si HX zeolite

+ RCH

CH2

Na+X-

Transmittance

b c

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Zeolite Entrapment
Ion Exchange Encapsulation

Size Discrimination

Properties

Ion-exchange

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Properties

Molecular Sieve Effect

Properties

Acidity

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Zeolite Used as Catalyst

Thermodynamics says NOTHING about the rate of a reaction. Thermodynamics : Will a reaction occur ? Kinetics : If so, how fast ?

Zeolite Used as Catalyst

Reaction path for conversion of A + B into AB

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Activation Energy
Activation Energy : The energy required to overcome the reaction barrier. Usually given a symbol Ea or G
The Activation Energy (Ea) determines how fast a reaction occurs, the higher Activation barrier, the slower the reaction rate. The lower the Activation barrier, the faster the reaction

Activation Energy
Catalyst lowers the activation energy for both forward and reverse reactions.

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Activation Energy

This means , the catalyst changes the reaction path by lowering its activation energy and consequently the catalyst increases the rate of reaction.

Zeolite membranes Recent developments and progress (see Chapter 4)

Development of articles in open literature with (zeolite* OR molecular sieve) AND (membrane* OR coating OR film).

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Scientific publications on membrane reactors and zeolite membrane reactors, respectively (Scifinder search)

Zeolites in the petrochemical industry

http://omusinternational.com/db3/00225/omusinternational.com/_uimages/nightrefinery.JPG

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Introduction

Zeolites contain void space that can host cations, water, or other molecules Molecular sieves

Do not allow molecules larger than 8 to 10 nm to enter lattice

Zeolites:

40 known natural zeolites > 140 synthetic zeolites

Introduction Major Applications

Adsorption

Drying, purification, and separation Powerful desiccants- able to hold 25% of their weight in water Remove volatile organic compound (VOC) from air streams & separate gases Shape-selective catalyst- on the basis of molecular diameter Acid catalysts used in the petrochemical industry Detergent formulas- replace phosphates as water softening agents Exchange Na in zeolite for Ca or Mg in water

Catalysis

Ion Exchange

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Introduction- Environment

Contribute to a cleaner, safer environment In powder detergents, zeolites replaced harmful phosphate builders Solid acids, zeolites reduce the need for corrosive liquid acids Redox catalysts and sorbents

Remove atmospheric pollutants, such as engine exhaust gases and ozone-depleting CFCs.

Picture: http://www.cerpa.appstate.edu/images/environment.jpg

Zeolites can also be used to separate harmful organics from water

Heavy metals and NH4+

Introduction - Environment

Zeolites can be regenerated by

Heating to remove adsorbed materials Ion exchanging with sodium to remove cations Pressure swing to remove adsorbed gases.
http://www.ecofriendlymag.com/wp-content/plugins/wp-o-matic/cache/3ad14_usimport-radioactive-waste.jpg

University of New York at Stony Brook

Developed a zeolite to trap radioactive strontium Heating the material makes the holes clamp shut, sealing the radioactive waste inside
http://jdlong.files.wordpress.com/2009/05/nuclear-plant.jpg

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Introduction- Applications

Introduction Membranes

Applications

Desalination

~90% salt rejection Replaces azeotropic distillation A method of CO2 sequestration

http://cdn.physorg.com/newman/gfx/news/hires/energyeffici.jpg

Ethanol Dehydration

Separate CO2 from air

H2 Separation

http://www.freepatentsonline.com/20040144712-0-large.jpg

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Introduction - Membranes

Research Efforts

Decrease membrane thickness

Increase flux

Determine sustainability/durability Analyze replacement time and cost for industrial applications

Potential to replace current energy consuming separation devices

Distillation Column
http://bioage.typepad.com/photos/uncategorized/2007/07/11/mitsui_2.png

Motivation

Reduce Operating Costs

Lower reaction temperature and pressure Superior control of reaction selectivity

Reduces feed costs less waste and treatment streams

Challenges

Energy efficiency CO2 emissions Product/Process specifications- heavier & dirtier crudes Changing feedstocks (biofuel, biomass, unconventional oils)

http://gozonews.com/wp-content/uploads/2008/05/biofuels.jpg

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Motivation- Global Market

http://www.theage.com.au/ffximage/2005/03/24/oil_generic_wideweb__430x317.jpg

Metal-Organic Framework (MOF)

Metal-organic frameworks (MOFs) are materials in which metal to-organic ligand interactions yield porous coordination networks with record-setting surface areas surpassing activated carbons and zeolites. The applications of MOFs include storage and separations of gases, sensors, catalysis and others.

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MOF

High Surface Area (MOF-14)

a surface area of 4526 m2/g

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Synthesis of MOFs

MOFs and zeolites alike are produced almost exclusively by hydrothermal or solvothermal techniques, where crystals are slowly grown from a hot solution of metal precursor, such as metal nitrates, and bridging ligands.

Zeolite synthesis often makes use of a variety of templates, or structure-directing compounds, and a few examples of templating, particularly by organic anions, are seen in the MOF literature as well.

A particular templating approach that is useful for MOFs intended for gas storage is the use of metal-binding solvents such as N,N-diethylformamide and water.

In these cases, metal sites are exposed when the solvent is fully evacuated, allowing hydrogen to bind at these sites.

MOFs for hydrogen storage

Hydrogen has the potential to be an attractive option because it has a high energy content (120 MJ/kg compared to 44 MJ/kg for gasoline), produces clean exhaust product (water vapour without CO2 or NOx), and can be derived from a variety of primary energy sources. However, the specific energy of uncompressed hydrogen gas is very low, and considerable attention must be given to denser storage methods if hydrogen is to emerge as a serious option for energy storage.

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MOFs for hydrogen storage

Metal Organic Frameworks (MOFs) attract attention as materials for adsorptive hydrogen storage because of their exceptionally high specific surface areas and chemically-tunable structures. MOFs can be thought of as a three-dimensional grid in which the vertices are metal ions or clusters of metal ions that are connected to each other by organic molecules called linkers. Hydrogen molecules are stored in a MOF by adsorbing to its surface. Compared to an empty gas cylinder, a MOF-filled gas cylinder can store more gas because of adsorption that takes place on the surface of MOFs.

MOFs for hydrogen storage

Furthermore, MOFs are free of dead-volume, so there is almost no loss of storage capacity as a result of spaceblocking by non-accessible volume. Also, MOFs have a fully reversible uptake-and-release behavior since the storage mechanism is based primarily on physisorption, there are no large activation barriers to be overcome when liberating the adsorbed hydrogen. The storage capacity of a MOF is limited by the liquidphase density of hydrogen because the benefits provided by MOFs can be realized only if the hydrogen is in its gaseous state.

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Metal organic frameworks for Hydrogen Storage

1 Hydrogen tank 2 Radiator 3 Stack Module (Hydrogen Fuel Cell) 4 System Module (Hydrogen Fuel Cell) 5 Power Distribution Unit 6 LiPoly Battery to start the fuel cell system 7 Total Rescue System

Why store Hydrogen?

We need

Clean

energy.

Hydrogen if combined with Oxygen releases energy (an energy carrier). Water is the byproduct (Completely harmless, clean). This reaction can replace another popular but polluting source of energy-gasoline. Hydrogen generated from diverse domestic resources can reduce demand for oil by more than 11 million barrels per day by the year 2040. For this reaction we need a source of hydrogen. (Attaching a hydrogen tank with the mobile vehicle.)

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How much Hydrogen?

DOE Targets (for 2010) : Future hydrogen cars should have :

Hydrogen storage tank carrying approximately 5 kg of H2 (a range of 300 miles (480 km)). Maximum allowed pressure of 100 bar for a storage device.

Capacity targets for a fueling system (including the tank and it's accessories) set at 6 wt% and 45g/l of unstable H2.
System should show not decay for 1000 consecutive fueling cycles and should allow filling to full capacity in 3 minutes. for 2015 - 9 wt%, 60g/l, 1500 cycles. and 2.5 min.

Storing Hydrogen (Conventional methods)

Compressed gas method requires huge amount of initial pressures and safety issues arise.

Cryogenic storage requires large amount of energy input for initial condensation of hydrogen.
In complex hydrides (eg. Mg2NiH4 ) desorption usually occurs at higher temperatures than targeted conditions. Other drawbacks are high cost, susceptibility to impurities and low reversible gravimetric capacity. One way to improve the kinetics of storage is to maintain the Molecular identity of H2 during the process.

Physisorbtion of molecular hydrogen in to highly porous materials.

Metal Organic Frameworks

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Storing Hydrogen in MOFs

MOF-177

MIL-53

MOFs have large apparent surface areas.

The dinitrogen isotherm measured for MOF-177 at 77 K exhibits the highest uptake of N2 for any material to date, and gives rise to a monolayer-equivalent surface area of 4500 m2 /g. This framework has cavities in the range of 11-12 A0.
(C: black, N : green,O : red, Zn : blue polyhedra, M: green octahedra).

IRMOF-8

Zn2-(bdc)2(dabco)

O. M.Yaghi and J. L. C. Rowsell, Angew. Chem. Int. Ed. 2005, 44, 4670 4679

Storing Hydrogen in MOFs

Kinetic diameter of H2 molecule = 2.98 A0

For an ideal adsorbate: Pore size should be same as its own diameter. Walls of the pore should be made of light elements (should be as thin as possible) Walls should be highly segmented (achieved in MOFs by reticular synthesis). Smaller pores in MOFs are needed to surpass the storage density of liquid hydrogen.
MOF-5: Pore diameter 15.2 A0 (Yellow sphere) An smaller pore analogue of MOF-5 can be stabilized by using a rigid linear dicarboxylate

1.

2.

C: black, H : white, O : red Zn : blue tetrahedra

3.

4.

A compromise between gravimetric and volumetric density of storage must be found out.

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Storing Hydrogen in MOFs

To bind the hydrogen in a better way, another adsorbate surface can be inserted inside the pore (approach is called impregnation) These surfaces also reduce the pore diameter. In this case also a compromise between gravimetric and volumetric capacity is reached.

MOF-177 molecule with C60 molecule inside its pore.

O. M.Yaghi and J. L. C. Rowsell, Angew. Chem. Int. Ed. 2005, 44, 4670 4679

Storing Hydrogen in MOFs

Storing hydrogen by framework catenation:

Repeat unit

Interpenetration

Interweaving

Modified Interweaving

Catenation of two identical frameworks can be used to restrict the dimensions of the pore considerably by interpenetration.

Though interpenetrated framework is more capacitive than interwoven but it has comparatively less stability.
O. M.Yaghi and J. L. C. Rowsell, Angew. Chem. Int. Ed. 2005, 44, 4670 4679

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Storing Hydrogen in MOFs

Using coordinatively unsaturated metal sites: An unsaturated metal site can attach to H2 directly (a substantial increase in H2 binding affinity) Some strategies for synthesizing such materials are: 1. Metal building units with coordinatevely unsaturated centers through solvent removal. 2. Incorporating Coordinatively Unsaturated Metal Centers within the Organic Linkers 3. Impregnation of Metal-Organic Frameworks with Metal Ions

Unsaturated metal centre

J. R. Long and M. Dinca Angew. Chem. Int. Ed. 2008, 47, 6766 6779 O. M.Yaghi and J. L. C. Rowsell, Angew. Chem. Int. Ed. 2005, 44, 4670 4679

Storing Hydrogen in MOFs

Other methods

Modifying organic linkers to increase the H2 affinity Introducing additional adsorptive sites on the SBUs. Using light metals to reduce the framework density.

J. R. Long and M. Dinca Angew. Chem. Int. Ed. 2008, 47, 6766 6779 O. M.Yaghi and J. L. C. Rowsell, Angew. Chem. Int. Ed. 2005, 44, 4670 4679

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Homework

A 2-page report, which can show how to synthesise, how to characterise, and how important it is, on one of porous materials below;

a. Mesoporous materials b. Zeolites c. Metal-organic framework (MOF)

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