* Porous inorganic

materials

Ana-Marija Bartolincic(AMBLab)

* Content tutorial
Introduction to chemistry of materials
Aluminasilicates and structure
Phosphates
Chalcogenid structure,nitrides and oxides
Synthesis method and development
Conclusion
References

* Introduction to

chemistry of materials

Significant development in the last 40 years in the

field of chemistry of materials
Natural materials have problem of sustaining
The new synthethic methods have been deployed
New MOF(metal organic frameworks),aerogels(aerogel
is a translucent, syntheticsolid-statesubstance with
extremely low density and excellent thermal
insulating properties) and xerogels(a solid formed from
a gel by drying with unhindered shrinkage)
Crystallinity

* Introduction porous
materials

The size of the ring and pores have been discussed

Coordination of metal centre around organic structure
2D and 3D structures have been found
Wide spread usage in the field of materials
Density issue depends on the size of pores

* Aluminosilicates
Zeolithe structure have been know since 19th century
Over 100 known structure types of natural zeolithes
The natural mine of zeolithe shown below

* Aluminosilicates
ZSM-5 structure

* Aluminosilicates
What is the structure ?-thetaedral

geometric shape

with common peaks/edges

Si/Al ration is different
Common pair of tetrahedral shapes per ring
Size of pores varies from 2,5 till 10

Sodalithe zeolithe

* Aluminosilicates
Small Si ratio makes them unstable on high temp
Sensitive to pH
Size of pores makes them suitable for catalysis
selectivity
Reduction-oxidation properties
Less stable then `condensed` forms
Used as :
Filters
Catalysators
Composits
Thin films

* Aluminosilicates

(Ca,K2,Na2)2[Al2Si4O12]212H2O

(eng. Chabasite)

* Main group phosphates

Originated from aluminosilicates
Structurally similar to aluminosilicates
Named :aluminophosphates and galium phosphates
Seven allotropic modification of AlPO4
Mostly combined tetrahedral structures connected
with corners or peaks
Mineralogical shape:trigonal bypiramid and octahedral
40 structural types known
Mostly odd and even number of tethraedral forms per
ring structure
Pores size to 13

* Aluminophosphates

NaAl3(PO4)2(OH)4-Brazilianite)
AlPO4-21

* Aluminophosphates
Properties :
Stability depends over pH from which they
came
Sometimes unstable
Insertion metal cations into grid makes it
polarized

* Galium phosphates
Last 30 years exploring others metals for replacing
aluminium
Mostly isotructural with alumophosphates
Gained with new synthethic methods

KFe2(PO4)2(OH) x 2(H2O) (Leucophosphite)

* Galium phosphates

Cloverite

* Indium phosphates
Octahedral coordination around Indium
Needed templates for synthesis
Amines and heterocyclic structures with nitrogen

[In2(HPO4)4]2-

* Indium phosphates

AlPO4 x 2H2O (Variscite)

* Other phosphates
Borium phosphate
Zinc phosphate
Berillium phosphate
Tin phosphate

[Sn4P3O10]-

* Transition elements
phosphates

Molybdenum phosphate
Vanadium
Iron
Cobalt(II)
Zirconium
Manganese(II)
Titanium phosphates

* Molybdenum
phosphates

First to be synthesized very complicated synthesis

Three classes of phosphates
I.class-MoO6 are isolated with PO4 groups
II.class-endless MoO6/2 chains with different chain lenght
III.class-structures have very small amount of MoO6 units
Share the same tops/corners and surface
Existance of MoP clusters can be find in some other
structures
Have unwanted properties

* Molybdenum
phosphate

KFe4(AsO4)3(OH)4 x (6-7)H2O (Pharmacosiderite)

* Molybdenum
phosphate

Spacial structure
shematics AgMo5P8O33

* Vanadium

phosphates

Started from vanadyl pyrophosphate

Very wide spectrum of compounds and properties
Nets of mixed oxidation states
Very large pores

Cs3[V5O9(PO4)2] x xH2O

* Iron phosphates
Very interesting as materials
Made of clusters
Structure very similar to galium phosphate
Used for chemical reactions like catalysis

Cacoxenite

* Chalcogen

phosphates

Sulphides and selenide phosphate compounds

Only very small amount of metal atoms in structure
Mixed sulphides

* Halide and nitride

phosphates

Synthesised in hard conditions

Chlorides are used as polymers -ZnCl42- i CuCl42Nitride complexes of silicium and phosphore

* Binary oxides
Very know representative is manganese dioxide
Small holes in structure
Defects in structure are made by cationic vacancies

MnO2 (Pyrolusite)

* Synthethic
methods

Hydromthermal
100 C
pH dependend reactions
Solvothermal reaction give better results
Templatic reactions
Flourid method and snythesis in present of complex
compounds

TREN-GaPO
ULM-15

* Flouride method
Presents fo F ions
Insertion of flouride into structure without breaking
structure integrity
Increasing the metal center coordination number

* Conclusion
Wide spread class of compounds
Not complicated synthesis
Wide usage
Novel synthesis of MOF and ZIF structures

* References
A. K. Cheetham, G. Frey, T. Loiseau,
Angew. Chem. Int. Ed. 38 (1999.) 3268.
www.wikipedia.com,
www.webmineral.com
www.mindat.com
Definition of xerogel taken from :
www.merriam-webster.com/dictionary/
xerogel
Definition of aerogel taken from:
whatis.techtarget.com