Content tutorial

Ana-Marija Bartolincic(AMBLab)Porous inorganic materialsIntroduction to chemistry of materials Aluminasilicates and structurePhosphatesChalcogenid structure,nitrides and oxidesSynthesis method and developmentConclusionReferences

Content tutorialSignificant development in the last 40 years in the field of chemistry of materialsNatural 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 to chemistry of 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 Introduction porous materials 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

Aluminosilicates

Sodalithe zeolitheSmall Si ratio makes them unstable on high tempSensitive to pH Size of pores makes them suitable for catalysis selectivityReduction-oxidation properties Less stable then `condensed` forms Used as :FiltersCatalysatorsCompositsThin films

Aluminosilicates Aluminosilicates

(Ca,K2,Na2)2[Al2Si4O12]212H2O (eng. Chabasite)Main group phosphatesOriginated from aluminosilicatesStructurally similar to aluminosilicates Named :aluminophosphates and galium phosphatesSeven allotropic modification of AlPO4Mostly combined tetrahedral structures connected with corners or peaksMineralogical shape:trigonal bypiramid and octahedral40 structural types knownMostly odd and even number of tethraedral forms per ring structure Pores size to 13 Aluminophosphates

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

AlPO4-21 Properties :Stability depends over pH from which they came Sometimes unstable Insertion metal cations into grid makes it polarized

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

Galium phosphates

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

CloveriteOctahedral coordination around IndiumNeeded templates for synthesis Amines and heterocyclic structures with nitrogen Indium phosphates

[In2(HPO4)4]2-Indium phosphates

AlPO4 x 2H2O (Variscite)Borium phosphateZinc phosphate Berillium phosphate Tin phosphateOther phosphates

[Sn4P3O10]-Molybdenum phosphate Vanadium Iron Cobalt(II)Zirconium Manganese(II)Titanium phosphates

Transition elements phosphates First to be synthesized very complicated synthesis Three classes of phosphates I.class-MoO6 are isolated with PO4 groupsII.class-endless MoO6/2 chains with different chain lenghtIII.class-structures have very small amount of MoO6 unitsShare the same tops/corners and surfaceExistance of MoP clusters can be find in some other structures Have unwanted properties Molybdenum phosphates Molybdenum phosphate

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

Spacial structure shematics AgMo5P8O33Vanadium 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 xH2OIron phosphates Very interesting as materials Made of clusters Structure very similar to galium phosphate Used for chemical reactions like catalysis

CacoxeniteChalcogen 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 CuCl42-Nitride 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 CpH dependend reactions Solvothermal reaction give better resultsTemplatic reactionsFlourid method and snythesis in present of complex compounds

TREN-GaPOULM-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.comwww.mindat.comDefinition of xerogel taken from :www.merriam-webster.com/dictionary/xerogelDefinition of aerogel taken from:whatis.techtarget.com