Metal phosphates [Elektronische Ressource] : from syntheses and structures to applications in sorption, catalysis and teeth erosion protection / presented by Khalid Hamad Abu-Shandi

Khalid Hamad Abu-Shandi

Sujets

• Gesundheit

Informations

• Publié par: albert-ludwigs-universitat_freiburg
• Publié le: 01 janvier 2003
• Nombre de lectures: 28
• Langue: English
• Poids de l'ouvrage: 7 Mo

Extrait

Metal phosphates: From syntheses and structures to applications in
sorption, catalysis and teeth erosion protection.






Thesis in partial fulfilment of the requirements of the
Doctoral Degree in
Chemistry


Faculty of Chemistry and Pharmacy
Albert-Ludwigs-University
Freiburg im Breisgau
Germany



Presented by
Khalid Hamad Abu-Shandi
From Irbid-Jordan



15-May-2003


































Vorsitzender des Promotionsausschusses: Prof. Dr. G. E. Schulz
1. Referent: Prof. Dr. Ch. Janiak
2. H. Vahrenkamp
Tag der Verkündigung des Prüfungsergebnisses: 15-5-2003









































iAcknowledgement
This thesis was prepared in the time period September-2000 to May-2003
First and foremost I should offer my thanks, obedience and gratitude to our God the great from
whom I receive guide and help. I wish to extend my thanks and appreciation to my supervisor:
Professor Dr. Christoph Janiak
For guidance, help, continuous support and valuable discussions which made it possible to
successfully complete this work.
I would like to thank the members of my supervisory committee Professor Dr. Heinrich
Vahrenkamp and Professor Dr. Willi Bannwarth.
Special thanks to my dear wife, the woman who I love, Rana Al-Zammar for her love,
encouragement and support as well as her patience to be separated from me for three years.
Special thanks to my lovely children Hana and Noor for their love and patience to be separated
from me for three years.
Special thanks to my parents who give so much and ask for so little and their continuous praying
to God to bless me and take my hand.
Special thanks to my brothers and sisters for their encouragement and love.
I extend my thanks to my colleges in the group Paul-Gerhard Lassahn, Thomas Dorn, Dr. Vasile
Lozan, Emma Craven, Dr. Cungen Zhang and Simon Blust. I can’t forget to thank Frau Dettinger
for her help in ordering chemicals as well as her kind behaviour.
Special thanks to Franziska Emmerling for her help in XRPD and valuable discussions.
Thanks to Dr. Biao Wu for his help in the crystal structure refinement.
Thanks to Emma Craven for her help in the potentiometric titrations.
Special thanks to my friend Rafat Ahmed, a PhD student in the Fritz-Haber-Institut (MPG),
Berlin-Germany, for valuable discussions about catalysis mechanisms.
Special thanks to my cousin Anwer Abu-Amer, a PhD student in Duisburg University, for valuable
discussions about fluoride NMR.
Special thanks to the people who helped in e collection of the X-ray data sets: Dr. Werner Deck,
Horst Brombacher, Paul-Gerhard Lassahn and Dr. Bert Kersting.
Thanks to the people who did the TGA/DTA measurements Mrs Schuler and Mr K. –P. Bickel.
Thanks to Mr. K. –P. Bickel for his help with the electronic repairs of the GC/MS system.
Thanks to Dr. Heiner Winkler in Lübeck University for carrying out Mössbauer studies.





iiList of contents
Page
Abstract………………………………………………………………………………………vi
Chapter 1 - Introduction…………………………………….……………….........................1
1.1 Crystal engineering and coordination polymers………………………….......................... 1
1.2 What are "coordination polymers"?..................................................................................... 1
1.3 The ligands in coordination polymers……………………………………………………...3
1.4 Porous coordination polymers, porosity, zeolitic behavior ………………………...……...4
1.5 Catalysis……………………………………………………………………………………6
1.6 Orthophosphoric acid and phosphates……………………………………......................... 6
1.7 Potentiometric titration........................................................................................................ 7
1.8 Metal-phosphate microporous coordination polymers………………………………….... 8
1.9 Hydrothermal reactions…………………………………………………............................9
1.10 Metal coordination with 4,4'-bipyridine and piperazine………………..……….............10
1.11 Hydrogen-bonded metal ligand networks……………………………………………….11
1.12 Aluminum phosphate, AlPO -n microporous frameworks……………….......................12 4
1.13 Gallium phosphate microporous frameworks...…………………………...................... 14
1.14 Iron phosphate microporous frameworks…………………………................................ 15
1.15 Metal-phosphate microporous frameworks with metals other than Al, Ga, and Fe….... 17
1.16 Crystallization problems.................................................................................................. 17
1.17 Framework stability of porous inorganic structures upon template extraction and
calcination…………………………………………………………...............................18
1.18 Methods employed to confirm the porosity of microporous materials............................ 18
1.18.1 X-ray powder diffraction……………………………......................................... 18
1.18.2 Gas chromatography……………………………................................................ 19
1.18.3 Infrared spectroscopy……………………………...............................................19
1.18.4 Nuclear magnetic resonance spectroscopy…………………….......................... 20
1.18.5 Gravimetric analyses ……………………………...............................................20
1.19 Purpose of the work..........................................................................................................20
Chapter 2 - Experimental part………………......................................................................22
2.1 Methods and instruments.................................................................................................22
2.1.1 Potentiometric titration...........................................................................................23
2.1.2 Autoclave for hydrothermal syntheses...................................................................25
2.1.3 Oven for calcination ..............................................................................................26
2.1.4 Gas chromatography...............................................................................................26
iii2.1.5 Autoclave used in catalytic reactions.....................................................................27
2.1.6 Mössbauer spectroscopy…………………………………………………………28
2.2 Synthesis of molecular (metal) phosphates…................................................................29
2.2.1 (C H N )(H PO ) ·2H O (1) .............................................................................29 10 12 2 2 4 2 2
2.2.2 (C H N )(HPO )·H O (2)…………………………………………...…………..29 4 12 2 4 2
2.2.3 [Co(H O) ](C H N )(HPO ) (3) and Co (PO ) ·8H O (4)…............................ 29 2 6 4 12 2 4 2 3 4 2 2
2.2.4 [Ni(H O) ](C H N )(HPO ) (5)..........................................................................30 2 6 4 12 2 4 2
2.2.5 (C H N )(HPO )·2H O (6)...................................................................................31 5 14 2 4 2
2.2.6 [Fe(H O) ](C H N )(HPO ) (7)......................................................................... 31 2 6 4 12 2 4 2
2.2.7 [Cu(4,4'-bipy) (H PO ) (H O) ] (8).......................................................................31 2 2 4 2 2 2
2.3 Syntheses of iron phosphate coordination polymers.....................................................32
2.3.1 {[Fe(H PO ) (4,4'-bipy)(H O) ]·(OH)(4,4'-bipy)} (9).........................................32 2 4 2 2 2 n
2.3.2 {[Fe(NO ) (4,4'-bipy)(H O) ]·(OH)(H O)} (10)..................................................32 3 2 2 2 2 n
2.4 Syntheses of metal phosphate (open) frameworks.........................................................33
2.4.1 {[(H N(CH ) NH ) ][Ga (PO ) (HPO ) (OH) F ]·6H O} (11)…….……….. 33 3 2 6 3 4 16 4 14 4 2 2 7 2 n
2.4.2 {[C H N ][Ga (PO ) (HPO )](H2O)} (12).........................................................34 4 12 2 3 4 3 4 n
2.4.3 {[NH ][Fe (PO ) (OH)H O)]·H O} (13)……......................................................34 4 2 4 2 2 2 n
2.4.4 {[C H N ] [Fe (PO )(H PO ) ]·H O} (14)…...............................................35 4 11.2 2 1.5 2 4 0.6 4 2 2 n
2.4.5 {[Fe (PO ) (H PO ) ]} (15)……….…..........................................................…35 7 4 2 0.5 4 4 n
2.4.6 {[C H N ][Fe (PO ) (HPO )](H O)} (16)...........................................................36 4 12 2 3 4 3 4 2 n
2.5 Syntheses of biphosphinic acids and their iron derivatives..........................................36
2.5.1 Na[H N(CH CH C(OH)(PO H )(PO H)]·H O (17)..............................................36 2 2 2 3 2 3 2
2.5.2 {Fe(H NCH CH H) ) } (18)..............................................................37 3 2 2 3 2 2 n
2.5.3 Na[H N(CH ) C(OH)(PO H)(PO H )] (19)...........................................................37 2 2 3 3 3 2
2.5.4 Na [H N(CH ) H) ]·2H O