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Identifier

000398688

Title

Development of novel coordination polymers

Alternative Title

Ανάπτυξη καινοτόμων πολυμερών συναρμογής

Author

Σπανόπουλος, Ιωάννης Δ.

Thesis advisor

Τρικαλίτης. Παντελής

Reviewer

Φρουδάκης, Γεώργιος
Μήλιος, Κωνσταντίνος
Βασιλικογιαννάκης, Γεώργιος
Στρατάκης, Εμμανουήλ
Στεριώτης, Θεόδωρος
Χαραλαμποπούλου, Γεωργία

Abstract

Metal Organic Frameworks (MOFs) is a novel class of crystalline hybrid nanomaterials comprised of both an organic and an inorganic part. This hybrid nature of MOFs can give rise to a plethora of unique properties and therefore MOFs are considered important candidates for numerous applications, including gas storage and gas separation. The objective of this thesis was the development of novel porous MOFs that would exhibit enhanced gas sorption properties and could be used in important industrial applications. These applications include CO₂, CH₄ and H₂ storage as well as CO₂/CH₄, CO₂/N₂ and Xe/Kr separation. This could be achieved by the use of organic ligands functionalized with polar, acidic or basic side groups that can enhance the interaction of the framework with gas molecules through dipole-induced dipole, or acid-base interactions. For that purpose more than 77 new tailor made organic linkers were exploited for the synthesis of more than 90 novel MOFs. So far successful activation, and evaluation of the gas sorption properties, was possible for less than the half of these materials. Nonetheless important structural characteristics and improved gas sorption properties were observed for most of them. In particular, utilization of expanded rectangular linkers resulted in the synthesis of new tbo-MOFs exhibiting a very high methane uptake at ambient temperature and high pressures. These materials are among the five best MOF candidates for CH₄ storage in terms of total gravimetric uptake and gravimetric working capacity. Another tailor made organic linker bearing PdCl₂ entities was used for the synthesis of a material exhibiting a notable CO₂ uptake at 298 K and 1 bar. This material is among the ten best MOF candidates for CO₂ storage under mild conditions. An NbO type of MOF based on an organic linker functionalized with sulfonic groups (-SO₃H) was synthesized, that exhibits a very high selectivity for the separation of Xe over Kr at RT. This value is among the five highest reported for MOFs, rendering this material a promising candidate for the separation of Xe over Kr. Using an elongated amide functionalized organic linker, it was possible to synthesize a UiO type of MOF with the largest unit cell and pore volume reported to date. Similarly, the use of a methoxy functionalized organic linker for the synthesis of a UiO-67 analogue revealed an impressive isosteric heat of methane adsorption with a value of 24.3 kJ mol^-1, the second highest reported in the family of MOFs. The important results of the present thesis provide new directions towards the development of functional MOFs that could find real applications in the field of gas storage/separation.

Language

English

Subject

Gas separation

Gas sorption

Gas storage

Heat of adsortpion

MOFs

Porosity

Selectivity

Surface area

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