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Supramolecular templating agents and metal organic frameworks: control over crystal size and assembly.

Supramolecular templating agents and metal organic frameworks: control over crystal size and assembly.
Supramolecular templating agents and metal organic frameworks: control over crystal size and assembly.
Metal organic frameworks(MOFs) are an interesting class of microcrystalline materials constituted by metal ions or clusters connected by organic linkers characterised by their high porosity and tunable structures. Due to their chemical variability and numerous applications they have received great attention during the last few decades.

Recently also the control of their physical form or macroscopic structure, such as crystal size, morphology and the aggregation of the crystals into superstructures, have received more attention since it would further develop and enhance properties and applications of these materials. Indeed beside all the inherent properties derived from the chemical composition and microporosity of MOFs the higher level of order or the control over the dimensionality or shape of the particles should enrich their overall performance and open new fields of application, such as drug delivery or integration into electronic sensor devices.

In this context three prototypical MOFs were investigated, namely HKUST-­1, ZIF-­8 and ZIF-­61; at first an overview of the behavior of HKUST-­1 in presence of templating agents was performed, which involved the use of Pluronic-P123 (HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H, EO20PO70EO20, EO=ethylene oxide, PO=propylene oxide) and two carboxylic acids, namely octanoic acid and dodecanoic acid, on the synthesis of HKUST-­1. As a proof of concept, this chapter underlined the importance of the synthetic conditions and of the interactions between MOF precursors and templating agents in directing the macroscopic structure of the MOF Thereafter the directional self-­assembly properties of ZIF-­8 in aqueous media with the templating agents SPAN-­80 and/or dodecane for the formation of hollow capsule and colloidosomes was investigated, again in relation to optimize the synthetic conditions and understand the mechanism behind the hollow structure formation, which finally depended on the nature of the templating agent and the MOF precursors-­templating agent interactions. Furthermore the etching effect of imidazole on the hollow capsule, which led to flower-­like microcapsules was analyzed.

Furthermore the optimization of the synthesis of zni phase in aqueous media and the topological and morphological conversion from zni phase (ZIF-­61) to sod phase (SALEM-­2) promoted by the surfactant SPAN-­80 was studied. The role of SPAN-­80 was further investigated also in light of the variation of the composition of the two ZIFs and the thermodynamic of the system.

Finally the thesis was an attempt to rationalized the mechanism of MOF macroscopic structures formation, considering the structural features of the starting MOF, the synthetic conditions and the choice of the templating agents, envisioning a design a priori of the macroscopic structure of MOFs.
Lupica Spagnolo, Lucia
18ffdc3d-d91d-4d51-9b58-ec908286ba1e
Lupica Spagnolo, Lucia
18ffdc3d-d91d-4d51-9b58-ec908286ba1e
Bradshaw, Darren
7677b11e-1961-447e-b9ba-4847a74bd4dd

(2016) Supramolecular templating agents and metal organic frameworks: control over crystal size and assembly. University of Southampton, Faculty of Natural and Environmental Science, Doctoral Thesis, 232pp.

Record type: Thesis (Doctoral)

Abstract

Metal organic frameworks(MOFs) are an interesting class of microcrystalline materials constituted by metal ions or clusters connected by organic linkers characterised by their high porosity and tunable structures. Due to their chemical variability and numerous applications they have received great attention during the last few decades.

Recently also the control of their physical form or macroscopic structure, such as crystal size, morphology and the aggregation of the crystals into superstructures, have received more attention since it would further develop and enhance properties and applications of these materials. Indeed beside all the inherent properties derived from the chemical composition and microporosity of MOFs the higher level of order or the control over the dimensionality or shape of the particles should enrich their overall performance and open new fields of application, such as drug delivery or integration into electronic sensor devices.

In this context three prototypical MOFs were investigated, namely HKUST-­1, ZIF-­8 and ZIF-­61; at first an overview of the behavior of HKUST-­1 in presence of templating agents was performed, which involved the use of Pluronic-P123 (HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H, EO20PO70EO20, EO=ethylene oxide, PO=propylene oxide) and two carboxylic acids, namely octanoic acid and dodecanoic acid, on the synthesis of HKUST-­1. As a proof of concept, this chapter underlined the importance of the synthetic conditions and of the interactions between MOF precursors and templating agents in directing the macroscopic structure of the MOF Thereafter the directional self-­assembly properties of ZIF-­8 in aqueous media with the templating agents SPAN-­80 and/or dodecane for the formation of hollow capsule and colloidosomes was investigated, again in relation to optimize the synthetic conditions and understand the mechanism behind the hollow structure formation, which finally depended on the nature of the templating agent and the MOF precursors-­templating agent interactions. Furthermore the etching effect of imidazole on the hollow capsule, which led to flower-­like microcapsules was analyzed.

Furthermore the optimization of the synthesis of zni phase in aqueous media and the topological and morphological conversion from zni phase (ZIF-­61) to sod phase (SALEM-­2) promoted by the surfactant SPAN-­80 was studied. The role of SPAN-­80 was further investigated also in light of the variation of the composition of the two ZIFs and the thermodynamic of the system.

Finally the thesis was an attempt to rationalized the mechanism of MOF macroscopic structures formation, considering the structural features of the starting MOF, the synthetic conditions and the choice of the templating agents, envisioning a design a priori of the macroscopic structure of MOFs.

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Published date: July 2016
Organisations: University of Southampton, Chemistry

Identifiers

Local EPrints ID: 401110
URI: http://eprints.soton.ac.uk/id/eprint/401110
PURE UUID: 03c5dd98-142b-442f-a200-98ff3163795a
ORCID for Darren Bradshaw: ORCID iD orcid.org/0000-0001-5258-6224

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Date deposited: 26 Oct 2016 15:43
Last modified: 29 Jul 2019 04:01

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