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Construction Of Metal-Organic Framework Hollow Nanostructures Modulated By Polyoxometalate

Posted on:2018-07-03Degree:DoctorType:Dissertation
Country:ChinaCandidate:X B XuFull Text:PDF
GTID:1361330566488019Subject:Chemistry
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Metal–organic frameworks(MOFs)are a class of porous crystalline materials that constructed by metal ions/clusters and organic ligands.As one of the most attractive porous materials known today,MOFs are widely applied in many important fields,such as gas adsorption and storage.The miniaturization of MOF crystals into nanoscale always brings enhanced or novel properties and fulfils specific needs.Particularly,construction of MOF hollow nanostructures has gradually drawn intensive attention because of their outstanding properties such as low density,enlarged specific area and reduced length for both mass and charge transport.However,the synthesis of MOF hollow nanostructures still remains a great challenge.In this dissertation,we design a unique synthetic approach modulated by polyoxometalate anions(POM,a class of early transition metal oxygen anion clusters).Firstly,various uniform morphologies of Cu3(BTC)2 nanocrystals are obtained by adopting Keggin-type POM as modulator.Furthermore,we rationally synthesize POM clusters incorporated Fe/Co-BTC hierarchical nanotubes.Due to the structural and compositional advantages,these nanotubes show excellent catalytic performance in the detoxification of sulfur compounds with O2 and remarkable cycling stability as anode materials for lithium ion batteries.It’s of great significance to construct molybdenum carbide hollow nanostructure,which is widely studied as high-performance hydrogen evolution reaction(HER)electrocatalyst,but still remains highly challenging.Therefore,we demonstrate a simple method.Initially,Mo-based POM anions incorporated Ni-MOF hollow structure is synthetized.After annealing process,robust molybdenum carbide-based hollow structure is prepared.Due to the unique composition and configuration,these hollow structures exhibit remarkable HER properties and stabilities.Considering the general of the interactions and diversity of compositions and structures of POMs and MOFs,it is possible to prepare diverse MOF-based nanomaterials with novel morphologies and uniform sizes by rationally designing synthetic systems.
Keywords/Search Tags:metal–organic framework, polyoxometalate, hollow nanostructure, supramolecular interaction, catalysis
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