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Postsynthetic Modification of Metal-...

Tanabe, Kristine Kimie.

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Postsynthetic Modification of Metal-Organic Frameworks.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Postsynthetic Modification of Metal-Organic Frameworks./
Author:	Tanabe, Kristine Kimie.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2011,
Description:	283 p.
Notes:	Source: Dissertation Abstracts International, Volume: 72-06, Section: B, page: 3435.
Contained By:	Dissertation Abstracts International72-06B.
Subject:	Inorganic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3445257
ISBN:	9781124543154

Postsynthetic Modification of Metal-Organic Frameworks.
Tanabe, Kristine Kimie.

Postsynthetic Modification of Metal-Organic Frameworks. - Ann Arbor : ProQuest Dissertations & Theses, 2011 - 283 p.

Source: Dissertation Abstracts International, Volume: 72-06, Section: B, page: 3435.

Thesis (Ph.D.)--University of California, San Diego, 2011.

Metal-organic frameworks (MOFs) are porous crystalline materials that are built from metal ions or metal ion clusters and organic ligands. There has been much interest in designing functionalized MOFs with enhanced host-guest interactions for potential applications in gas storage, catalysis, and separation. However, it has remained a challenge to synthesize functionalized MOFs directly through traditional MOF synthesis. This dissertation focuses on the development of postsynthetic modification (PSM) as a method for functionalizing MOFs. A systematic overview of PSM will be presented to highlight PSM as a general, versatile approach for enhancing the physical and chemical properties of MOFs.

ISBN: 9781124543154Subjects--Topical Terms:

3173556
Inorganic chemistry.

Postsynthetic Modification of Metal-Organic Frameworks.
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100 1 $a Tanabe, Kristine Kimie. $3 3278662
245 1 0 $a Postsynthetic Modification of Metal-Organic Frameworks.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2011
300 $a 283 p.
500 $a Source: Dissertation Abstracts International, Volume: 72-06, Section: B, page: 3435.
500 $a Adviser: Seth M. Cohen.
502 $a Thesis (Ph.D.)--University of California, San Diego, 2011.
520 $a Metal-organic frameworks (MOFs) are porous crystalline materials that are built from metal ions or metal ion clusters and organic ligands. There has been much interest in designing functionalized MOFs with enhanced host-guest interactions for potential applications in gas storage, catalysis, and separation. However, it has remained a challenge to synthesize functionalized MOFs directly through traditional MOF synthesis. This dissertation focuses on the development of postsynthetic modification (PSM) as a method for functionalizing MOFs. A systematic overview of PSM will be presented to highlight PSM as a general, versatile approach for enhancing the physical and chemical properties of MOFs.
520 $a In the first half of this dissertation, IRMOF-3, an amino-containing MOF, is modified with a series of alkyl anhydrides, and the effects of reagent size on modification extent are explored. In the next chapter, other amino-containing MOFs systems (DMOF-1-NH2 and UMCM-1-NH2) are synthesized and modified using PSM. Through this study, PSM is shown to be a practical approach for functionalizing MOFs, and also indicates MOF topology can influence the modification outcome. The second half of this dissertation focuses on using PSM to develop MOFs for gas storage and catalysis applications. IRMOF-3, DMOF-1-NH2, and UMCM-1-NH2 are modified and tested for H2 storage. The MOFs are modified with certain functionalities (e.g., alkyl vs. aromatic) to determine if H2 uptake and heat of adsorption is improved. In a separate study, UMCM-1-NH2 is modified with metal binding substituents, and is metallated with different metal ions to generate a series of potential Lewis acid MOF catalysts. The metallated UMCM MOFs are tested for the Mukaiyama aldol reaction and for epoxide ring opening catalysis, and the catalytic results are presented.
520 $a Lastly, a new functionalization technique, named postsynthetic deprotection (PSD), is introduced. Two new BDC ligands are synthesized with photolabile protecting groups and are incorporated into MOFs. The MOFs are then exposed to UV light, which results in the removal of the photolabile groups to produce MOFs with free, uncoordinated hydroxyl groups. This is the first example of using light to unmask functionalities in a MOF, and presents a novel route for obtaining MOFs with more complex functionalities.
590 $a School code: 0033.
650 4 $a Inorganic chemistry. $3 3173556
650 4 $a Organic chemistry. $3 523952
690 $a 0488
690 $a 0490
710 2 $a University of California, San Diego. $b Chemistry. $3 1023460
773 0 $t Dissertation Abstracts International $g 72-06B.
790 $a 0033
791 $a Ph.D.
792 $a 2011
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3445257