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Oxidative Studies in Decontamination and Water Oxidation Catalysis.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Oxidative Studies in Decontamination and Water Oxidation Catalysis./
作者:	Sullivan, Kevin P.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2019,
面頁冊數:	201 p.
附註:	Source: Dissertations Abstracts International, Volume: 81-08, Section: B.
Contained By:	Dissertations Abstracts International81-08B.
標題:	Polymer chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=27659860
ISBN:	9781392532263

Oxidative Studies in Decontamination and Water Oxidation Catalysis.
Sullivan, Kevin P.

Oxidative Studies in Decontamination and Water Oxidation Catalysis. - Ann Arbor : ProQuest Dissertations & Theses, 2019 - 201 p.

Source: Dissertations Abstracts International, Volume: 81-08, Section: B.

Thesis (Ph.D.)--Emory University, 2019.

This item is not available from ProQuest Dissertations & Theses.

Oxidation reactions are ubiquitous throughout our society. The development of oxidation catalysts has propelled the advancement of civilization and allowed for significant advancements in science and technology. However, the Earth is currently entering a period in which human activities are causing substantial damage both through chemical pollution and global warming resulting from production of greenhouse gasses. This work addresses issues related to both these concerns, by outlining efforts towards the development of oxidation catalysts in three systems relevant to mitigating the impacts of toxic or polluting chemicals. In the first, synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations is described. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues. The second project describes efforts towards the development of rapid aerobic oxidation catalysts for sulfoxidation reactions. Systems involving tetrabutylammonium tribromide and tetrabutylammonium nitrate are studied and optimized for catalyzing the aerobic oxidation of the mustard gas analogue 2-chloroethyl ethyl sulfide. The addition of Cu(II) to this system results in significant rate enhancements, as well as provides a detection capability by changing color in the presence of sulfides, followed by recovery of the original color when the sulfoxidation is complete. Finally, the third project described in this work details stability studies conducted on the water oxidation catalyst Na10[Co4(H2O)2(VW9O34)2] • 26 H2O. This polyoxometalate has been the subject of an ongoing debate regarding its stability under water oxidation catalysis conditions. Solution studies are examined clarifying the stability limitations in this system through 51V NMR resonance experiments on the polyoxometalate. The study demonstrates that the observed catalytic activity cannot be explained simply by Co(II)aq, but arises from multiple active water oxidation catalyst species in solution.

ISBN: 9781392532263Subjects--Topical Terms:

3173488
Polymer chemistry.
Subjects--Index Terms:

Kinetics

Oxidative Studies in Decontamination and Water Oxidation Catalysis.
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520 $a Oxidation reactions are ubiquitous throughout our society. The development of oxidation catalysts has propelled the advancement of civilization and allowed for significant advancements in science and technology. However, the Earth is currently entering a period in which human activities are causing substantial damage both through chemical pollution and global warming resulting from production of greenhouse gasses. This work addresses issues related to both these concerns, by outlining efforts towards the development of oxidation catalysts in three systems relevant to mitigating the impacts of toxic or polluting chemicals. In the first, synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations is described. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues. The second project describes efforts towards the development of rapid aerobic oxidation catalysts for sulfoxidation reactions. Systems involving tetrabutylammonium tribromide and tetrabutylammonium nitrate are studied and optimized for catalyzing the aerobic oxidation of the mustard gas analogue 2-chloroethyl ethyl sulfide. The addition of Cu(II) to this system results in significant rate enhancements, as well as provides a detection capability by changing color in the presence of sulfides, followed by recovery of the original color when the sulfoxidation is complete. Finally, the third project described in this work details stability studies conducted on the water oxidation catalyst Na10[Co4(H2O)2(VW9O34)2] • 26 H2O. This polyoxometalate has been the subject of an ongoing debate regarding its stability under water oxidation catalysis conditions. Solution studies are examined clarifying the stability limitations in this system through 51V NMR resonance experiments on the polyoxometalate. The study demonstrates that the observed catalytic activity cannot be explained simply by Co(II)aq, but arises from multiple active water oxidation catalyst species in solution.
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