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Hydroxyl-Presenting Metal-Organic Fr...
~
Nguyen, Huong Giang Thai.
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Hydroxyl-Presenting Metal-Organic Frameworks as Support Platforms for Vanadium- and Titanium-Based Oxidation Catalysts.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
Hydroxyl-Presenting Metal-Organic Frameworks as Support Platforms for Vanadium- and Titanium-Based Oxidation Catalysts./
作者:
Nguyen, Huong Giang Thai.
面頁冊數:
221 p.
附註:
Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.
Contained By:
Dissertation Abstracts International76-10B(E).
標題:
Analytical chemistry. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3705328
ISBN:
9781321782448
Hydroxyl-Presenting Metal-Organic Frameworks as Support Platforms for Vanadium- and Titanium-Based Oxidation Catalysts.
Nguyen, Huong Giang Thai.
Hydroxyl-Presenting Metal-Organic Frameworks as Support Platforms for Vanadium- and Titanium-Based Oxidation Catalysts.
- 221 p.
Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.
Thesis (Ph.D.)--Northwestern University, 2015.
Heterogeneous catalysts such as supported vanadium oxides have great potential to be developed into economically viable oxidation catalysts if they can exhibit greater selectivity; however, their current syntheses often yield a mixture of species, rendering the analysis of structure-activity relationships for each possible vanadium oxide species difficult and, thus, frustrating efforts to improve catalyst activity and selectivity. To address this issue, two metal-organic framework (MOF) systems possessing well-defined and single-site catecholate supports for monomeric vanadyl species were synthesized and their catalytic activities were tested.
ISBN: 9781321782448Subjects--Topical Terms:
3168300
Analytical chemistry.
Hydroxyl-Presenting Metal-Organic Frameworks as Support Platforms for Vanadium- and Titanium-Based Oxidation Catalysts.
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Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.
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Advisers: SonBinh T. Nguyen; Joseph T. Hupp.
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Heterogeneous catalysts such as supported vanadium oxides have great potential to be developed into economically viable oxidation catalysts if they can exhibit greater selectivity; however, their current syntheses often yield a mixture of species, rendering the analysis of structure-activity relationships for each possible vanadium oxide species difficult and, thus, frustrating efforts to improve catalyst activity and selectivity. To address this issue, two metal-organic framework (MOF) systems possessing well-defined and single-site catecholate supports for monomeric vanadyl species were synthesized and their catalytic activities were tested.
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Through post-synthesis grafting of catechol-presenting dopamine to the unsaturated Cr centers of MIL-101, followed by metallation with vanadyl ion, vanadyl monocatecholate-functionalized V(dop)-MIL-101 was obtained. V(dop)-MIL-101 can efficiently catalyze the oxidation of an organic sulfide and exhibited tunable selectivity for the sulfoxide product. In an alternative strategy, a series PG-CatBrO (PG = protecting group) paddlewheel MOFs were constructed from ZnII ions, tetracarboxylate struts, and protected catecholate dipyridyl struts, which could be deprotected and subsequently metallated with vanadyl ions to give V-CatBrO MOF. This MOF can catalyze the benzylic oxidation of tetralin to tetralol and tetralone.
520
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To demonstrate that MOF-based catalysts are viable for gas-phase reactions, a thermally stable hydroxyl-presenting MOF, UiO-66, was explored as a MOF-based support. V-UiO-66 proved to be an effective analogue of hydroxyl-presenting solid supports for VV species in gas-phase oxidation reactions, catalyzing the oxidative dehydrogenation of cyclohexene to benzene at high temperatures (350 °C). Generalization of the metallation of the hydroxyl-presenting nodes of UiO-66 to other redox-active metals, such as titanium, has also allowed other chemical oxidations to be accessed.
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