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Utilizing Mechanistic Insight for th...

Shaw, Travis William.

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Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction./
Author:	Shaw, Travis William.
Description:	189 p.
Notes:	Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.
Contained By:	Dissertation Abstracts International76-12B(E).
Subject:	Inorganic chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3714143
ISBN:	9781321912302

Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction.
Shaw, Travis William.

Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction. - 189 p.

Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.

Thesis (Ph.D.)--Princeton University, 2015.

Soluble manganese complexes were studied using voltammetry and preparative techniques for their ability to electrocatalytically reduce carbon dioxide to carbon monoxide. The key observation that these catalysts require water for their ability to perform catalytic CO2 reduction led to the hypothesis that the second coordination sphere of the manganese complex could be favorably influenced by placing a hydrogen-bonding proton near the binding site for carbon dioxide. This proposition was tested by synthesizing the species MnBr(6-(2-hydroxyphenol)-2,2'-bipyridine)(CO)3, which includes a ligand framework with a phenolic proton in close proximity to the CO 2 binding site that allows for facile proton-assisted C-O bond cleavage. This new complex not only exhibited a 46-fold increase in turnover frequency, but also displayed an overpotential of 440 mV, which is excellent relative to other state-of-the art CO2 reduction electrocatalysts. Phenolic methylation led to a complex with catalytic properties similar to the parent complex, MnBr-(2,2'-bipyridine)(CO)3, which suggests a key role for the phenolic proton in catalysis. The mode of action of the pendant phenolic proton was investigated by synthesizing regioisomeric complexes where the phenol was systematically moved away from the metal center by placing it at different positions around the 2,2'-bipyridine ring. These complexes did not exhibit enhanced ability to perform electrocatalytic CO2 reduction leading to the conclusion that the precise placement of the phenol is crucial for enhanced reactivity. Additional information was garnered from voltammetric experiments, including the observation the a pendant phenol allows for catalysis without the need for an additional proton source, confirming that the phenolic proton plays a role in the C---O bonding break step during catalysis.

ISBN: 9781321912302Subjects--Topical Terms:

3173556
Inorganic chemistry.

Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction.
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245 1 0 $a Utilizing Mechanistic Insight for the Improved Design of Homogeneous Manganese Electrocatalysts for CO2 Reduction.
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500 $a Source: Dissertation Abstracts International, Volume: 76-12(E), Section: B.
500 $a Adviser: Andrew B. Bocarsly.
502 $a Thesis (Ph.D.)--Princeton University, 2015.
520 $a Soluble manganese complexes were studied using voltammetry and preparative techniques for their ability to electrocatalytically reduce carbon dioxide to carbon monoxide. The key observation that these catalysts require water for their ability to perform catalytic CO2 reduction led to the hypothesis that the second coordination sphere of the manganese complex could be favorably influenced by placing a hydrogen-bonding proton near the binding site for carbon dioxide. This proposition was tested by synthesizing the species MnBr(6-(2-hydroxyphenol)-2,2'-bipyridine)(CO)3, which includes a ligand framework with a phenolic proton in close proximity to the CO 2 binding site that allows for facile proton-assisted C-O bond cleavage. This new complex not only exhibited a 46-fold increase in turnover frequency, but also displayed an overpotential of 440 mV, which is excellent relative to other state-of-the art CO2 reduction electrocatalysts. Phenolic methylation led to a complex with catalytic properties similar to the parent complex, MnBr-(2,2'-bipyridine)(CO)3, which suggests a key role for the phenolic proton in catalysis. The mode of action of the pendant phenolic proton was investigated by synthesizing regioisomeric complexes where the phenol was systematically moved away from the metal center by placing it at different positions around the 2,2'-bipyridine ring. These complexes did not exhibit enhanced ability to perform electrocatalytic CO2 reduction leading to the conclusion that the precise placement of the phenol is crucial for enhanced reactivity. Additional information was garnered from voltammetric experiments, including the observation the a pendant phenol allows for catalysis without the need for an additional proton source, confirming that the phenolic proton plays a role in the C---O bonding break step during catalysis.
590 $a School code: 0181.
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650 4 $a Chemistry. $3 516420
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