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First Principles Modeling of the Ele...

Dickens, Colin Forest.

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First Principles Modeling of the Electrochemical Oxygen Evolution Reaction: From Electronic Structure to Kinetics.

Record Type:	Electronic resources : Monograph/item
Title/Author:	First Principles Modeling of the Electrochemical Oxygen Evolution Reaction: From Electronic Structure to Kinetics./
Author:	Dickens, Colin Forest.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2019,
Description:	137 p.
Notes:	Source: Dissertations Abstracts International, Volume: 82-06, Section: B.
Contained By:	Dissertations Abstracts International82-06B.
Subject:	Molecular chemistry. -
Online resource:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28112983
ISBN:	9798698502760

First Principles Modeling of the Electrochemical Oxygen Evolution Reaction: From Electronic Structure to Kinetics.
Dickens, Colin Forest.

First Principles Modeling of the Electrochemical Oxygen Evolution Reaction: From Electronic Structure to Kinetics. - Ann Arbor : ProQuest Dissertations & Theses, 2019 - 137 p.

Source: Dissertations Abstracts International, Volume: 82-06, Section: B.

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

This item must not be sold to any third party vendors.

The efficient storage of intermittent, renewable energy in the form of chemical bonds is critical to successfully transition away from fossil-derived fuels and chemicals. The oxygen evolution reaction (OER) plays a central role in many of these storage technologies by splitting water molecules to supply reactive protons and electrons. The activity of OER electrocatalysts directly influences the efficiency of these technologies by reducing the overpotential required to achieve reasonable production rates.Density functional theory (DFT) is a useful tool for investigating potential OER catalyst active sites at the atomic scale in an effort to either explain experimental observation or suggest new experiments to perform. Such theoretical studies are popular for a variety of electrochemical and thermochemical reactions, but OER catalysts are particularly challenging to model because of the highly oxidizing conditions at which they operate, leading to corrosion via oxidation and dissolution of the catalyst surface. In the first part of this thesis, we examine two state-of-the-art OER catalysts, SrIrO3 and RuO2, that are known experimentally to dissolve under reaction conditions and use DFT to explore possible active sites that might form. In the case of SrIrO3 we consider various Sr-deficient surface structures, while for RuO2 we consider defect motifs such as Ru-vacancies, steps, and kinks, and in both cases we identify sites with higher theoretical activities than the ideal, defect-free surfaces. These studies are computationally expensive because they require individually probing the activity of possible active sites by calculating the stability of OER intermediates OH*, O*, and OOH* at each site. Towards circumventing these calculations, we identify an electronic structural descriptor, namely the average 2p-state energy of adsorbed atomic oxygen, that correlates strongly with the theoretical OER activity and allows for screening multiple active sites at once with a single DFT calculation.In the second part of this thesis, we attempt to move beyond the conventional thermodynamic analysis of theoretical OER activity with microkinetic modeling, which allows for a more direct comparison to experimental results. This involves explicitly modeling the aqueous-solid electrochemical interface and computing kinetic barrier heights for reactions that involve charge transfer across the interface. We find that the intrinsic barrier height for one elementary step in particular, OOH* formation, is significantly higher than the others for rutile (110) surfaces and directly accounts for the non-negligible OER overpotential observed experimentally. The resultant microkinetic model, which assumes OOH* formation to be the sole rate determining step, is analyzed in the context of experimental observations including Tafel behavior and is used to construct an OER volcano consisting solely of experimental data.

ISBN: 9798698502760Subjects--Topical Terms:

1071612
Molecular chemistry.
Subjects--Index Terms:

Oxygen evolution reaction

First Principles Modeling of the Electrochemical Oxygen Evolution Reaction: From Electronic Structure to Kinetics.
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300 $a 137 p.
500 $a Source: Dissertations Abstracts International, Volume: 82-06, Section: B.
500 $a Advisor: Jaramillo, Thomas;Noerskov, Jens;Qin, Jian.
502 $a Thesis (Ph.D.)--Stanford University, 2019.
506 $a This item must not be sold to any third party vendors.
520 $a The efficient storage of intermittent, renewable energy in the form of chemical bonds is critical to successfully transition away from fossil-derived fuels and chemicals. The oxygen evolution reaction (OER) plays a central role in many of these storage technologies by splitting water molecules to supply reactive protons and electrons. The activity of OER electrocatalysts directly influences the efficiency of these technologies by reducing the overpotential required to achieve reasonable production rates.Density functional theory (DFT) is a useful tool for investigating potential OER catalyst active sites at the atomic scale in an effort to either explain experimental observation or suggest new experiments to perform. Such theoretical studies are popular for a variety of electrochemical and thermochemical reactions, but OER catalysts are particularly challenging to model because of the highly oxidizing conditions at which they operate, leading to corrosion via oxidation and dissolution of the catalyst surface. In the first part of this thesis, we examine two state-of-the-art OER catalysts, SrIrO3 and RuO2, that are known experimentally to dissolve under reaction conditions and use DFT to explore possible active sites that might form. In the case of SrIrO3 we consider various Sr-deficient surface structures, while for RuO2 we consider defect motifs such as Ru-vacancies, steps, and kinks, and in both cases we identify sites with higher theoretical activities than the ideal, defect-free surfaces. These studies are computationally expensive because they require individually probing the activity of possible active sites by calculating the stability of OER intermediates OH*, O*, and OOH* at each site. Towards circumventing these calculations, we identify an electronic structural descriptor, namely the average 2p-state energy of adsorbed atomic oxygen, that correlates strongly with the theoretical OER activity and allows for screening multiple active sites at once with a single DFT calculation.In the second part of this thesis, we attempt to move beyond the conventional thermodynamic analysis of theoretical OER activity with microkinetic modeling, which allows for a more direct comparison to experimental results. This involves explicitly modeling the aqueous-solid electrochemical interface and computing kinetic barrier heights for reactions that involve charge transfer across the interface. We find that the intrinsic barrier height for one elementary step in particular, OOH* formation, is significantly higher than the others for rutile (110) surfaces and directly accounts for the non-negligible OER overpotential observed experimentally. The resultant microkinetic model, which assumes OOH* formation to be the sole rate determining step, is analyzed in the context of experimental observations including Tafel behavior and is used to construct an OER volcano consisting solely of experimental data.
590 $a School code: 0212.
650 4 $a Molecular chemistry. $3 1071612
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653 $a Density functional theory
653 $a Water molecules
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773 0 $t Dissertations Abstracts International $g 82-06B.
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791 $a Ph.D.
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