Controlling Electrocatalytic Interfaces using Thin Films and Nanostructures for Energy Applications
type: CreativeWork
description: The release of greenhouse gases such as CO2 due to various human activities and the use of fossil fuels causes climate change and increases global temperature. For this reason, we must create new technologies that help shift energy production away from fossil fuels to renewable energy sources. Over the past few decades, researchers in academia and industry have focused on developing novel techniques for clean and renewable energy, which could in part be mediated by H2 fuel cells. The oxygen reduction reaction (ORR) occurs at the cathode of fuel cells and is the rate-limiting reaction. Water can be electrolyzed using electricity from renewable sources to generate H2 in a green manner. The oxygen evolution reaction (OER) is the rate-limiting reaction for water electrolysis. Unfortunately, catalysts based on Pt and Ir have the best performance for the ORR and OER, respectively. However, the widespread application of these catalysts is limited because of the high cost and scarcity of Pt- and Ir-based catalysts. Non-precious metal catalysts such as those based on Cu and Ni are promising alternatives. In this dissertation, I have developed a new electrochemical platform that allows for the study of the control of electron and proton transfer in the ORR. Specifically, I use Cu as one of the non-precious metal catalysts to study the ORR. I prepared a dinuclear Cu ORR catalyst that can be covalently attached to thiol-based self-assembled monolayers (SAMs) on Au electrodes using azide-alkyne click chemistry. Using this architecture, the electron transfer rate to the catalyst is modulated by changing the length of the SAM, and the proton transfer rate to the catalyst is controlled with an appended lipid membrane modified with proton carriers. By tuning the relative rates of proton and electron transfer, the current density of the lipid-covered catalyst was enhanced significantly without altering its core molecular structure. Also, I utilized designer small-molecule proton carr…
abstract: The release of greenhouse gases such as CO2 due to various human activities and the use of fossil fuels causes climate change and increases global temperature. For this reason, we must create new technologies that help shift energy production away from fossil fuels to renewable energy sources. Over the past few decades, researchers in academia and industry have focused on developing novel techniques for clean and renewable energy, which could in part be mediated by H2 fuel cells. The oxygen reduction reaction (ORR) occurs at the cathode of fuel cells and is the rate-limiting reaction. Water can be electrolyzed using electricity from renewable sources to generate H2 in a green manner. The oxygen evolution reaction (OER) is the rate-limiting reaction for water electrolysis. Unfortunately, catalysts based on Pt and Ir have the best performance for the ORR and OER, respectively. However, the widespread application of these catalysts is limited because of the high cost and scarcity of Pt- and Ir-based catalysts. Non-precious metal catalysts such as those based on Cu and Ni are promising alternatives. In this dissertation, I have developed a new electrochemical platform that allows for the study of the control of electron and proton transfer in the ORR. Specifically, I use Cu as one of the non-precious metal catalysts to study the ORR. I prepared a dinuclear Cu ORR catalyst that can be covalently attached to thiol-based self-assembled monolayers (SAMs) on Au electrodes using azide-alkyne click chemistry. Using this architecture, the electron transfer rate to the catalyst is modulated by changing the length of the SAM, and the proton transfer rate to the catalyst is controlled with an appended lipid membrane modified with proton carriers. By tuning the relative rates of proton and electron transfer, the current density of the lipid-covered catalyst was enhanced significantly without altering its core molecular structure. Also, I utilized designer small-molecule proton carr…
author: Gautam, Rajendra Prasad
date published: 2022
date modified: 2026-07-27T21:47:58Z
provider: University of Nevada - Reno
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: University of Nevada - Reno

PropertyValue
property ID: Handle
value: http://hdl.handle.net/11714/8146