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Yang Shao-Horn. Hong, Wesley T. (Wesley Terrence) Massachusetts Institute of Technology. Department of Materials Science and Engineering. Massachusetts Institute of Technology. Department of Materials Science and Engineering 2016-09-13T19:09:56Z 2016-09-13T19:09:56Z 2016 2016 http://hdl.handle.net/1721.1/104185 958135469 Thesis: Ph. D., Massachusetts Institute of Technology, Department of Materials Science and Engineering, 2016. Cataloged from PDF version of thesis. Includes bibliographical references (pages 143-160). Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to enabling solar fuels, fuel cells, electrolyzers, and metal-air batteries. Non-precious transition metal oxides show promise as cost-effective materials in such devices. Leveraging the wealth of solid-state physics understanding developed for this class of materials in the past few decades, new theories and strategies can be explored for designing optimal catalysts. This work presents a framework for the rational design of transition-metal perovskite oxide catalysts that can accelerate the development of highly active catalysts for more efficient energy storage and conversion systems. We describe a method for the synthesis of X-ray emission, absorption, and photoelectron spectroscopy data to experimentally determine the electronic structure of oxides on an absolute energy scale, as well as extract key electronic parameters associated with the material. Using this approach, we show that the charge-transfer energy - a parameter that captures the energy configuration of oxygen and transition-metal valence electrons - is a central descriptor capable of modifying both the oxygen evolution kinetics and mechanism. Its role in determining the absolute band energies of a catalyst can rationalize the differences in the electron-transfer and proton-transfer kinetics across oxide chemistries. Furthermore, we corroborate that the charge-transfer energy is one of the most influential parameters on the oxygen evolution reaction through a statistical analysis of a multitude of structure-activity relationships. The quantitative models generated by this analysis can then be used to rapidly screen oxide materials across a wide chemical space for highthroughput materials discovery. by Wesley T. Hong. Ph.D. 160 pages eng Massachusetts Institute of Technology M.I.T. theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. See provided URL for inquiries about permission. http://dspace.mit.edu/handle/1721.1/7582 Materials Science and Engineering. Rational design strategies for oxide oxygen evolution electrocatalysts Thesis application/pdf false Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="1637da5a-41e7-493f-aeb7-e5a2318982d8"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Language>eng</Language> <Title>Rational design strategies for oxide oxygen evolution electrocatalysts</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2016</PublicationDate> <Authors> <Author> <DisplayName>Hong, Wesley T. (Wesley Terrence)</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>http://dspace.mit.edu/handle/1721.1/7582</License> <Keyword>Materials Science and Engineering.</Keyword> <Abstract>Understanding and mastering the kinetics of oxygen electrocatalysis is instrumental to enabling solar fuels, fuel cells, electrolyzers, and metal-air batteries. Non-precious transition metal oxides show promise as cost-effective materials in such devices. Leveraging the wealth of solid-state physics understanding developed for this class of materials in the past few decades, new theories and strategies can be explored for designing optimal catalysts. This work presents a framework for the rational design of transition-metal perovskite oxide catalysts that can accelerate the development of highly active catalysts for more efficient energy storage and conversion systems. We describe a method for the synthesis of X-ray emission, absorption, and photoelectron spectroscopy data to experimentally determine the electronic structure of oxides on an absolute energy scale, as well as extract key electronic parameters associated with the material. Using this approach, we show that the charge-transfer energy - a parameter that captures the energy configuration of oxygen and transition-metal valence electrons - is a central descriptor capable of modifying both the oxygen evolution kinetics and mechanism. Its role in determining the absolute band energies of a catalyst can rationalize the differences in the electron-transfer and proton-transfer kinetics across oxide chemistries. Furthermore, we corroborate that the charge-transfer energy is one of the most influential parameters on the oxygen evolution reaction through a statistical analysis of a multitude of structure-activity relationships. The quantitative models generated by this analysis can then be used to rapidly screen oxide materials across a wide chemical space for highthroughput materials discovery.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>