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The Aqueous Chemistry of Oxides$
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Bruce C. Bunker and William H. Casey

Print publication date: 2016

Print ISBN-13: 9780199384259

Published to Oxford Scholarship Online: November 2020

DOI: 10.1093/oso/9780199384259.001.0001

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PRINTED FROM OXFORD SCHOLARSHIP ONLINE (oxford.universitypressscholarship.com). (c) Copyright Oxford University Press, 2021. All Rights Reserved. An individual user may print out a PDF of a single chapter of a monograph in OSO for personal use. date: 17 June 2021

An Overview of Oxide Structures and Compositions

An Overview of Oxide Structures and Compositions

2 An Overview of Oxide Structures and Compositions
The Aqueous Chemistry of Oxides

Bruce C. Bunker

William H. Casey

Oxford University Press

This entire book is devoted to exploring the chemistry of compounds that contain one simple anion: the O2− ion. Except under high-vacuum conditions (see Chapter 6), the species in oxides that interact with water and other environmental chemicals are O2− ions, because the charge-compensating cations are invariably buried beneath an oxide surface layer. One might wonder how we can fill an entire volume discussing the chemical interactions between this single anion and a single chemical: the water molecule. The single most important concept that must be appreciated to understand the contents of this book is that the chemistry and properties of O2− anions are critically dependent on all the cations to which the O2− ions are bound. Each bound cation modifies the electron distributions around the O2− site, changing its local charge, local bonding configurations, acid–base chemistry, ion exchange chemistry, electrochemical properties, chemical stability, and electrical and optical properties. None of these changes are subtle, and in fact most oxide properties are staggering in their diversity. Before considering the chemistry of oxides, it is important to gain an appreciation of just how diverse the structures of oxide materials really are. As this introduction makes clear, there is no such thing as a single, simple O2− ion. There are a myriad of different O2− sites found in the oxides that we encounter often in our daily lives, each of which exhibits its own unique properties. The purpose of this book is to provide a framework that can be used to predict, rationalize, and exploit the rich chemistry associated with those sites. The number of different structures and compositions that can be generated for oxides is almost limitless. The O2− ion forms compounds with more than 90 elements in the Periodic Table that are capable of losing electrons to form cations. The oxide anion combines with cations with charges that range from +1 to +7. Many elements exhibit more than one stable oxidation state, pushing the total number of chemically distinct cations with which O2− can interact to well more than 120.

Keywords:   anion exchangers, bond-valence principle, cation exchanger, density functional theory, electrostatic valence principle, formal charges, hexagonal close packing, ionic radius, modifier cations, octahedral coordination geometry

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