The Rare Earth Elements E-Book

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Serie: EIC Books
• Sprache: Englisch

Seitenzahl: 1651

Veröffentlichungsjahr: 2013

Beschreibung

Lanthanides are of great importance for the electronic industries, this new book (from the EIBC Book Series) provides a comprehensive coverage of the basic chemistry, particularly inorganic chemistry, of the lanthanoid elements, those having a 4f shell of electrons. A chapter is describing the similarity of the Group 3 elements, Sc, Y, La, the group from which the lanthanoids originate and the group 13 elements, particularly aluminum, having similar properties. Inclusion of the group 3 and 13 elements demonstrates how the lanthanoid elements relate to other, more common, elements in the Periodic Table. Beginning chapters describe the occurrence and mineralogy of the elements, with a focus on structural features observed in compounds described in later chapters. The majority of the chapters is organized by the oxidation state of the elements, Ln(0), Ln(II), Ln(III), and Ln(IV). Within this organization the chapters are further distinguished by type of compound, inorganic (oxides and hydroxides, aqueous speciation, halides, alkoxides, amides and thiolates, and chelates) and organometallic. Concluding chapters deal with diverse and critically important applications of the lanthanoids in electronic and magnetic materials, and medical imaging.

Leseprobe

Encyclopedia of Inorganic and Bioinorganic Chemistry

Editorial Board

Editor-in-Chief

Robert A. ScottUniversity of Georgia, Athens, GA, USA

Section Editors

David A. AtwoodUniversity of Kentucky, Lexington, KY, USA

Timothy P. HanusaVanderbilt University, Nashville, TN, USA

Charles M. LukehartVanderbilt University, Nashville, TN, USA

Albrecht MesserschmidtMax-Planck-Institute für Biochemie, Martinsried, Germany

Robert A. ScottUniversity of Georgia, Athens, GA, USA

Editors-in-Chief Emeritus & Senior Advisors

Robert H. CrabtreeYale University, New Haven, CT, USA

R. Bruce KingUniversity of Georgia, Athens, GA, USA

International Advisory Board

Wolfram BodeMartinsried, Germany

Michael BruceAdelaide, Australia

Tristram ChiversCalgary, Canada

Mirek CyglerSaskatchewan, Canada

Marcetta DarensbourgTX, USA

Michel EphritikhineGif-sur-Yvette, France

Robert HuberMartinsried, Germany

Susumu KitagawaKyoto, Japan

Thomas PoulosCA, USA

David SchubertColorado, USA

T. Don TilleyCA, USA

Karl E. WieghardtMülheim an der Ruhr, Germany

Vivian YamHong Kong

This edition first published 2012© 2012 John Wiley & Sons Ltd

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Front Cover image credit:This figure was published in: Uh H. and Petoud S. Novel antennae for the sensitization of near infrared luminescent lanthanide cations. C. R. Chimie 13 (2010) 668–680. Copyright © 2010 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.

A catalogue record for this book is available from the British Library.ISBN-13: 978-1-119-95097-4

Set in 9½ 11½ pt TimesNewRomanPS by Laserwords (Private) Limited, Chennai, India. Printed and bound in Singapore by Markono Print Media Pte Ltd.

EIBC Books

Application of Physical Methods to Inorganic and Bioinorganic ChemistryEdited by Robert A. Scott and Charles M. LukehartISBN 978-0-470-03217-6

Nanomaterials: Inorganic and Bioinorganic PerspectivesEdited by Charles M. Lukehart and Robert A. ScottISBN 978-0-470-51644-7

Computational Inorganic and Bioinorganic ChemistryEdited by Edward I. Solomon, R. Bruce King and Robert A. ScottISBN 978-0-470-69997-3

Radionuclides in the EnvironmentEdited by David A. AtwoodISBN 978-0-470-71434-8

Energy Production and Storage: Inorganic Chemical Strategies for a Warming WorldEdited by Robert H. CrabtreeISBN 978-0-470-74986-9

The Rare Earth Elements: Fundamentals and ApplicationsEdited by David A. AtwoodISBN 978-1-119-95097-4

Forthcoming

Metals in CellsEdited by Valeria Culotta and Robert A. ScottISBN 978-1-119-95323-4

Metal-Organic Frameworks MaterialsEdited by Leonard R. MacGillivray and Charles M. LukehartISBN 978-1-119-95289-3

Encyclopedia of Inorganic and Bioinorganic Chemistry

The Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC) was created as an online product in 2012 as a merger of the Encyclopedia of Inorganic Chemistry (which published online in 2006) and the Handbook of Metalloproteins (which published online in 2006). The resulting combination proves to be the defining reference work in the field of inorganic and bioinorganic chemistry. The online edition is regularly updated and expanded. For information see:

http://www.wileyonlinelibrary.com/ref/eibc

Contents

Contributors

Series Preface

Volume Preface

Geology, Geochemistry, and Natural Abundances of the Rare Earth ElementsScott M. McLennan and Stuart Ross Taylor

Sustainability of Rare Earth ResourcesDavid A. Atwood

The Electronic Structure of the LanthanidesAna de Bettencourt-Dias

Variable ValencyAndrew W.G. Platt

Group TrendsAndrew W.G. Platt

Solvento Complexes of the Lanthanide IonsSimon A. Cotton and Jack M. Harrowfield

Lanthanides in Living SystemsSimon A. Cotton and Jack M. Harrowfield

Lanthanides: Coordination ChemistrySimon A. Cotton and Jack M. Harrowfield

Organometallic Chemistry Fundamental PropertiesStephen T. Liddle

Lanthanides: ‘‘Comparison to 3d Metals’’Simon A. Cotton

LuminescenceJulien Andres and Anne-Sophie Chauvin

Lanthanides: Luminescence ApplicationsJulien Andres and Anne-Sophie Chauvin

MagnetismBing-Wu Wang and Song Gao

The Divalent State in Solid Rare Earth Metal HalidesGerd Meyer

Lanthanide HalidesTimothy J. Boyle and Leigh Anna M. Steele

Lanthanide Oxide/Hydroxide ComplexesZhiping Zheng

Lanthanide AlkoxidesTimothy J. Boyle and Leigh Anna M. Steele

Rare Earth SiloxidesClemens Krempner and Brian McNerney

Thiolates, Selenolates, and TellurolatesJohn G. Brennan

CarboxylateJia-sheng Lu and Ruiyao Wang

Lanthanide Complexes with Amino AcidsZhiping Zheng

β-DiketonateKe-Zhi Wang

Rare Earth Borides, Carbides and NitridesTakao Mori

Lanthanide Complexes with Multidentate LigandsXiaoping Yang, Richard A. Jones and Wai-Kwok Wong

AlkylSimon A. Cotton

ArylsSimon A. Cotton

Trivalent Chemistry: CyclopentadienylRoman A. Kresinski

Tetravalent Chemistry: InorganicFarid M.A. Sroor and Frank T. Edelmann

Tetravalent Chemistry: OrganometallicFarid M.A. Sroor and Frank T. Edelmann

Molecular Magnetic MaterialsBing-Wu Wang and Song Gao

Near-Infrared MaterialsLining Sun and Liyi Shi

Superconducting MaterialsAntonio J. Dos santos-García, Miguel Á. Alario-Franco and Regino Sáez-Puche

Metal–Organic FrameworksJohn Hamilton Walrod II and David A. Atwood

Upconversion Nanoparticles for Bioimaging ApplicationsJiefu Jin and Wing-Tak Wong

Oxide and Sulfide NanomaterialsTakuya Tsuzuki

Rare Earth Metal Cluster ComplexesGerd Meyer

Organic SynthesisYuichiro Mori and Shũ Kobayashi

Homogeneous CatalysisYingming Yao and Kun Nie

Heterogeneous CatalysisJohn Hamilton Walrod II and David A. Atwood

Supramolecular Chemistry: from Sensors and Imaging Agents to Functional Mononuclear and Polynuclear Self-Assembly Lanthanide ComplexesJonathan A. Kitchen and Thorfinnur Gunnlaugsson

Endohedral FullerenesDaniel L. Burriss and David A. Atwood

Lanthanide Shift ReagentsCarlos F.G.C. Geraldes

Lanthanides: Magnetic Resonance ImagingSophie Laurent, Luce Vander Elst, Sebastien Boutry and Robert N. Muller

Luminescent BioprobesAnne-Sophie Chauvin

Sensors for Lanthanides and ActinidesGabriela I. Vargas-Zúñiga and Jonathan L. Sessler

Index

Contributors

Miguel Á. Alario-Franco

Universidad Complutense de Madrid, Madrid, Spain (EU)

• Superconducting Materials

Julien Andres

École Polytechnique Fédérale de Lausanne, Vaud, Switzerland

• Lanthanides: Luminescence Applications• Luminescence

David A. Atwood

University of Kentucky, Lexington, KY, USA

• Endohedral Fullerenes• Heterogeneous Catalysis• Metal–Organic Frameworks• Sustainability of Rare Earth Resources

Ana de Bettencourt-Dias

University of Nevada, Reno, NV, USA

• The Electronic Structure of the Lanthanides

Sebastien Boutry

University of Mons, Mons, Belgium

• Lanthanides: Magnetic Resonance Imaging

Timothy J. Boyle

Sandia National Laboratories, Albuquerque, NM, USA

• Lanthanide Alkoxides• Lanthanide Halides

John G. Brennan

Rutgers, The State University of New Jersey, Piscataway, NJ, USA

• Thiolates, Selenolates, and Tellurolates

Daniel L. Burriss

University of Kentucky, Lexington, KY, USA

• Endohedral Fullerenes

Anne-Sophie Chauvin

École Polytechnique Fédérale de Lausanne, Vaud, Switzerland

• Lanthanides: Luminescence Applications• Luminescence• Luminescent Bioprobes

Simon A. Cotton

University of Birmingham, Birmingham, UK

• Alkyl• Aryls• Lanthanides: ‘‘Comparison to 3d Metals’’• Lanthanides: Coordination Chemistry• Lanthanides in Living Systems• Solvento Complexes of the Lanthanide Ions

Antonio J. Dos santos-García

Universidad Complutense de Madrid, Madrid, Spain (EU)

• Superconducting Materials

Frank T. Edelmann

Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, Magdeburg, Germany

• Tetravalent Chemistry: Organometallic• Tetravalent Chemistry: Inorganic

Song Gao

Peking University, Beijing, People’s Republic of China

• Magnetism• Molecular Magnetic Materials

Carlos F.G.C. Geraldes

University of Coimbra, Coimbra, Portugal

• Lanthanide Shift Reagents

Thorfinnur Gunnlaugsson

School of Chemistry, Trinity College, University of Dublin, Dublin 2, Ireland

• Supramolecular Chemistry: from Sensors and Imaging Agents to Functional   Mononuclear and Polynuclear Self-Assembly Lanthanide Complexes

Jack M. Harrowfield

Université de Strasbourg, Strasbourg, France

• Lanthanides: Coordination Chemistry• Lanthanides in Living Systems• Solvento Complexes of the Lanthanide Ions

Jiefu Jin

The University of Hong Kong, Pokfulam, Hong Kong

• Upconversion Nanoparticles for Bioimaging Applications

Richard A. Jones

University of Texas at Austin, Austin, TX, USA

• Lanthanide Complexes with Multidentate Ligands

Jonathan A. Kitchen

School of Chemistry, Trinity College, University of Dublin, Dublin 2, Ireland

• Supramolecular Chemistry: from Sensors and Imaging Agents to Functional   Mononuclear and Polynuclear Self-Assembly Lanthanide Complexes

Shũ Kobayashi

The University of Tokyo, Tokyo, Japan

• Organic Synthesis

Clemens Krempner

Texas Tech University, Lubbock, TX, USA

• Rare Earth Siloxides

Roman A. Kresinski

Kingston University, Kingston-upon-Thames, UK

• Trivalent Chemistry: Cyclopentadienyl

Sophie Laurent

University of Mons, Mons, Belgium

• Lanthanides: Magnetic Resonance Imaging

Stephen T. Liddle

University of Nottingham, Nottingham, UK

• Organometallic Chemistry Fundamental Properties

Jia-sheng Lu

Queen’s University, Kingston, ON, Canada

• Carboxylate

Scott M. McLennan

State University of New York at Stony Brook, Stony Brook, NY, USA

• Geology, Geochemistry, and Natural Abundances of the Rare Earth Elements

Brian McNerney

Texas Tech University, Lubbock, TX, USA

• Rare Earth Siloxides

Gerd Meyer

Universität zu Köln, Köln, Germany

• Rare Earth Metal Cluster Complexes• The Divalent State in Solid Rare Earth Metal Halides

Takao Mori

National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, Japan

• Rare Earth Borides, Carbides and Nitrides

Yuichiro Mori

The University of Tokyo, Tokyo, Japan

• Organic Synthesis

Robert N. Muller

University of Mons, Mons, Belgium

• Lanthanides: Magnetic Resonance Imaging

Kun Nie

Soochow University, Suzhou, People’s Republic of China

• Homogeneous Catalysis

Andrew W.G. Platt

Staffordshire University, Stoke-on-Trent, UK

• Group Trends• Variable Valency

Regino Sáez-Puche

Universidad Complutense de Madrid, Madrid, Spain (EU)

• Superconducting Materials

Jonathan L. Sessler

University of Texas at Austin, Austin, TX, USA

• Sensors for Lanthanides and Actinides

Liyi Shi

Shanghai University, Shanghai, People’s Republic of China

• Near-Infrared Materials

Farid M.A. Sroor

Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, Magdeburg, Germany

• Tetravalent Chemistry: Inorganic• Tetravalent Chemistry: Organometallic

Leigh Anna M. Steele

Sandia National Laboratories, Albuquerque, NM, USA

• Lanthanide Alkoxides• Lanthanide Halides

Lining Sun

Shanghai University, Shanghai, People’s Republic of China

• Near-Infrared Materials

Stuart Ross Taylor

Australian National University, Canberra, Australia

• Geology, Geochemistry, and Natural Abundances of the Rare Earth Elements

Takuya Tsuzuki

Deakin University, Geelong, VIC, Australia

• Oxide and Sulfide Nanomaterials

Luce Vander Elst

University of Mons, Mons, Belgium

• Lanthanides: Magnetic Resonance Imaging

Gabriela I. Vargas-Zúñiga

University of Texas at Austin, Austin, TX, USA

• Sensors for Lanthanides and Actinides

John Hamilton Walrod II

University of Kentucky, Lexington, KY, USA

• Heterogeneous Catalysis• Metal–Organic Frameworks

Bing-Wu Wang

Peking University, Beijing, People’s Republic of China

• Magnetism• Molecular Magnetic Materials

Ke-Zhi Wang

Beijing Normal University, Beijing, People’s Republic of China

• β-Diketonate

Ruiyao Wang

Queen’s University, Kingston, ON, Canada

• Carboxylate

Wai-Kwok Wong

Hong Kong Baptist University, Kowloon Tong, Hong Kong, People’s Republic of China

• Lanthanide Complexes with Multidentate Ligands

Wing-Tak Wong

The Hong Kong Polytechnic University, Hunghom, Kowloon, Hong Kong

• Upconversion Nanoparticles for Bioimaging Applications

Xiaoping Yang

University of Texas at Austin, Austin, TX, USA

• Lanthanide Complexes with Multidentate Ligands

Yingming Yao

Soochow University, Suzhou, People’s Republic of China

• Homogeneous Catalysis

Zhiping Zheng

Xi’an Jiaotong University, Xi’an, Shanxi, People’s Republic of China and University of Arizona, Tucson, AZ, USA

• Lanthanide Complexes with Amino Acids• Lanthanide Oxide/Hydroxide Complexes

Series Preface

The success of the Encyclopedia of Inorganic Chemistry (EIC), pioneered by Bruce King, the founding Editor in Chief, led to the 2012 integration of articles from the Handbook of Metalloproteins to create the newly launched Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC). This has been accompanied by a significant expansion of our Editorial Advisory Board with international representation in all areas of inorganic chemistry. It was under Bruce’s successor, Bob Crabtree, that it was recognized that not everyone would necessarily need access to the full extent of EIBC. All EIBC articles are online and are searchable, but we still recognized value in more concise thematic volumes targeted to a specific area of interest. This idea encouraged us to produce a series of EIC (now EIBC) Books, focusing on topics of current interest. These will continue to appear on an approximately annual basis and will feature the leading scholars in their fields, often being guest coedited by one of these leaders. Like the Encyclopedia, we hope that EIBC Books continue to provide both the starting research student and the confirmed research worker a critical distillation of the leading concepts and provide a structured entry into the fields covered.

The EIBC Books are referred to as ‘‘spin-on’’ books, recognizing that all the articles in these thematic volumes are destined to become part of the online content of EIBC, usually forming a new category of articles in the EIBC topical structure. We find that this provides multiple routes to finding the latest summaries of current research.

I fully recognize that this latest transformation of EIBC is built upon the efforts of my predecessors, Bruce King and Bob Crabtree, my fellow editors, as well as the Wiley personnel, and, most particularly, the numerous authors of EIBC articles. It is the dedication and commitment of all these people that is responsible for the creation and production of this series and the ‘‘parent’’ EIBC.

Robert A. Scott

University of Georgia

Department of Chemistry

November 2012

Volume Preface

The rare earth elements (REE) include lanthanum and the f-block elements, cerium through lutetium. Scandium and yttrium are included in this group as they have ionic radii similar to the lighter f-block elements and are found together in the same ores. The chemical similarities of the 17 REE make them unique in comparison to the other metals in the periodic table where two adjacent elements in a period typically have significantly different chemical properties. This makes the REE relatively difficult to separate from one another, although there are minerals where the lighter (La–Eu) and heavier (Y and Gd–Lu) REE are concentrated. REE research has benefited from this similarity, however, as compounds and materials formed with one REE can often be replicated with one or more of the other REE.

The sequential filling of the f orbitals beginning with cerium gives the REE very unique electronic, optical, luminescent, and magnetic properties. Over the past several decades these properties have been utilized in a wide range of synthetic, catalytic, electronic, medicinal, and military applications. The REE are now found in a multitude of consumer products such as computers, cell phones, and televisions. REE are used in automotive catalytic converters, petroleum refining, lasers, fuel cells, light-emitting diodes, magnetic resonance imaging (MRI), hybrid electric vehicles, solar energy, and windmills, to name but a few examples. REE are not only ubiquitous in modern society; they will be of critical importance in achieving a carbon-free, sustainable, global energy supply.

The Rare Earths: Fundamentals and Applications provides the knowledge of fundamental REE chemistry necessary to understand how the elements are currently being used and how they might be used in the future. The book is organized to provide a comprehensive description of the breadth of REE chemistry in four sequential sections: fundamental chemistry (Chapters 1–12), important representative compounds (Chapters 13–30), examples of solid-state materials (Chapters 31–36), and current and potential new applications (Chapters 37–45). It is designed to provide students, instructors, academic researchers, and industrial personnel with a fundamental understanding of the electronic, chemical, and physical properties of the rare earth elements. This knowledge may be used to understand the current use of the elements and, it is hoped, will inspire and encourage new developments. With the possibility that REE resources and supplies will become limited in the near future, some of the new REE developments should include reducing the environmental impacts related to mining and isolation, recovering and recycling the elements from existing products, finding elements and compounds that could be substituted for REE, and ultimately, designing products where the elements or product components can be readily and economically reused.

While this book describes many of the more important aspects of the REE, it would be impossible for a single volume to incorporate the vast number of compounds, materials, and applications that contain or utilize REE. New information will be addressed in future articles in the Encyclopedia of Inorganic and Bioinorganic Chemistry (EIBC). For example, there will be new REE articles on mining and extraction, metals and alloys, similarities of the REE with elements in Groups 1, 2, and 13, computational studies, carbonate, silicate, and polyoxometallate solid state materials, single-molecule magnets, environmental speciation, recycling, and many others.

The Rare Earths: Fundamentals and Applications is an ideal starting point and foundation for educating students, instructors, academic researchers, and industrial personnel on the unique chemistry and applications associated with the rare earth elements. New EIBC articles will supplement the contents of the book and will provide information on a broader range of rare earth compounds, materials, applications, and new developments.

I am grateful to the many authors who made substantial contributions to the outline and content of this book while it was being organized. I am especially grateful to Simon Cotton for the excellent expert assistance, information, and ideas he provided throughout the process.

David A. Atwood

University of Kentucky, Lexington, KY, USA

May 2012

THE RARE EARTH ELEMENTS:Fundamentals andApplications

Geology, Geochemistry, and Natural Abundances of the Rare Earth Elements

Scott M. McLennan

State University of New York at Stony Brook, Stony Brook, NY, USA

and

Stuart Ross Taylor

Australian National University, Canberra, Australia

1 SUMMARY

The rare earth elements (REE) are trace elements in most geological settings and are of great utility in understanding a wide variety of geological, geochemical, and cosmochemical processes that take place on the Earth, other planets, and other planetary bodies (e.g., Moon, asteroids). The properties that lead to this importance include the following: REE are an extremely coherent group of trace elements, by geochemical standards, in terms of ionic radius, charge, and mineral site coordination, which makes them especially valuable for monitoring magmatic processes; slight variations in their overall refractory nature provides insights into early solar system high-temperature processes; the distinctive redox chemistries of europium and cerium result in unique insights into magmatic and aqueous processes, respectively; their generally insoluble character in geological settings and resistance to remobilization beyond the mineralogical scale during weathering, diagenesis, and metamorphism makes them important tracers for characterizing various geochemical “reservoirs” (e.g., planetary crusts and mantles).

In addition to being of great value to general geochemistry investigations, the REE have proven of increasingly great commercial value. Modern applications involve many that are useful in high technology, including some of strategic/military use. Accordingly, understanding the geological conditions leading to REE concentrations that are sufficient for economically viable extraction is also seen as increasingly important.

This chapter addresses geological and geochemical factors that control REE distributions in rocks and minerals, both in the Earth and on other planetary bodies, and the processes that give rise to economic concentrations of REE in the Earth’s crust. We begin with a discussion of the fundamental geochemistry and cosmochemistry of REE. This is followed by describing processes that influence the distribution of REE in rocks and minerals and the geological conditions that give rise to ore-grade concentrations. Finally, we characterize abundances and distributions of REE in various reservoirs, such as bulk solar system, bulk Earth, crust, oceans, and so forth, that are relevant to understanding the origin and evolution of the Earth.

2 INTRODUCTION

Geochemists have long recognized the misnomer associated with the REE, aptly captured in the title of one early paper, “Dispersed and not-so-rare earths.”1 Although REE occur as trace elements in the vast majority of geological environments, their natural abundances in crustal rocks, mostly ranging from hundreds of parts per billion (terbium, holmium, thulium, lutetium) to tens of parts per million (lanthanum, cerium, neodymium), are not exceptionally low compared to many other elements. Thus, depending on the estimate, the most common REE, cerium, is approximately the 27th most abundant element in the continental crust of the Earth. Regardless of absolute amounts, the REE arguably are the single most important coherent suite of elements in nature for the purposes of interpreting a wide variety of geological processes for reasons discussed below. Accordingly, the absolute concentrations and embedded radiogenic isotopic systems (e.g., 147Sm–143Nd, 146Sm–142Nd, 176Lu–176Hf, 138La–138Ce) have been studied in exhaustive detail in a wide variety of rocks, minerals, and aqueous fluids on the Earth and other available solar system bodies.

Industrial uses of REE metals and compounds have expanded greatly over the past century, from the early application of mixing small amounts of cerium oxide with thorium oxide to produce incandescent gas light mantles, developed in the late nineteenth century, to being crucial components in a wide variety of cutting-edge technology applications.2 Modern uses of the REE in high-technology applications include many of considerable strategic value.3 Accordingly, geological processes giving rise to ore-grade concentrations of REE are also of increasing interest.