Coordination Polymers and Metal Organic Frameworks:: Properties, Types and Applications

318 Pages·2012·17.432 MB·English

by  Oscar L. Ortiz, Luis D. Ramirez

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY

C P
OORDINATION OLYMERS AND
M O F :
ETAL RGANIC RAMEWORKS
P , T
ROPERTIES YPES
AND APPLICATIONS

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C E
HEMICAL NGINEERING
M T
ETHODS AND ECHNOLOGY

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CHEMICAL ENGINEERING METHODS AND TECHNOLOGY

C P
OORDINATION OLYMERS AND
M O F :
ETAL RGANIC RAMEWORKS
P , T
ROPERTIES YPES
AND APPLICATIONS

OSCAR L. ORTIZ AND LUIS D. RAMÍREZ
EDITORS

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Library of Congress Cataloging-in-Publication Data

Coordination polymers and metal organic frameworks : properties, types, and applications /
editors, Oscar L. Ortiz and Luis D. Rammrez.
p. cm.
Includes bibliographical references and index.
ISBN (cid:28)(cid:26)(cid:27)(cid:16)(cid:20)(cid:16)(cid:25)(cid:20)(cid:23)(cid:26)(cid:19)(cid:16)(cid:28)(cid:20)(cid:22)(cid:16)(cid:27) ((cid:40)(cid:16)(cid:37)(cid:82)(cid:82)(cid:78))
1. Coordination polymers. I. Ortiz, Oscar L. II. Rammrez, Luis D.
QD382.C67C66 2011
547'.7--dc23
2011027339

Published by Nova Science Publishers, Inc. † New York
CONTENTS

Preface i
Chapter 1 Hybrid Vanadates, towards Metal-Organic Frameworks 1
Edurne S. Larrea, Roberto Fernández de Luis, José L. Mesa,
José L. Pizarro, M. Karmele Urtiaga, Teófilo Rojo
and María I. Arriortua
Chapter 2 Structure and Magnetic Properties of Mono - and Polynuclear
Complexes Containing Rhenium(IV) 59
Carlos Kremer and Raúl Chiozzone
Chapter 3 The Applications of Metal Organic Frameworks in the Fields of
Hydrogen Storage and Catalysis 99
Yaoqi Li, Ping Son, Yan Li and Xingguo Li
Chapter 4 MOF-Based Mixed-Matrix-Membranes for Industrial
Applications 129
Hoang Vinh-Thang and Serge Kaliaguine
Chapter 5 Coordination Polymers: Opportunities in Heterogeneous
Catalysis 169
Francesc X. Llabrés i Xamena
Chapter 6 High Pressure Gas Storage on Porous Solids: A Comparative
Study of MOFs and Activated Carbons 197
A. Linares-Solano, D. Cazorla-Amorós, J. P. Marco-Lozar
and F. Suárez-García
Chapter 7 Metal-Organic Frameworks for CO Capture: What are
2
Learned from Molecular Simulations 225
Jianwen Jiang
Chapter 8 Halogen Bonding in the Assembly of High-Dimensional
Supramolecular Coordination Polymers 249
Ya-Juan Fan, Shuang-Quan Zang, Yong-Li Wei,
Chen-Xia Du and Hong-Wei Hou
vi Contents
Chapter 9 Subtractive Approach for Introducing Functional Groups onto
Metal–Organic Framework 277
Teppei Yamada and Hiroshi Kitagawa
Chapter 10 Performance of Metal-Organic Framework MIL-101 in the
Liquid Phase Adsorption of Heterocyclic Nitrogen Compounds 291
Alexey L. Nuzhdin, Konstantin A. Kovalenko,
Vladimir P. Fedin and Galina A. Bukhtiyarova
Index 297
PREFACE

In this book, the authors present topical research in the study of coordination polymers
and metal organic frameworks. Topics discussed include hybrid vanadates and metal organic
frameworks; structure and magnetic properties of mono- and polynuclear complexes
containing Re(IV)l; metal organic framework applications in the fields of hydrogen storage
and catalysis; MOF-Based mixed-matrix-membranes for industrial applications; coordination
polymers in heterogeneous catalysis; high pressure gas storage on porous solids; metal
organic frameworks for CO capture and halogen bonding in the assembly of high-
2
dimensional supramolecular coordination polymers. (Imprint: Nova)
Chapter 1 - The combination of metal-organic polymers with different inorganic
oxoanions has become a great strategy to obtain highly complex crystal architectures. Those
materials present metal-organic and inorganic subnets combined in the same crystal structure.
In this sense, hybrid vanadates exhibit a vast crystal chemistry, ranging from structural
archetypes comparable to that of the aluminophosphates or transition metal phosphates to
flexible structures similar to MOFs. Hybrid vanadates with first-row transition metals exhibit
several structural archetypes according to the metal center, the geometry of the ligand and the
vanadium oxide subunit. Vanadium shows a wide variety of oxidation states, each of them
taking different coordination environments. In addition, vanadium polyhedra have a great
ability to polymerize, giving rise to clusters, rings, chains, layers and three-dimensional
substructures. The polymer grade is closely related to the synthetic conditions and, specially,
to the pH during the reaction. The geometry of the ligand and the coordination environment
of the metal centers also plays an important role in the final complexity, dimensionality and
functionality of the crystal structures of hybrid vanadates. Consequently, a deep analysis of
the crystal archetypes observed in hybrid vanadates has allowed us to propose a classification
based on the metal-organic and inorganic substructure dimensionalities. The properties of
these materials are directly related to the structural characteristics, depending directly on the
synergetic interaction between the metal-organic and vanadium oxide subunits. This way, the
loss of solvent in hybrid vanadates could generate a flexible, dynamical and reversible
response of the crystal structure, as in some MOFs, or rigid behaviors, without significant
structural changes, as in inorganic zeolites. Likewise, in the hybrid vanadates, the loss of
coordinated water molecules bonded to the metal centers gives rise to irreversible structural
transformations with a drastic reduction of the crystallinity. The magnetic properties in hybrid
vanadates depend on the connectivity between the metal centers. The magnetic exchange can
also take place through the vanadate oxoanion, giving rise to dimmeric or one-dimensional
magnetic behaviors. The catalytic and photocatalitic tests of several hybrid vanadates reveal
ii Oscar L. Ortiz and Luis D. Ramírez
that they could be active materials in oxidation reactions or for the decomposition of
pollutants.
Chapter 2 - One of the major goals in inorganic supramolecular chemistry today is the
design of polynuclear coordination arrays and the study of their magnetic properties. With the
generation of well-defined architectures it is possible to understand the different factors which
determine the exchange coupling between spin carriers. Most of the results found in the
literature are focused on polynuclear complexes containing metal ions belonging to the first
transition series. Once the magnetic interaction between 3d metal ions is well understood, the
study of those systems containing 4d or 5d metal ions becomes very interesting. In this
review we revise the structure and magnetic properties of Re(IV) complexes. Rhenium(IV), a
5d3 ion, usually forms octahedral complexes which are reasonably stable against redox
processes and inert to ligand substitution. This is the basis for the preparation of mononuclear
species that can act as ligands towards first-row transition metal ions. For example,
complexes containing dicarboxylic ligands, [ReX (ox)]2– and [ReX (mal)]2– (X = Cl, Br; ox =
4 4
oxalato; mal = malonato), or N-donor ligands, [ReCl (pyz)]– (pyz = pyrazine) have been used
5
as building blocks to construct heteropolynuclear complexes. The different designed
structures, from discrete binuclear complexes to extended chain-like compounds, are
reviewed in this work. In addition, the magneto-structural studies of these mono- and
polynuclear complexes are also included and discussed.
Chapter 3 - MOFs (metal organic frameworks) are porous frameworks constructed by the
coordination centers of metal ions and polyatomic organic bridging ligands. Nowadays,
MOFs have attracted much attention as they have been widely investigated for hydrogen
storage, gas separation and catalysis. The microporous porosity, the large specific surface
area and especially the controllable framework have made MOFs superior to traditional
inorganic porous materials such as zeolites and activated carbon. For gas storage and
separation, physisorption on MOFs is one significant approach for future application. By
crystal engineering, both the pore size and the electronic and chemical nature of the interior
surface, on which gas molecules will be adsorbed, can be modified by careful designs. Not
only the porous structure, but also the metal sites and the organic linkers in the frameworks
should greatly affect the interactions between the gas molecules and MOFs. Comparing with
other microporous materials, the low framework density, the high specific surface area,
especially the controllable crystal structure have made MOFs be a favorable research interest.
Furthermore, the frameworks of MOFs contain various structures and large amounts of
essential metal ions, which should be helpful to promote molecular separations and chemical
reactions. Therefore, MOFs can be potentially applied as a heterogeneous catalyst. MOFs
have been used as good precursors of catalysts and special substrates for dispersed active
sites. The existence of abundant metal ions, the large surface areas and the tailorable
microporous structures in MOFs clearly help to obtain highly efficient catalysts.
Chapter 4 - Modern membrane gas separation technology has enjoyed a rapid
development of its commercial applications in the chemical, petrochemical, semiconductor,
food, pharmaceutical, biotechnology and environmental industries, due to their low energy
consumption, compelling low cost and ease of large-scale operation.
Mixed-matrix membranes (MMMs) combine some of the assets of polymer membranes
with the increased separation selectivities associated with the presence of a load of inorganic
particles. In this chapter the potential advantages of metal-organic frameworks (MOFs) as the
discrete phase in MMMs are reviewed.
Preface iii
Chapter 5 - Coordination Polymers (CPs) are an emerging class of materials that are
attracting considerable interest in recent years. Their unique properties make these materials
very promising for applications in a number of fields, including heterogeneous catalysis. In
this chapter, with 126 references, we will revise the main strategies that have been
specifically developed for introducing catalytic active sites in these materials. The enormous
possibilities of this class of materials will be outlined throughout selected examples taken
from the recent literature. I hope that this chapter will be useful either as an introductory
lecture to those who approach the field of CPs or heterogeneous catalysis for the first time, as
well as an updated state-of-the-art vision for all scientists working in this field.
Chapter 6 - Porous materials provide an alternative for satisfying gas storage demands for
on-board storage in transportation technologies (e.g. CH and H ) and for capture, storage and
4 2
transport (e.g. CO ). The principle of their storages is the use of a high pressure adsorption
2
process (or physisorption), as a supercritical gas (e.g. H andCH ) or as a subcritical one (e.g.
2 4
CO ). Such adsorption process has some advantages as: its high storage capacity (very much
2
depending on the surface area, porosity and pore size of the material), its fast kinetic of
storage and release (reversibility), its short refueling time, its low heat evolution and its
efficient cyclability. Additionally, the porous solid (the adsorbent) presents advantages;
different types are available (e.g., zeolites, porous carbons, MOFs, all of them with a large
variety of materials), its porosity, morphology, size and shape are tunable. Among them, two
types of porous solids stand out: 1) the ―calssical‖ activated carbons and 2) the ―ercent and
new‖ type of porous materials (i.e. MOFs and COFs). Most of the papers report the gas
storage capacity of an adsorbent refereed per unit of weight (i.e. gravimetric basis). However,
for applications where the volume of the tank is an important controlling factor (e.g. in
transportation), the gas storage capacity should also be reported per unit of volume
(volumetric basis). And, the density of material used should be consistently measured (i.e. tap
or packing). Unfortunately, this is not always the case and very frequently (as it happens with
―ercent and new‖ porous materials) calculated density (e.g. crystal density) is used. Using
such crystal density, impressive volumetric storage capacities have been reported for MOFs
(also COFs), claiming that they can achieve higher storage capacities for H , CH and CO
2 4 2
than other porous materials such as zeolites and porous carbons. In our opinion, such claimed
superior gas storage capacity of MOFs in relation to activated carbons needs further
evaluations. In this chapter, we comparatively analyses the adsorption capacity of two
activated carbons (ACs) and MOF-5 for storing gases (H , CH and CO ) at different
2 4 2
temperatures (77K and RT) and pressures (from 0.1MPa to 20MPa) both on gravimetric and
volumetric basis paying attention to the data reported in the literature as well as on the
suitability of different densities employed. We advance that, from the data presented and
discussed in this chapter, the outstanding adsorption capacities of MOFs in relation to ACs on
volumetric basis, frequently claimed in the literature, is mainly due to the use of an unrealistic
high density (crystal density) which, not including the inter-particle space of the adsorbents,
gives an apparently high volumetric gas storage capacity. Using a density measured similarly
in both types of adsorbents (e.g. tap density) MOF presents, on volumetric basis, and for all
gases and conditions studied, lower adsorption capacities than ACs, due to its lower inherent
density.
Chapter 7 - CO capture is currently a topical issue in environmental protection and
2
sustainable development. This chapter reviews the recent molecular simulation studies for
CO capture in metal-organic frameworks (MOFs). Emerged as an intriguing class of
2