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Introduction to Porous Materials

Edited by

Pascal Van Der Voort

Ghent University
Ghent, Belgium

 

Karen Leus

Ghent University
Ghent, Belgium

 

Els De Canck

Recticel NV Insulation
Belgium

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Preface

This book is the first of its kind to discuss the development and applications of porous materials since their early start in the 1950s until now, the end of 2018. It is intended for students interested in materials science at the Masters or undergraduate level, but it is also intended for Ph.D. students who start their research in the field of porous materials.

Surprisingly, we noted that a comprehensive overview of the most important inorganic porous materials, combined with the necessary theory and characterization methods that can be used as a complete course or introduction to the field, does not exist. There are many books and monographs, but they tend to be either a collection of individual papers with less consistency, or they are high level monographs focusing on one type of material only.

The chapters in this book are almost chronological, starting with nature's materials, and then followed by the zeolites, silicas, aluminas, and carbons. After that, we discuss the materials of the twenty‐first century; advanced carbons, PMOs (Periodic Mesoporous Organosilicas), MOFs (Metal‐Organic Frameworks), and COFs (Covalent Organic Frameworks).

We have included one “theoretical” chapter, providing the reader with a solid introduction to the models of adsorption, heterogeneous catalysis, and surface area and pore volume measurements. We believe that this chapter is necessary to be able to understand the rest of the book.

We have made the choice to integrate other theoretical sections in the materials chapters at the point where we need these techniques first. So, solid state infrared spectroscopy is discussed in the silica chapter, XRD (X‐Ray Diffraction) in the zeolite chapter, TEM (transmission electron microscopy) in the MOF chapter, and so on.

The year 1999 was a magical one; in that year, many synthetic new classes of porous materials were reported, including the very famous MOFs and the PMOs. These materials are referred to as hybrid materials, as they contain both inorganic and organic functionalities. The book ends with the COFs. These are basically organic materials, but are often researched in inorganic groups, illustrating that the divisions “organic,” “inorganic,” and “analytical” become more and more obsolete in modern science.

We hope you will enjoy this book and that you will learn a lot from it. We are open to any comments and suggestions you may have regarding the content of this book.

Pascal Van Der Voort

Karen Leus

Els De Canck

April 2019

About the Authors

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Pascal Van Der Voort (1967) started his professional career in 1989 as an assistant at the University of Antwerp, preparing a Ph.D. thesis on the surface decoration of silica, using a technique called “Chemical Surface Coating.” This technique is in fact very similar to the Molecular Layering technique used in the former USSR (Malygin – Saint Petersburg) and the Atomic Layer Deposition method described by Suntola.

Throughout my research career, I have worked on almost every material that is described in this book except for the zeolites, although I was surrounded by zeolite researchers in the group in the early stages and was almost literally walled by large models of zeolites.

So, during my post‐doctoral career, lasting an astonishing 10 years, I continued to work on the beloved silica supports and went to Georgia Tech to use the surface decoration method “Molecular Designed Dispersion,” a name created by Mark White at the time. During that period the MCM‐materials (and later the SBA‐materials) broke through, and I remember looking for the original Mobil patent at Georgia Tech, using these microfilm machines that are guaranteed to give you an incredible headache. In collaboration with Galen Stucky's group, I wrote on my first paper on the MCM‐48 material for catalysis, as I already understood then the benefits of a 3D open pore structure. During a short stay in Montpellier with François Fajula and Anne Galarneau, we continued to work on this topic.

A few years later, I discovered the so‐called “Plugged Hexagonal Mesoporous Silica” (PHTS), a name too difficult to be remembered by anyone. It was a partially blocked and a partially open SBA‐15 variant and I was so proud when it got its own hysteresis loop in the latest IUPAC report on porous materials (hysteresis loop H5).

After a break, I returned to the academic world in 2006, when I was appointed Assistant Professor at Ghent University, where I founded the COMOC (Center for Ordered Materials, Organometallics, and Catalysis) in 2007. We decided to work on hybrid materials, starting with PMOs and porous phenolic resins. The group needed to be built up from scratch, but soon became sizeable with the necessary work force and instruments. So, the research on MOFs started a few years later and the most recent addition to the research are covalent organic materials. Currently, still at Ghent University as a full professor, I have published 265 papers indexed in Web of Science on silica and alumina, clays and layered double hydroxides, mesoporous ordered silicas, PMOs, MOFs, carbons and phenolic resins, COFs, and CTFs.

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Els De Canck (1985) started her career at Ghent University in the COMOC group. Her Ph.D. (2013) was on the development of novel Periodic Mesoporous Organosilicas (PMOs) for heterogeneous catalysis and adsorption. She worked closely with Abdel Sayari (Ottawa) on the development of PMOs for CO2 capture and with Dolores Esquivel (Córdoba) for the catalytic applications.

The PMO group in COMOC made remarkable discoveries. We were the first to create a diastereoisomeric pure ethene bridged PMO, and were the first to report on the thiol PMO, the allyl‐ring PMO and on the easy thiol‐ene click reaction in PMO modification. We work closely with Shinji Inagaki (one of the inventors of PMOs) and with several European groups on PMO materials. Els is now (since 2017) International Lab Officer at Recticel NV Insulation, a Belgian‐founded international company researching and producing polyurethane‐based insulation materials.

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Karen Leus (1985) also started her career at Ghent University in the COMOC group. Her Ph.D. (2012) was on the development of Metal–Organic Frameworks for heterogeneous catalysis. During her post‐doctorate at COMOC, she went to the labs of Herme Garcia and Avelino Corma at ITQ‐Valencia to learn more about nanoparticles in MOFs and oxidation reactions. She has focused a lot on V‐based MOFs, nanoparticles, and ALD, and on mixed‐metal MOFs to tune the breathing behavior of flexible MOFs.

In recent years, she has been focusing on Covalent Triazine Frameworks (CTFs). She did an extensive stay at the labs of Professor Markus Antonietti (MPI Potsdam) and is now initiating a research line on electrocatalysis. In her young career, she has published 50 papers so far, all indexed in the Web of Science and all on MOFs and COFs. She won the Belgian Incentive Award for young researchers.