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 Structure
Property
Correlations
for
Nanoporous
Materials

82744_Book.indb 1 4/13/10 10:17:24 AM

82744_Book.indb 2 4/13/10 10:17:24 AM
 Structure
Property
Correlations
for
Nanoporous
Materials

Abhijit Chatterjee

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

82744_Book.indb 3 4/13/10 10:17:24 AM

CRC Press
Taylor & Francis Group
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© 2010 by Taylor and Francis Group, LLC

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 Contents
Foreword....................................................................................................................ix
Preface.......................................................................................................................xi
Acknowledgments..................................................................................................... xv
Author.....................................................................................................................xvii

Chapter 1. Basic Aspects of Nanoporous Materials...............................................1

1.1 Definition....................................................................................2
1.2 Classification..............................................................................3
1.3 Key Materials of Interest............................................................4
1.4 Major Applications.....................................................................9
1.4.1 Catalytic Applications................................................. 10
1.4.2 Application as Separator, Sensor, and Storage............ 11
1.4.3 Biological Applications............................................... 14
1.4.4 Polymer Applications.................................................. 15
1.5 The Challenges......................................................................... 16
1.6 The Future................................................................................ 17
References........................................................................................... 18

Chapter 2. Molecular Modeling............................................................................ 21

2.1 General Introduction................................................................ 21
2.2 Methods.................................................................................... 23
2.2.1 Quantum Mechanical Calculations.............................24
2.3 Monte Carlo Simulation...........................................................24
2.4 Molecular Mechanics............................................................... 33
2.4.1 Potential Energy Surface............................................. 33
2.5 Molecular Dynamics................................................................ 42
2.6 Challenges................................................................................ 51
References........................................................................................... 52

Chapter 3. Density Functional Theory................................................................. 55

3.1 Basic Wave Mechanics............................................................. 56
3.2 Density Matrix.......................................................................... 59
3.2.1 The Density Matrix and Density Operator.................60
3.3 Chemical Potential................................................................... 63
3.4 Modeling of Chemical Bonds................................................... 67
3.4.1 The Hybrid Orbital Model.......................................... 68
3.4.2 The Molecular Orbital Model..................................... 68
3.4.3 The Electron Tunneling Model................................... 68

82744_Book.indb 5 4/13/10 10:17:25 AM

 vi Contents

3.5 Challenges................................................................................ 72
3.6 Future........................................................................................ 73
References........................................................................................... 75

Chapter 4. Local Reactivity Descriptors............................................................... 77

4.1 Electronic Fukui Function........................................................ 79
4.2 Nuclear Fukui Function............................................................ 82
4.3 Local Softness and Local Hardness......................................... 83
4.4 Philicity.................................................................................... 85
References...........................................................................................92

Chapter 5. Synthesis of Nanoporous Materials.................................................... 95

5.1 Nucleation and Growth............................................................. 95
5.2 Screening Raw Materials....................................................... 103
5.3 Optimizing the Bulk Structure with Varied
Composition........................................................................ 109
5.4 Stability Test with High Temperature and Pressure............... 113
5.5 Microscopic Understanding................................................... 117
References......................................................................................... 119

Chapter 6. Characterization of Nanoporous Materials....................................... 123

6.1 Chemical Composition........................................................... 124
6.2 Spectroscopic Analysis........................................................... 147
6.3 Mechanical Stability............................................................... 164
6.4 Bulk Porosity — Comparison with Adsorption
Isotherms...............................................................................168
References......................................................................................... 176

Chapter 7. Surface Activity Measurement.......................................................... 183

7.1 Surface Area........................................................................... 184
7.2 Surface Chemistry.................................................................. 190
7.3 Surface Confinement.............................................................. 195
7.4 Surface Activity......................................................................204
7.4.1 Adsorption of Alkanes..............................................205
7.4.2 Adsorption and Diffusion of Aromatics....................207
7.4.3 Adsorption of Others, Mainly CO2 and H2...............208
7.5 Chemisorption/Physisorption................................................. 212
7.6 Surface Characterization — A Comparison
with Experimental Tools........................................................ 221
References......................................................................................... 222

82744_Book.indb 6 4/13/10 10:17:25 AM

 Contents vii

Chapter 8. Application of Nanoporous Materials............................................... 229

8.1 Photonic Crystals.................................................................... 229
8.2 Bio‑Implants........................................................................... 231
8.3 Sensors.................................................................................... 233
8.4 Separation............................................................................... 245
References.........................................................................................260

Chapter 9. Catalytic Reactions............................................................................ 263

9.1 Shape Selectivity.................................................................... 263
9.2 Chemical Adsorption.............................................................. 288
9.3 Transition State....................................................................... 298
References......................................................................................... 326
Index....................................................................................................................... 331

82744_Book.indb 7 4/13/10 10:17:25 AM

82744_Book.indb 8 4/13/10 10:17:25 AM
 Foreword
Nanomaterials are a major focus of nanoscience and technology. It is a grow‑
ing field of study attracting tremendous interest, insight, and effort in research
and development around the world for its multidomain applications. Nanoporous
materials are nanostructured materials, which possess unique surface, structural,
and bulk properties with applications in fields such as ion exchange, separation,
catalysis, sensor applications, and molecular isolation and purification in biology.
Nanoporous materials are of scientific and technological importance because of
their immense capability to adsorb and interact with atoms, ions, and molecules
on the large interior surfaces of the nanometer‑sized pores. They also offer new
opportunities in inclusion chemistry, guest–host syntheses, and molecular manipu‑
lations and reactions at a nanoscale for making nanoparticles, nanowires, and other
quantum nanostructures.
Research on nanoporous materials can benefit from computer modeling/simulation
studies not only to explain the experimental observations but to design new materials
of interest. Materials with targeted properties can even be designed computationally.
Modeling techniques can help in formulating the synthesis strategies and character‑
izing the materials from laboratory to pilot plant and further to plant production.
There is a need, in this context, for a book that introduces, reviews the litera‑
ture, and discusses the correlation between the structure and property relationships
of nanoporous materials and that can serve as a “bridge” between experiment and
theory, simulation/modeling while addressing key issues in the area of nanoporous
materials. This book is novel in its kind and its timely publication will be of interest
to experimentalists in this area. Commercially available software is used through‑
out the book, which enhances its utility to the nonspecialist. The author has many
years of research and experience in exploring, learning, and understanding the field
of molecular modeling of nanoporous materials, especially those areas of interest in
catalysis.

Dr. Paul Ratnasamy

INSA‑Ramanujan Research Professor
National Chemical Laboratory
Dr. Homi Bhabha Road
Pune, 411 008 India

ix

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82744_Book.indb 10 4/13/10 10:17:25 AM
 Preface
Nanoporous materials consist of a regular organic or inorganic framework support‑
ing a regular, porous structure. Due to the unique structure–property relation, nano‑
porous materials have huge potential for a wide range of applications.
Molecular modeling techniques are nonexperimental reasonings to explain or
predict chemical phenomena, much of which has in fact fallen under the heading
of computational chemistry; i.e., the application of computation to the solution of
problems in chemistry. Chemical theorists have also used the power of statistical
mechanics to provide a bridge between the microscopic phenomena of the quantum
world and the macroscopic bulk properties.
To compare theoretical calculations with experimental, synthesizing a new mate‑
rial is always a challenge, starting from the choice of raw material, followed by several
characterization techniques to determine the bulk and physical properties of the mate‑
rial. Moreover, the application of the material — for instance, as catalyst — demands
molecular‑level understanding to describe the mechanism, which is unknown most of
the time and hence it is difficult to optimize the respective parameters. The optimiza‑
tion process is time consuming, requires expensive instruments, and still lacks molec‑
ular visualization for precise prediction. To solve this problem, computer simulation
is an effective measure and is cost effective, convenient to study anytime, and has the
potential to include complex, hazardous, real‑world processes. Hence, I believe that
computer simulation is an integral part of applied science, especially for materials.
This book aims to direct the experimentalist toward the capability of simulation
as well as the level of accuracy on which one can depend on the technology. That
belief then only will turn one’s interest to really design the novel material of interest
or explain the chemical phenomenon underneath by comparing the experiments with
computer simulation.
To provide a comprehensive overview of the area of nanoporous materials,
Chapter 1 begins with a definition of nanoporous materials followed by classifica‑
tions, the importance of nanomaterial, current applications, challenges, and future
prospects. The definitions in relation to porous materials and nanoporous materials
are necessary to understand the concept of nanoporous materials in context to their
applications. Following this introduction, the classification and scope of nanopo‑
rous materials are presented. The properties and their characterization and measure‑
ment methods are briefly described before major applications in various fields are
reviewed. Finally, in this chapter, key scientific and engineering issues and future
directions are identified as challenges and opportunities for researchers in this field.
In Chapter 2 the focus is on defining molecular modeling and showcasing different
methodologies to solve the nanomaterial problem. The main focuses are on atomistic
simulation techniques with Monte Carlo and molecular mechanics. Finally, the chal‑
lenges and the future of these techniques within this domain are also discussed.
In Chapter 3 the focus is on introducing a density functional theory (DFT) tech‑
nique to the readers. The methodology is introduced with a context of the basic wave

xi

82744_Book.indb 11 4/13/10 10:17:25 AM

 xii Preface

mechanics, followed by an explanation of density matrix. The chemical potential is

then explained to address the issue with the modelling of chemical bonds. This is the
main motivation of modeling to reproduce and explain the experimental scenarios.
The challenges and the future of the DFT technology are described at the end of this
chapter.
Chapter 4 aims to define and explain localized reactivity descriptors. The local soft‑
ness and hardness paradigm along with philicity concepts has been explained to provide
a basic idea of the concept, as well as to provide a background to discuss and rationale
for the applications of these methodologies to understand the experimental postulates.
Structural complexity evolves during synthesis, and therefore one way of captur‑
ing such complexity within atomistic models is to “simulate synthesis,” as explained
in the Chapter 5. The discussion starts with the nucleation and growth of nanoporous
material, which is where the synthesis process starts in an experimental workroom.
This involves selection of raw materials, which includes changing the chemical com‑
position and optimizing the bulk structure of the varied composition including the
role of metal incorporation. Further demand is to look into the effect of pressure and
temperature in the reaction process. This is performed to mimic the synthesis condi‑
tion and to rationalize the synthesis process of nanoporous materials.
Experiments have their own limitations; thus, the combination of experiment and
computer simulation is necessary to obtain a desired material with specific func‑
tionalities for proper applications. Chapter 6 covers the area of the structural char‑
acterization of the material mainly in terms of chemical composition, spectroscopic
analysis, mechanical stability, and porosity to show the capability of simulation to
justify and validate experimental observations. This also can provide a lot of space
for experimentation where analysis is ambiguous.
The design of new nanoporous materials in terms of their specific applications like
surface adsorption phenomena, sensors, or catalysts for various organic syntheses is
the main theme of Chapter 7. Nanoporous materials are widely used as catalysts
because of their large internal surface area and the consequent presence of controlla‑
ble large voids. Microporous materials like zeolites are mainly used as heterogeneous
redox catalysts in the petroleum industry, in various shape selective reactions, and in
separation. In discussing the catalytic activity of the microporous material, it must
be mentioned that the transition metal–substituted microporous materials (TMSM)
with aluminosilicate or aluminophosphate framework are covering a large part of
the catalysis. TMSM mainly take part in the various oxidative transformations in the
presence of a mild oxidizing agent like hydrogen peroxide or oxygen. A number of
applications in waste treatment processes, including removal of heavy metals and
radioactive species, as well as ammonia, different phosphates, and toxic gases from
water, soil, and air, are due to the unique structural and surface physico‑chemical
properties of microporous materials, such as excellent absorption and ion‑exchange
capacities. The details of these applications are described in Chapter 8, “Application
of Nanoporous Materials.” So, each of the functions demands a specific surface prop‑
erty such as pore architecture, pore size, surface area, and acidity or basicity of the
matrix. Considering the surface properties, adsorption is generally used to character‑
ize the surface structure. However, it is a complicated process and it is difficult to
obtain a molecular‑level scenario on an experimental basis. Thus, simulation can

82744_Book.indb 12 4/13/10 10:17:25 AM

 Preface xiii

play a significant role in simulating the actual situation occurring at the molecular
level by comparing the binding energy or the attachment energy and by comparing
the surface chemistry and producing a result to show the probability of physisorption
and chemisorption.
Nanoporous materials combine with the advantages of porous materials. These
tiny materials provide a huge surface area, controllable pore sizes, morphology, and
capable of any surface‑related applications. Due to their considerably small‑size
porous structure, material properties have increased compared to their bulk coun‑
terpart. Therefore, it is obvious that the revolutionary properties of nanoporous
materials make them a strong contender for its wide range of applications. The
main interest of Chapter 8 is in providing some promising applications of nanopo‑
rous materials, such as (a) photonic crystals, (b) bio‑implants, (c) sensors, and (d)
separation.
Now, the designed material, which is synthetically viable and technically appli‑
cable in terms of pore architecture, metal loading and other related parameters as
established through experimental technique and computer simulation technology
needs to be tested further to confirm the functionality. In Chapter 9 we focus on the
catalytic activity of the nanoporous material. The discussion covers related topics of
catalysis starting from shape‑selective reactions within nanopores, chemical adsorp‑
tion reactions, cracking, and the mechanistic aspect of a reaction using transition
state theory, especially the activation barrier, the intrinsic reaction coordinate, and
the effect of solvent on catalytic reactions. This chapter provides a detailed expla‑
nation of the methodology of simulation, so that one can follow these cases and
approach their own problems for a solution.
I hope this book will convey the significance of the combination of traditional
experimental work and molecular simulation to the researcher. I think this book
will stimulate the interest of bench chemists in molecular modeling and remove the
hurdle of understanding what simulation can provide and how one can successfully
design a matrix for a specific application.

82744_Book.indb 13 4/13/10 10:17:25 AM

82744_Book.indb 14 4/13/10 10:17:25 AM
 Acknowledgments
I would like to take this opportunity to thank all my mentors and collaborators,
Prof. Sukalayan Basu, Dr. Rajappan Vetrivel, Dr. Paul Ratnasamay, Prof. Akira
Miyamoto, Prof. Kazuo Tori, Dr. Takashi Iwasaki, Dr. Toshihige Suzuki, Prof. Fujio
Mizukami, Prof. Paul Geerlings, Prof. John Newsam, Prof. Alfred Mortier, Prof.
Kimiko Hirao, Dr. Sourav Pal, Dr. Asit K. Chandra, and Dr. Debasis Bhattacharya.
My special thanks go to Dr. Rajappan Vetrivel for introducing me to the amazing
world of computer simulation application in the field of nanoporous catalysis and
material science.
I am grateful from the bottom of my heart to my father, Prof. K. N. Chatterjee, for
making me fascinated with chemistry from my school days and my mother for her
continuous encouragement and contemplation.
I wish to specially thank my wife, Dr. Maya Chatterjee. The writing of this book
would not have been possible without her involvement and continuous inspiration.
She has contributed as a collaborator by participating in a very fruitful scientific
discussion to share her experimental experience with nanoporous material synthe‑
sis and reaction, which enriched the book immensely. I am thankful to my daughter
for her patience and help with proofreading. I wish to thank all of my extended
family members.
I also wish to thank all my colleagues in Accelrys for their support and
consideration.

xv

82744_Book.indb 15 4/13/10 10:17:25 AM

82744_Book.indb 16 4/13/10 10:17:25 AM
 Author
Abhijit Chatterjee was born in Chandananagore, a little town near Kolkata,
India. He was a student of Kanailal Vidyamandir and received his Master’s and
Ph.D. from Burdwan University, West Bengal, India. After graduating from
University with his Ph.D. in physico‑analytical chemistry in 1992, he moved to
the National Chemical Laboratory, Pune, India, and worked there until 1995 as a
Research Associate in the Catalysis Division. He exposed himself to the simula‑
tion of catalytic material. He has traveled around the world and collaborated with
many groups in catalysis before settling down in Japan as a researcher in the
field of computational chemistry and established himself in this field with more
than 100 papers in international journals of repute; he has presented invited talks
at many international and national symposiums, and written chapters in books
published by Elsevier, Taylor & Francis, and Wiley. He served as a member of
the editorial board of the International Journal of Molecular Science. He is a
member of many leading scientific societies (ACS, IOP, IZA, etc.). His research
interest is focused on density functional theory and its application on different
materials, especially related to catalysis (zeolite, clay, oxides). He also explored
other materials of interest like composites, semiconductors, and metal clusters to
rationalize the structure–property correlation and finally was involved in deriving
reactivity index, Fukui function, and simpler algorithms to help experimentalists
to design a novel material.

xvii

82744_Book.indb 17 4/13/10 10:17:26 AM

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