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Heterogeneous Catalysis
 Heterogeneous Catalysis
Fundamentals, Engineering, and
Characterizations (with accompanying
presentation slides and instructor’s manual)
Giovanni Palmisano
Department of Chemical Engineering, Khalifa University, Abu Dhabi,
United Arab Emirates

Samar Al Jitan
Department of Chemical Engineering, Khalifa University, Abu Dhabi,
United Arab Emirates

Corrado Garlisi
Luxembourg Institute of Science and Technology, Luxembourg
Contents

Preface.................................................................................................................. ix

Chapter 1: Introduction .......................................................................................... 1

1.1 Historical background ............................................................................................ 1
1.2 Fundamental concepts and quantities in catalysis .................................................. 7
1.2.1 Fractional coverage .....................................................................................7
1.2.2 Catalytic activity .........................................................................................7
1.2.3 Conversion, yield, and selectivity .............................................................11
1.3 Importance of heterogeneous catalysis in today’s industry ................................... 17
1.3.1 Ammonia synthesis ...................................................................................18
1.3.2 Sulfuric acid production ............................................................................19
1.3.3 Catalytic cracking .....................................................................................20
1.3.4 Polymerization of alpha-olefins ................................................................21
1.4 Questions and problems ....................................................................................... 22
References ................................................................................................................... 23

Chapter 2: Fundamentals of the adsorption process ............................................... 27

2.1 Physical and chemical adsorption ........................................................................ 27
2.2 Thermodynamics and energetics of adsorption .................................................... 36
2.2.1 Heat of adsorption.....................................................................................37
2.2.2 Binding energy of adsorbates ....................................................................39
2.3 Kinetics of adsorption .......................................................................................... 42
2.3.1 Adsorption time ........................................................................................42
2.3.2 Adsorption rate .........................................................................................44
2.3.3 Potential energy diagrams .........................................................................47
2.3.4 The Elovich equation in chemisorption kinetics ........................................54
2.3.5 Desorption rate .........................................................................................56
2.4 Questions and problems ....................................................................................... 59
References ................................................................................................................... 60

v
vi Contents

Chapter 3: Adsorption models, surface reaction, and catalyst architectures ............. 63

3.1 Adsorption isotherms and their classification ....................................................... 63
3.1.1 Langmuir isotherm ....................................................................................68
3.1.2 Henry’s isotherm.......................................................................................70
3.1.3 Freundlich isotherm ..................................................................................71
3.1.4 Temkin isotherm .......................................................................................72
3.1.5 BET isotherm............................................................................................72
3.1.6 Potential theory of Polanyi ........................................................................75
3.1.7 Recent approaches to model adsorption isotherms ....................................77
3.2 Adsorption isobars and isosteres .......................................................................... 79
3.3 Models for surface reactions ................................................................................ 81
3.4 Catalysts, cocatalysts, and supports...................................................................... 86
3.4.1 Catalyst supports .......................................................................................87
3.4.2 Cocatalysts ................................................................................................92
3.5 Questions and problems ....................................................................................... 95
References ................................................................................................................... 97

Chapter 4: Surface area and porosity ...................................................................101

4.1 Estimation of the surface area ............................................................................ 101
4.1.1 Gravimetric and dynamic methods ..........................................................102
4.1.2 Volumetric methods ................................................................................104
4.2 Estimation of porosity and pore size .................................................................. 108
4.2.1 Dubinin Radushkevich and Dubinin Astakhov methods ......................110
4.2.2 Horvath Kawazoe method .....................................................................110
4.2.3 Saito Foley method ...............................................................................112
4.2.4 Barrett Joyner Halenda method ...........................................................113
4.2.5 Dollimore Heal method .........................................................................114
4.2.6 Density functional theory ........................................................................115
4.2.7 Mercury porosimetry...............................................................................116
4.3 Hysteresis and capillary condensation ................................................................ 117
4.4 Pore models—morphology................................................................................. 123
4.5 Mechanisms of diffusion within catalyst pores .................................................. 128
4.6 Questions and problems ..................................................................................... 135
References ................................................................................................................. 138

Chapter 5: Catalytic reaction engineering .............................................................141

5.1 Catalytic reaction steps ...................................................................................... 141
5.1.1 External diffusion ...................................................................................142
 Contents vii

5.1.2 Internal diffusion.....................................................................................144

5.1.3 Adsorption ..............................................................................................144
5.1.4 Surface reaction ......................................................................................147
5.1.5 Desorption ..............................................................................................149
5.2 Reaction mechanism and the rate-limiting step .................................................. 149
5.3 Catalytic reactor design ..................................................................................... 155
5.4 Diffusion and reaction in heterogeneous catalysis .............................................. 162
5.4.1 Mass transfer-limited and reaction rate-limited reactions ........................162
5.4.2 Diffusion with reaction in a catalyst pellet ..............................................164
5.4.3 Thiele modulus .......................................................................................168
5.4.4 Internal and overall effectiveness factors ................................................170
5.4.5 Weisz Prater and the Mears criteria ......................................................175
5.5 Multiple steady states and thermal hysteresis ..................................................... 176
5.6 Catalyst deactivation and regeneration ............................................................... 179
5.7 Questions and problems ..................................................................................... 187
References ................................................................................................................. 191

Chapter 6: Green heterogeneous catalysis ............................................................193

6.1 Conversion of biomass to biofuels ..................................................................... 194
6.1.1 Biomass feedstock ..................................................................................194
6.1.2 Traditional thermochemical processes for catalytic conversion of
biomass ...................................................................................................197
6.1.3 Aqueous-phase reforming for hydrogen and alkanes production .............202
6.2 Electrocatalysis .................................................................................................. 205
6.2.1 Fundamentals of electrocatalytic processes .............................................205
6.2.2 Water electrolysis ...................................................................................209
6.2.3 Electrochemical CO2 reduction ...............................................................214
6.3 Photocatalysis .................................................................................................... 218
6.3.1 Fundamentals of photocatalytic processes ...............................................218
6.3.2 Water and wastewater purification ..........................................................224
6.3.3 Organic synthesis ....................................................................................230
6.4 Questions and problems ..................................................................................... 234
References ................................................................................................................. 237

Chapter 7: Characterization techniques ................................................................243

7.1 X-ray diffraction .............................................................................................. 243
7.2 X-ray photoelectron spectroscopy .................................................................... 250
7.3 X-ray absorption spectroscopy ......................................................................... 254
7.4 Electron microscopy ........................................................................................ 259
viii Contents

7.5 Infrared and Raman spectroscopy .................................................................... 266

7.6 Temperature-programed methods ..................................................................... 272
7.7 Electrochemical techniques .............................................................................. 277
7.7.1 Voltammetry ......................................................................................... 279
7.7.2 Electrochemical impedance spectroscopy.............................................. 283
7.8 UV visible and photoluminescence spectroscopy ........................................... 286
7.8.1 UV visible spectroscopy...................................................................... 286
7.8.2 Photoluminescence spectroscopy .......................................................... 290
7.9 Solid-state nuclear magnetic resonance and electron paramagnetic
resonance spectroscopies.................................................................................. 293
7.9.1 Nuclear magnetic resonance.................................................................. 293
7.9.2 Electron paramagnetic resonance .......................................................... 296
7.10 Computational tools: density functional theory and molecular
dynamic simulations ........................................................................................ 301
7.11 Questions and problems ................................................................................... 305
References ................................................................................................................. 309

Index ..................................................................................................................315
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Preface
Heterogeneous catalysis is a multidisciplinary subject of relevance to a large number of
students, scholars, practitioners, and industries, touching in different ways chemical
engineering, chemistry, and materials science. Its significance is evident looking at the
current applications in the industrial synthesis of a wide range of commodities and fine
chemicals, as also at the continuous efforts in the scientific activities targeting the
preparation of more efficient catalysts followed by characterizations aimed at the
understanding of their performance, along with the investigations on novel catalytic
processes and reactors.
In the last decades, a number of textbooks and scientific books have appeared dealing with
specific aspects of catalysis or trying to achieve a more holistic presentation of the
fundamentals and applications.
Unlike other disciplines, heterogeneous catalysis does not allow for a straight and rigorous
theoretical development of its principles to justify observed phenomena, since an all-
embracing theory has not been developed to date, due to the complexity of the mechanisms
behind it.
For this reason, former authors have usually covered only a few fundamental aspects of
catalysis, moving forward to discuss the implications in terms of applications and materials’
characterizations.
This book presents an overview of the fundamentals of heterogeneous catalysis in
Chapter 1, Introduction, and Chapter 2, Fundamentals of the Adsorption Process, covering
the basic concepts and quantities for the less experienced reader with few examples of
industrial catalytic processes, followed by the adsorption theory starting with the molecular
orbital approach. The thermodynamics and kinetics of adsorption/desorption are described
with graphical exemplifications for a better understanding. A handful of examples taken for
literature are also provided to guide the reader through the complex interpretation of the
catalysts’ features. The Focus sections in these two chapters report case studies on how the
configuration and the supports of catalysts can affect their electronic properties and activity,
and present a number of solved numerical examples.

ix
x Preface

Chapter 3, Adsorption Models, Surface Reaction, and Catalyst Architectures, describes the
traditional adsorption models with an overview on recent developments covered in the
Focus sections, which are found throughout the book and point mostly to the correlation
between materials preparation/properties and catalytic performance, along with numerical
examples. The chapter ends with the models for surface reaction and the role of cocatalysts
and supports.
Chapter 4, Surface Area and Porosity, deals with the assessment of the surface area and
porosity, with insights on the old and more recent hysteresis classifications and models to
estimate porosity and pore size distribution. This chapter presents a significant number of
examples taken from recent literature that are intended to develop the reader’s skills on the
interpretation of isotherms with hysteresis loops and pore size distributions. Focus sections
describe the working principles and the equipment used for the assessment of the textural
properties of catalysts, numerical examples on the BET equation, tortuosity and diffusivity,
along with a case study on the design of catalysts for the enhancement of diffusion.
Overall, the first four chapters give a unique overview of the fundamentals of catalysis,
inclusive of all the kinetic and thermodynamic aspects related to adsorption/desorption,
followed by a detailed and updated presentation on the assessment of surface area and
porosity.
Chapter 5, Catalytic Reaction Engineering, covers the reaction engineering topics of
heterogeneous catalysts, particularly useful for readers without a background in chemical
engineering who did not study catalytic reaction engineering and reactor modeling. The
Focus sections describe different types of catalytic reactors, the modeling of diffusion and
transport in porous catalysts, the design and preparation of catalyst pellets for fixed bed
reactors, and they also include solved reaction engineering problems.
Chapter 6, Green Heterogeneous Catalysis, is a survey on green catalysis, ranging from
electrocatalysis to photocatalysis and the catalytic conversion of biomass to biofuel. The
chapter is focused on the applications after a quick introduction to the principles of these
three green approaches. Focus sections cover the preparation aspects of recently developed
catalysts and the connection between catalyst properties and activity/selectivity.
To conclude, the most popular characterization techniques used for solid catalysts are
discussed in Chapter 7, Characterization Techniques, where the fundamentals of all
techniques are explained followed by examples of their applications. This chapter is
approachable by both a newcomer and a more expert reader who would like to be
introduced to a characterization technique he/she is not familiar with and analyze few data
describing catalysts reported in the literature. The application of in-situ techniques, the
characterization of catalysts during their synthesis, and the description of a synchrotron
facility are among the topics covered in the Focus sections.
 Preface xi

The book, which is reader friendly and accessible to a heterogeneous readership ranging
from senior undergraduate students up to Master’s and PhD level students, along with
experienced scholars and practitioners, is supplemented with Presentation Slides for each
chapter, useful for classes, seminars, workshops. An Instructor’s Manual is also available
upon request with the answers to the proposed questions and problems. Case studies
addressing materials preparation among other topics and numerical examples can be found
in the Focus sections of each chapter. End of chapter Questions and Problems are proposed
for self-tests and as a reference for assignments/exams to be arranged by instructors.
The authors are thankful to Mr. Mujeeb Oladipupo Kareem for his contribution to the
Instructor’s Manual and his useful suggestions.

Giovanni Palmisano
Samar Al Jitan
Corrado Garlisi

To access the Instructor’s Manual including answers to proposed questions and problems
please go to the following website and register to use: https://textbooks.elsevier.com/web/
Login.aspx?MREDIR=../web/Manuals.aspx?isbn=9780323898454
 CHAPTER 1

Introduction
Catalytic reactions are subdivided into two distinct categories depending on the phases of
both the catalyst and the reacting mixture. If the catalyst is in solution with at least one of
the reactants, then the process is defined as homogenous catalysis. On the contrary, if the
process involves more than one phase (e.g., solid catalyst with reactants in the liquid or gas
phase), then it is defined as heterogeneous catalysis. Of these two types, heterogeneous
catalysis is more common. This is mainly attributed to the simple and complete separation
of the reaction products from the solid catalyst. Catalysts are quite valuable and their reuse
is in high demand. Hence, the possibility of catalyst recycling makes heterogeneous
catalysis economically much more attractive.
Today, heterogeneous catalysis plays a key role in many important industrial processes,
since it involves c. 80% of the industrial chemical conversions. As such, it is applied in
(1) the production of organic and inorganic chemicals, (2) crude oil refining and
petrochemistry, (3) environmental protection, and (4) energy-conversion processes.
Heterogeneous catalysis takes place through surface reactions, with adsorption of at least
one of the reactants on the catalyst surface as the initial step.
A catalyst is defined as a substance that increases the rate of a chemical reaction without
itself undergoing a chemical change. A good catalyst must possess high activity, the desired
selectivity, and long-term stability. The activity of a catalyst may be assessed via different
parameters, including its turnover frequency (TOF), conversion, yield, and, most
importantly, selectivity. These fundamental catalysis terms will be thoroughly defined and
explained within this chapter after a historical account of heterogeneous catalysis.

1.1 Historical background

The Swedish chemist Jöns Jacob Berzelius has been credited with coining the term catalysis
(from the Greek kata-, “down,” and lyein, “loosen”) in 1835. In an attempt to connect a
series of observations made by other scientists in the late 18th and early 19th centuries,
Berzelius concluded that in addition to affinity, there was a further force, namely, the
catalytic force, able to trigger decomposition in bodies and form new compounds. Some of
the most significant studies that served as a background for Berzelius to formulate the

Heterogeneous Catalysis.
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2 Chapter 1

concept of catalysis were the transformation of starch to sugar by acids observed by Gustav
Kirchhoff, the enhanced combustion of a variety of gases in the presence of platinum
observed by Humphry Davy, and the oxidation of alcohol to acetic acid in the presence of
fine platinum powder [1].
In 1834 Michael Faraday observed the catalytic action of platinum that catalyzed the
spontaneous combustion of hydrogen and oxygen in water electrolysis. He was the first to
introduce the concept of what we know as adsorption and hypothesize that catalytic
reaction occurs on the catalyst surface following the simultaneous adsorption of the
reactants involved in the process [2]. Presently, water electrocatalysis is being widely
applied in the industrial production of high-purity hydrogen [3].
An important contribution to catalysis as we know it now was given by Wilhelm Ostwald
in 1897, who defined a catalyst as a material that modifies the reaction rate without
appearing in the final products, thereby recognizing catalysis as a kinetic phenomenon for
the first time [4]. In the same years, Paul Sabatier investigated the hydrogenation reaction
catalyzed by metals, such as nickel, other than platinum. He proposed the formation and
decomposition of intermediate complexes with the surface catalysts, resulting in a lowering
of the Gibbs energy of the system [5].
A fundamental step in catalysis occurred in 1909, when the chemist Fritz Haber discovered
that a significant amount of ammonia could be generated from hydrogen and nitrogen in the
presence of osmium and uranium catalysts. The potential for industrial application of these
processes could be increased by working at high pressure, and to that end, the Haber’s
laboratory apparatus was converted to a high-pressure large-scale industrial apparatus by
Carl Bosh. Afterward, Badische Anilin und Soda Fabrik (BASF) started a large program to
develop a cheaper and effective catalyst. Alvin Mittasch, together with his colleagues, Wolf
and Stern, identified magnetite (Fe3O4) as the best candidate for ammonia production [6].
In the wake of these results, in 1923, BASF also developed the first plant for the synthesis
of methanol from syngas produced from coal in the presence of ZnO/Cr2O3 catalysts
operating at c. 400
C and 200 bar [7].
In 1938 Fischer and Tropsch studied the conversion of syngas to hydrocarbons and alcohols
catalyzed by metals such as cobalt and iron (i.e., FischerTropsch synthesis) [8].
In the early 20th century, a greater understanding of the mechanisms behind the catalytic
processes was gained thanks to the studies conducted by Irving Langmuir on adsorption
and Hugh Stott Taylor on surface active sites. The latter especially focused on the
heterogeneity of the catalyst surface, which usually presents vacancies, kinks, terraces,
ledges, etc., being hosting sites where metal atoms have different coordination numbers and
thus catalytic activities [2]. Meanwhile, Stephen Brunauer, Paul Hugh Emmett, and Edward
Teller explained the physical adsorption of gas molecules on a solid surface; Eric Rideal,
 Introduction 3

Mikhail Temkin, Michel Boudart, and many others provided a valuable contribution to a
greater understanding of the kinetics of catalytic reactions [9].
In the 1930s catalytic cracking was introduced in the petroleum refining industry. This
process allowed to break the CaC bonds in large petroleum molecules, converting them
into high-octane fuels using an aluminum chloride catalyst (i.e., FriedelCrafts catalysts).
Yet, the foundation of modern petroleum refining was established in 1942 with the
commercialization of fluid catalytic cracking (FCC). These processes enabled to maintain
the catalyst particles in suspension by a stream of vaporized hydrocarbons blown through
the reactor and successively passed through the regenerator [7].
An important landmark was the advent of synthetic zeolites, aluminosilicate catalysts, in the
1960s, when amorphous silicaalumina catalysts used in FCC were gradually replaced by
synthetic faujasites (zeolites X and Y) (Fig. 1.1). The zeolite catalysts were orders of
magnitude more active than the conventional ones and ensured a much higher yield of
gasoline, the key product in FCC plants. This type of catalyst, characterized by a broad
variety of structures, rapidly found applications in further processes in petroleum refining
and basic petrochemistry. Fig. 1.1 shows some of the typical structures, along with the
distinctive micropore systems and dimensions of zeolites. Among these, the synthetic
zeolite ZSM-5 is one of the most used industrially, being the prototype of shape-selective
catalysts and finding application in the synthesis of ethylbenzene, conversion of methanol
to gasoline, and isomerization of xylenes [10].

Figure 1.1
Four examples of zeolite structures with their micropore system and dimensions. Source: Reproduced
from [10].
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4 Chapter 1

From the 1960s, the evolution of the transportation industry, the increase in industrial
activity, and the severe rise in air-born pollutants have led to the establishment of new laws
that regulate vehicle and stationary emissions [11]. Driven by these regulations, global
attention and widespread interest in environmental catalysis grew substantially.
Environmental catalysis addresses problems relating directly to emission control, NOx
removal, volatile organic compound conversion, and waste treatment. Presently, the
research focus of environmental catalysis has expanded from pollutant abatement to include
pollutant prevention. Accordingly, new catalytic routes have been explored for the synthesis
of value-added products without the formation of undesirable pollutants and for the
production of new clean fuels with low sulfur content [12].
The engineering of semiconductors, especially of titanium oxide, has led to growing
attention toward heterogeneous photocatalysis during the 20th century, which nowadays is a
hot topic in applied catalysis for the possibility to efficiently degrade any organic pollutants
and produce alternative clean fuels by the irradiation of a catalyst. The earliest reference on
photocatalysis dates back to 1911, when Alexander Eibner studied the effect of the
illumination of ZnO on the bleaching of Prussian blue. However, in the absence of practical
applications, these processes remained a curiosity for much of the 20th century. In the
1970s Akira Fujishima and Kenichi Honda [13] observed the electrochemical photolysis of
water in a cell consisting of an ionically conducting separator and a rutile TiO2 electrode
irradiated by near-UV light and connected to a platinum counter electrode via an electrical
load (Fig. 1.2). The HondaFujishima effect attracted the attention of the whole scientific

Figure 1.2
Schematic of the electrochemical cell employed by Fujishima and Honda for the photolysis of
water: (1) rutile electrode, (2) platinum counter electrode, (3) ionically conducting separator,
(4) gas burette, (5) load resistance, and (6) voltmeter. Source: Reproduced from [14].
 Introduction 5

community because of its potential to overcome the dependence on petroleum by producing

clean hydrogen from abundant and inexpensive water and sunlight.
Energy-efficient catalytic processes such as those that utilize renewable energy sources
have also seen a very fast development [12]. One example is the industrial production of
hydrogen through renewable energy-powered water electrocatalysis in a process known as a
power-to-gas (PtG). Fig. 1.3 shows the main components of a PtG system in which
electricity is converted into hydrogen by water electrocatalysis. The produced hydrogen is
stored to be later reconverted back into electricity either through fuel cells or hydrogen
combustion engines. Other applications of hydrogen are presented in Fig. 1.3. Solar and
wind energy are the most commonly applied renewable energy sources in PtG systems. Due
to strong fluctuations in supply, however, renewable power is frequently coupled with
public electricity from the grid. As of 2013, 12 pilot-scale PtG systems have utilized solar
energy as a source of renewable power for water electrocatalysis, while wind energy has
been applied in nine other pilot-scale plants of the same [15].
The application of automotive catalysts as principal emission-control tools in the
detoxification of exhaust gases has seen unqualified success. Here, hydrocarbons and
carbon monoxide are oxidized into CO2 and water, while NOx is reduced to N2 and O2.
Shortly following their positive implementation in US vehicles of the model year 1975,
automotive catalysts were also later adopted in Japan and Europe sometime in the 1980s
[16]. Initially, Pt and Pd, in different proportions, were chosen as catalysts for the oxidation
reaction. However, after exhibiting a significantly enhanced activity in the catalytic
reduction of nitrogen oxides, Rh was also later introduced into the automotive catalytic
system [17]. Currently, Pd, Pd/Rh, Pt/Rh, and Pt/Pd/Rh catalysts are all in commercial use.

Figure 1.3
The main components of a power-to-gas system and the various types of applications for it.
Source: Reproduced from [15].
6 Chapter 1

In the 21st century, catalytic asymmetric synthesis methods, developed by Knowles, Noyori,
and Sharpless, have seen great significance in the industrial production of pharmaceuticals
and agro-chemicals [18]. Catalytic asymmetric synthesis refers to catalytic methods in
which one of the enantiomers is formed in preference to the other. Here, a chiral catalyst is
used to produce large quantities of an optically active compound from a precursor that may
be chiral or achiral. On this basis, many organic chemists have recently developed
numerous methods that convert prochiral substrates into chiral products with high
enantioselectivity.
Pd-catalyzed carboncarbon bond-forming reactions, developed by Heck, Negishi, and
Suzuki, have also had a huge influence on synthetic organic chemistry during the 21st
century [19]. A large number of natural products and biologically active compounds in the
fine chemical and pharmaceutical industries are presently being synthesized by these Pd-
catalyzed cross-coupling reactions. This is mainly attributed to the mild reaction conditions
and the tolerance of a wide range of functional groups. In Pd-catalyzed cross-coupling
reactions, two molecules assemble on Pd via the formation of metalcarbon bonds. The
carbon atoms bound to Pd are, therefore, in very close proximity to one another.
Accordingly, the two carbon atoms couple together and a new carboncarbon single bond
is formed.

Focus 1.1: Effect of Zn:Cr ratio on the structure and reactivity of ZnO/Cr2O3
catalysts for methanol synthesis
Advances on the ZnO/Cr2O3 catalyst developed by BASF in 1923 for the synthesis of
methanol from syngas have been recently achieved by Song et al. [20] who studied the
effect of different Zn:Cr ratios—from 100:0 to 0:100—on the catalytic performance. The
catalysts with ratios from 65:35 to 55:45 consisted of ZnCr2O4 spinel with a low degree of
crystallinity and high surface area. In particular, the sample with 65:35 exhibited the
highest reactivity due to the optimum Zn:Cr ratio corresponding to that of the
hydrotalcite-like precursor Zn4Cr2(OH)12CO3. This precursor, formed during the synthesis
of the catalysts by coprecipitation, decomposed during calcination to the
nonstoichiometric ZnCr spinel, which is the active phase of ZnO/Cr2O3 in methanol
synthesis. On the other hand, the lower activity of Cr-rich catalysts was mainly ascribed to
the formation of chromates during the calcination, having a detrimental impact on
methanol synthesis.
Density functional theory calculations showed that (100) surface of the spinel has favorable
oxygen vacancy formation energies. Fig. 1.4 displays the calculated local structure for the
spinel with excess 60% Zn content (26.66% doping). The nonstoichiometric surface is
terminated by an amorphous-like thin layer of ZnO, which is the active phase for methanol
production, since it possesses a low oxygen vacancy formation energy, as well as not too
strong adsorption of hydrogen and carbon monoxide.
(Continued)
 Introduction 7

Focus 1.1: Effect of Zn:Cr ratio on the structure and reactivity of ZnO/Cr2O3
catalysts for methanol synthesis (Continued)

Figure 1.4
Local structure for the spinel structure with 26.66% Zn doping. Source: Reproduced from [20].

1.2 Fundamental concepts and quantities in catalysis

1.2.1 Fractional coverage

The extent of surface fractional coverage θ indicates the portion of catalytic sites occupied
by an adsorbed species (adsorbate) and it can be defined in the following way:
Number of adsorption sites occupied
θ5 (1.1)
Total number of adsorption sites
This quantity is usually calculated from the volume of adsorbate adsorbed (V) by θ 5 V/Vm,
where Vm is the volume of adsorbate corresponding to a complete monolayer (i.e., a single
layer of atoms or molecules adsorbed on the surface of a catalyst). The volumes V and Vm
are of the free gas measured in the same conditions of temperature and pressure [21]. When
θ reaches the value of 1, the surface catalytic sites are completely occupied, and adsorption
of further layers is possible only on top of the first one (multilayer adsorption), as it will be
widely discussed in the following chapters.

1.2.2 Catalytic activity

The catalytic activity is related to the ability of a catalyst to change the reaction rate, which, in
turn, can be defined in many ways depending on the reaction system. In general, the reaction rate
(R) is a function of temperature and partial pressure or concentration of the reactants. It can be
8 Chapter 1

expressed as the product of an apparent coefficient (k) and a function ( f ) of the partial pressure
(gassolid system) or concentration (liquidsolid system) of the reactant i:
R 5 k f ðpi Þ ðgas2solid systemÞ (1.2)
R 5 k f ðci Þ ðliquid2solid systemÞ (1.3)
where pi and ci are the partial pressure and concentration of the reactant i, respectively. The
reaction rate expresses a change in the number of moles (of a reactant or product) per unit
time per unit mass (or surface) of a catalyst. The rate constant can be expressed through the
Arrhenius equation:


2 ERT
k 5 Ae (1.4)
where A is the preexponential factor not changing with temperature, R is the universal
gas constant, T is the absolute temperature, and E is the apparent activation energy. E
is usually different from the true activation energy since the concentration of the
reactant at the catalyst surface may be temperature dependent, although the catalyst
structure may not be affected by temperature changes. To avoid resorting to the
activation energy, most of the time catalytic activity is expressed in terms of TOF,
which is defined as the number of molecular reactions or catalytic cycles (n) per active
site of the catalyst per unit time. Being a reaction rate, TOF depends on the reaction
conditions including temperature and composition of the reacting system. In general,
TOF can be expressed as:
1 dn
TOF 5 (1.5)
S dt
where t stands for reaction time and S indicates the number of active sites. For the most
relevant heterogeneous catalytic reactions in industry, TOF is in the range of
1022a102 s21. The main difficulty in determining TOF lies in counting active sites.
Moreover, sites may not be all identical. In such situations, S is usually replaced by the
total exposed area, mass, or volume of the catalyst [7].
Fig. 1.5 presents the results of a study conducted on the catalytic gas-phase hydrogenation
of p-nitrobenzonitrile (p-NBN) to p-aminobenzonitrile (p-ABN) using a series of oxides
as support for the catalyst consisting of gold (Au) particles with a mean size 38 nm.
Different supports resulted in different Au nanoparticle sizes, impacting the hydrogen
chemisorption (Fig. 1.5A) and TOF (Fig. 1.5B). The variation of the TOF with the mean
Au size coincided with that observed for H2 uptake, indicating a strong correlation
between the hydrogenation rate and H2 dissociation capacity. The reduced TOF at small
Au size (,3 nm) is due to the semiconducting properties of the catalysts to the detriment
of the metallic ones [22].
 Figure 1.5
Variation of (A) H2 uptake and (B) TOF of p-NBN with metal particle size for the hydrogenation
of p-nitrobenzonitrile over Au catalysts supported on various oxides. Source: Reproduced from [22].

Focus 1.2: Single-atom catalysis for hydrogen evolution reaction

Single-atom catalysis has been a hot topic in research over the last few years. Given the high cost of
many catalytic materials, especially noble metals, reducing the nanostructures to atomically
distributed metal centers supported on a suitable catalyst can considerably decrease metal usage
and maximize atom efficiency. A recent study in this area reports the enhanced catalytic activity of a
single-atom Pt supported on nanoporous (np) nonstoichiometric cobalt selenide (denoted as Pt/np-
Co0.85Se) catalyst [23]. The atomic engineering of np-Co0.85Se by single Pt atoms doping is an
effective strategy to produce a robust electrocatalyst for hydrogen evolution reaction (HER), ensuring
a TOF much higher than those achieved by np-Co0.85Se alone and many reported catalysts.
Fig. 1.6 depicts the schematic of the HER mechanism over Pt/np-Co0.85Se in neutral media.
The water molecules are selectively adsorbed on the Co sites. Later on, H2O is dissociated into
intermediate Hads and OHads by Co sites. The formed Hads can be adsorbed on a nearby
empty Co site or Pt site and be finally converted into H2.

Figure 1.6
Schematic illustration of the HER mechanism over np-Co0.85Se catalyst. HER, Hydrogen evolution
reaction. Source: Readapted from [23].
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 Damascus

The first charm of Damascus as a whole city lies in the contrast

which those brown sandhills behind it make with the green strip of
the Barada Valley. Journeying from Ludd through the monotony of
lank, brown growth that straggles to the horizon from the road, you
give up hope of ever seeing foliage again, until you pass El Kunneitra.
Then you see the green of Barada; and it is the richer for the hills
behind it—browner, more desolate by far, than any landscape
skirting Galilee or the Jordan. Far up the clay feet of those rocky hills
straggles the brown-and-white suburb of Salahiye, all square-built
and flat-topped—from the distance like bricks inserted in the clay
soil. The line of hills is cleft cleanly by the Pass, the scene of that
hideous slaughter by our machine guns. If you climb into the fringe
of Salahiye you see the curious shape of Damascus—a jagged comet-
form, all the angles and serrations of the brown tail defined with
unnatural clearness by the depth of the green about it. In the
amorphous head are a few minarets—like jewels. In Cairo there are
too many minarets as you look from the Bey’s Leap: they protrude
like a porcupine’s quills. In Damascus the city’s flat brownness is just
relieved by them. When we came to Damascus it was drought-
stricken. Soon afterward, it rained torrentially for a day. Then the
sun shone and drew from the city such colour as we never dreamed
was there. Nor had we dreamed that the trees were dusty—so green
they seemed after the southern country. But, washed, they helped to
throw up the wonderful colour of “that great city,” as it is called in
Scripture.
It is a relief to be delivered from the sight of the everlasting cactus-
hedge of the southern towns. The cactus does flourish in Damascus;
but so thick is the foliage that it is lost in the mass. You cannot look
down on Nazareth without being obsessed by the ubiquitous pest.
You can look down on Damascus and be unconscious of it. It
straggles about the leafy roads in patches beside the mud walls. That
you can bear, because it does not rise above the all-enclosing foliage.
The smells of Damascus you will remember for ever. Cairo is clean
by comparison: the alleys of Cairo are not foul. The stinks of
Damascus are literally overpowering. There is offal, refuse, foul
puddles in every street of the Bazaars. The Abana is a foul river. “Are
not Abana and Pharpar, rivers of Damascus, better than all the
waters of Israel”? The answer is: Certainly not. There is an ill-
kemptness about the place that carries Oriental slackness a bit too
far. In the streets that thread the heart of the city are ruts and holes
that break the springs of M.T. every day. The tramline protrudes
eight inches. This gives rise to deadlocks in traffic that hold up
movement for an hour. Incredibly narrow and tortuous are the
highways of the city. The only decent road is that which skirts the
fountained promenade near the Hedjaz Station. I am sure the
Damascans look on this bit of orderliness as a Western intrusion;
just as I am sure that if they found themselves in an English town
guileless of smells they would call it insipid....
In the bazaars there is a baffling complexity of colour, of race, of
wares. The Mousky is less heterogeneous. In the Square, in the street
which is called Strait, in the gold bazaar, grain bazaar, sweets bazaar,
silk bazaar, you have all the various colour of tarbooshed Cairo, and
more. Here the soldiers of the King of the Hedjaz throng; there is
endless variety in their clothes and their flowing head-dress. The
Moslem women, who veil their faces, affect far more variety than the
Mohamedan women of Cairo, with their yashmaks. The French are
here. The Australian hat and plume is everywhere. I never saw so
great a number of Australian soldiers moving at random in any city.
There is great jostling in these narrow streets, more than the normal
jostling you get in any crowd.
The dusty bazaars are in semi-darkness; their streets bear a
covered roof of iron; they must get protection from rain. In Cairo all
is open; for there it rains but rarely. Not only are the bazaar streets in
Cairo without roofs that would stop a shower, but the shops,
themselves, full of treasures. Here the rain comes in a deluge. From
some of the street roofs the enemy had taken the iron for military
use. What the state of these roofless streets will be when the rains
come is sad to think. They will be flooded all winter.
Except that there is greater diversity of peoples—both buyers and
sellers—the bazaars of Damascus are much like those of the Mousky.
There are the same well-defined areas for specific commodities; the
same little cubicles for shops, where vendors squat and “reach for
things”; there is the same voluble haggling—the same conversations
carried on in tones that you would first mistake for quarrelsome;
there are the same crying, peripatetic vendors of limonade, quoit-
shaped cakes and toffee; the shoe-blacks are here, but they are ahead
of Cairo, with their gongs to attract the uncleanly-shod. There is a
more incessant stream of laden donkeys through the bazaars here. In
Cairo the donkeys are chiefly for pleasure riding; here they are
mercantile, over-laden with the striped sacks of grain and fabric.
There are additions to the bazaars of Cairo in the goldsmiths’ bazaar,
the sweets bazaar. The goldsmiths work with their blowpipes and
tiny forges and tiny tools, moulding and fashioning. It is curious to
see the workshop as part of the sale-shop. The belts, brooches, rings
and trays exposed for sale in a showcase were made two yards away
by that cunning Oriental fashioner squatting on his haunches. The
sweets bazaar tempts you hideously. Eastern nutted sweets and
Turkish-delight and toffees look as well as they taste. Mere assorted
chocolates—such as you get at Groppi’s—are crude by comparison.
There are great serpentine coils of Turkish-delight lurking in icing-
sugar—nut toffee that is all nuts—none of your miserable paucity of
nuts such as one gets in English almond-rock: nuts form the matrix
here.... But enough of that; here, if ever, you are tempted to generate
a liver the size of your hat.
Public baths abound in the heart of the bazaars. Fronting the street
is the final, open, divaned, cooling-off room—an amphitheatre of
couches upholstered with a kind of gay-coloured towelling. A
fountain plays in the midst. The bathed sit swaying in the ecstasy of
reaction from the steam, with closed eyes. No Roman ever bathed
more voluptuously. No one minds your going in nor your penetrating
to the bowels of the establishment. Room after room you pass, with
swinging doors; each is hotter than the last. In the last, and hottest
room, the smell of man is overpowering; you hastily retrace your
steps through the series of chambers and regain the comparative
sweetness of the bazaars.
Foul as this city may be, there is beauty in every foot of it. The
beauty of Cairo lies rather in the view you get of “chunks” of it—the
vista of the street, the space of a market-place, the mass of a mosque.
Here the beauty lies in little pieces of wall, looked at minutely, in a
tiny piece of domestic architecture. It is a beauty in colour rather
than in form. Form in Cairo counts for much—in Damascus for
almost nothing. Here there is dilapidation in a degree undreamt of in
Cairo. But dilapidation does not necessarily make for beauty, though
some people think it does. I believe the beauty of colour in Damascus
lies in extreme age—in the mellowing of age. After Cairo, the intense
antiquity of the older city—of every fragment of it—comes to you
impressively. You feel the age of it as you pace every yard of its alleys.
Cairo is comparatively modern, and comparatively garish. There is a
fine, if filthy, harmony in Damascus.
Intimate in the memory of most Light Horsemen will always be
certain features of Damascus. Our men will not forget the Hedjaz
Headquarters in the heart of the city, the German Club, the Local
Resources Office, the filthy Turkish hospital, the English and French
hospitals in the suburb, the littered railway station, the suburban
roads, unspeakably rough and muddy, the afternoon perambulations
of blatant under-dressed bints in gharries, the guards—on the
aerodrome, on the Ottoman Bank, on the captured grain stores, on
the captured guns—the plentiful lack of ordnance and canteen stores,
the corpses of dogs and horses in open spaces, the multitudinous
beggars, the exorbitant prices asked for German razors that cost their
vendors nothing, the moderate cost of silver and brass ware, the
Hedjaz recruiting processions, the glut of matches, the potency of
arak, the cunning of the plausible English-speaking small boys, the
puzzling complexity and fluctuation of the currency, the paucity of
mails, the liberty and the usefulness of Turkish prisoners, the fitful
and lawless discharge of firearms about the city all through the night,
the suddenness with which sickness made its descent upon the
apparently immune, the daily receipt and despatch to time-table of
official mails by air, the dancing lights of Salahiye that burned till
dawn....
H. W. D.
 Malaria

You, with your winding, creeping course,

What of the men of our Southern Horse?
Valley of night, with your wingèd pest,
What of our heroes now at rest,
Down by your Dead, salt Sea?
What of the ones we have left behind?
What of these men of our kith and kind,
Nigh where your blood streams hiss?
Better the true and unerring shot!
Better the Death when their blood runs hot—
Than this,
Malaria! Malaria!

You, with your agèd river’s flow,

What of our Riders laid below?
Valley of Death, with your torpid heat,
Look where your swirling hill streams meet,
Down by your Dead, salt Sea!
Look to the ones on your mounded knoll!
Look to the ones of your chosen toll!
Those of your fevered kiss!
Better the blast of the rending shell!
Better the toll of the War God’s knell,
Than this,
Malaria! Malaria!

“KOOLAWARRA.”
 Fall Out the 1914 Men

After four years’ service, the remnants of the First and Second
Contingents were assembled preparatory to return to Australia. Such
a prolonged absence from their homes might have led one to expect a
wild emotional outburst; but they received the tidings casually.
As they fell into line to be farewelled by the
Brigadier, they presented an inspiring sight; shoulder
to shoulder, each man a history in himself; true
mates, every one of them: their fellowship cemented
by the blood of fallen comrades. Alert they stood,
hardened by the privations and hardships of long
years of campaigning, but—true test of manhood—
ready to face it all over again if their principles were
involved.
As they waited for the “Old Man,” as the Brig. is
affectionately termed, visions of the past began to
take form before their eyes. Mine saw the silent,
winding streams of human life, being hurried through the streets of
sleeping cities on their way to grim, silent transports. No gay
farewells, no playing of bands, no gathering of gaily-dressed crowds
to wave them farewell on their way to foreign shores. As they
strained their eyes for a last glimpse of their native land, many must
have tried to visualize their return. None realized how or when, and
many of the stout hearts on those sea-sprayed ships who gazed with
loving eyes on their sunny land were saying the last farewell. Their
graves are in strange lands, their deeds imperishable memories.
“Boys”—it was the Old Man speaking—“we come together to say
good-bye.” He outlined his association with the Brigade, and touched
briefly on the outstanding incidents of its career. He humorously
alluded to their “weakness” in a few respects, but he was proud to say
that no man had ever complained of his punishment. Everybody had
played the game, and his life was infinitely richer because of his
association with them. He wished all a bright future, and they were
never to forget him if they were ever in any difficulty.
At the close of the homily, I am afraid, the etiquette of military
discipline was violated in many ways. “Good old Brig., the whitest
ever made,” and such-like remarks were punctuated by cheering and
the waving of hats. A personal handshake with each man and wishes
of “good luck”; and then came the farewells round the camp, when
mates of years bade each other good-bye, and turned away.
Friendship such as this will stand the test of time.
“BATAGGI.”

MRS. CHISHOLM’S CANTEEN AT KANTARA

BETHLEHEM
TROOPERS ENTERING JERICHO

DAMASCUS
 “Old Horse o’ Mine”

Hoof-beats, that rang on the crowded street,

Had never beat unto me
All the wealth of the gold in your old black hide,
All the grit of your loyalty;
But deep in the sand of a lonely land,
Out on many a far flung trail,
Your old hoofs spoke of a heart you broke
For me, that you might not fail.

Great eyes, that dusked in the green gums’ wave,

Though I recked not that you were there,
That danced or dulled at the whim mayhap
Of a fancy unaware—
How the mateship grew in the depths of you,
When the waste spread its gauntness wide.
How you parched with me, how you marched with me,
Through that Hell of a thirst denied.

Brave Soul that sprung in the colt of you,

Unguessed in the years far back,
Ere your Fate ran out from a land of streams
To the drought of a sun-blazed track—
For the days since seen, for the pals we’ve been,
When Old Time sees us through—
O! If then there be for the likes o’ me,
A Heav’n—it must hold you, too.

T. V. B.
 Concerning Machine Guns

“Vickers Light Automatic, ·303,” so saith the machine gun

handbook. Further on, it informs the reader that the gun weighs 38
lbs. when the water jacket is filled. These statements have been the
subject of many bitter outbursts, and not a few have wondered
whether they had a pair of scales at the War Office (this unfortunate
institution is, of course, responsible for everything that goes wrong).
There have been countless instances where a sweating, cursing
Billjim, struggling up a scorching precipice with the said Vickers
Light Automatic, would have betted all his deferred pay that it
weighed at least ten times as much as the handbook implies. Even on
such kindergarten exercises as gun drill, wonder has often been
expressed that “they” had the blooming neck to print such a fib. Still
another proof that the real weight greatly exceeds the official figures.
Watch the hefty No. 2, capable of lifting an 18 pdr., as, after
continuous firing, he gets the order, “Out of action!” In a flash, the
pins are wrenched out, he seizes the smoking gun where the
protecting piece of puttee, numnah pad or sock isn’t, and instantly
drops the weapon to the ground. Isn’t that convincing?
There are other minor details about the machine gun handbook
that are apt to be misleading. It states that there is a No. 1, who is the
boss and only carries the tripod—a flimsy toy of some 48 lbs. of brass
and steel; next, a No. 2, who juggles with a Vickers Light Automatic;
also a No. 3, who has nothing to do but carry a few boxes of
ammunition, these being mere tin cases no bigger than the handbag
he used to carry his pyjamas in, and containing only one belt; then
there are a few other superfluous hangers-on; a No. 4, who aids the
No. 3; a No. 5, who aids him; and so ad infinitum down to that
humble creature, the pack leader, who holds three horses during an
action.
 Thus far, the handbook is perfect, photographic plates and all.
Where the discrepancy comes in, is that there is no advice regarding
a hitch. It has nothing to say about this: A person is observed toiling
along with the tripod, a box of 250 cartridges hanging on each leg,
straddled across his shoulders; some distance behind him wobbles
another sagging individual, bearing the gun, more belt boxes, a pick
and a shovel; while a third—sometimes—struggles on with still more
belt boxes, range-finder, spare parts wallet, a can of water, steam
escape tube, a bag to prevent dust at the gun’s muzzle, and a few
other trifles; and down in some more or less protected hollow, three
or four distracted pack leaders curse away their last remaining hope
of salvation trying to keep untangled the twenty-odd hungry brutes
that crane their necks to nibble at infinitesimal, dead grass stalks. Let
us dismiss the handbook.
The machine gun can be put to many uses. As a seat, it is
admirable, also as a clothes horse for small gear; and as a horse rack,
providing the animal doesn’t pull it over, it stands alone. It has also
been known to remove Turkish folks from their ration strength—but
accidents will happen.
The gunner is at his best when using his gun as anti-aircraft. He
reverses the position of the gun on the tripod in order to get a
sharper angle, and lies down on his back beneath it, pillowing his
shoulders on some soft substance, such as the spare parts box. The
No. 2 crouches alongside to tuck in—at this angle—the reluctant belt;
the Taube approaches at a reasonable altitude, and then ratta-tatta-
tatta stutters the gun.
A heartrending episode occurred in the Jordan Valley one
morning. The guns, at the top of the precipitous cliffs lining the
Jordan, were being snugly tucked away in their little dust-proof
positions for the day, when sinister humming in the sky was heard.
Out of the woolly, cumulus clouds a flock of Taubes dived and began
their fell work. In a twinkling, the guns were violently slammed on
the tripods, fresh, full belts rattled into the feed-blocks, and the
gunners flopped into their positions, grimly inviting the visitors to
come a bit closer and “have a fly.” They did, and answered the
prompt leaden stream with their own guns.
One gun had been firing merrily at the wheeling Taubes for some
time when the prostrate, grim-jawed No. 1 uttered a wild, squealing
yell, and writhed fearfully. “Good God, Percy is hit!” cried young
Bobbie, the No. 2, and he turned in alarm to his friend, who was out-
writhing any live wire.
The No. 1 gasped and stuttered in his agony, but managed to
ejaculate: “Hit, be dinged! It’s the bloomin’ hot shells that trickled
inside me shirt. Hop into ’em!”
I give this illustration merely to show the risks attached to
machine gunnery.
The Machine Gun Squadron is regarded as a desirable unit. It has
numerous advantages over the Regiments; notably, there are no
duties or fatigues to speak of, except, perhaps, stables, watering,
rations, cook’s, Q.M.’s, road-making, laying interminable miles of
stones in line, whitewashing same, erecting this, that and the other,
cleaning saddlery, polishing reluctant steel work, an odd guard or
two (mostly odd), and a few other trifles, which the conscientious
soldier performs with assiduity and alacrity.
There is little else about machine guns to learn, they are so perfect
that a machine gunner is now made in six weeks instead of six years.
They have performed some remarkable work during the war, moral
effect being one of their greatest assets—observe the sprightly vigour
with which the officer inspecting outposts bounds away from the
front of a machine gun position, where he has wandered by
misadventure, when the man on guard sings out, “Machine gun here,
Sir!”
The boys will be sorry to say good-bye to their vicious, stuttering
pets; and let us hope that, the guns, when they are returned to
Ordnance, will cease to (metaphorically) curl their lips in disdain at
their humble and erratic poor relations, the Hotchkiss rifles of the
Regiments.
“SARG.”
 Delivered!

A wounded earth is free again,

The barriers of the East are down;
With many a mound above the slain,
The zones of battle, bare and brown,
Shall feel the tears of wintertide,
(War’s aftermath of sorrowing)
Till Nature heals their scars of pride
And flowers perfume a deathless spring.

“GERARDY.”
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 TRANSCRIBER’S NOTES
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