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Heterogeneous Catalysis in Sustainable
Synthesis
Advances in Green and Sustainable
Chemistry
Heterogeneous Catalysis
in Sustainable Synthesis
Béla Török
Christian Schäfer
Anne Kokel
Elsevier
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Contents
Preface xi
1. Heterogeneous catalysis for organic synthesis:

Historical background and fundamentals
1.1 Introduction and historical background 1
1.2 Catalysis 3
1.2.1 Fundamentals and basic definitions 3
1.2.2 Heterogeneous catalysis 9
1.3 Conclusions and outlook 15
References 15
2. Solid catalysts for environmentally benign synthesis

2.1 Introduction 23
2.2 Metal catalysts 23
2.2.1 Unsupported metals 28
2.2.2 Supported metal catalyst 30
2.2.3 Heterogenized metal complexes and
organocatalysts 37
2.2.4 Metal nanoparticle-based catalysts 38
2.3 Nonmetallic catalysts 39
2.3.1 Metal oxides 41
2.3.2 Heteropoly acids 44
2.3.3 Clays 45
2.3.4 Zeolites 48
2.3.5 Ion exchange resins 51
2.3.6 Metal-organic frameworks 53
2.3.7 Other nonmetallic catalytic materials 55
2.4 Conclusions and outlook 57
References 58
3. Application of heterogeneous catalysis in the

development of environmentally benign synthetic
processes
References 82
v
vi Contents
3.1 Hydrogenation
3.1.1 Introduction 85
3.1.2 Carbon-carbon multiple bond hydrogenations: Alkenes,
alkynes, dienes 86
3.1.3 Hydrogenation of aromatic and heteroaromatic
compounds 96
3.1.4 Reduction of carbonyl compounds by heterogeneous
catalytic hydrogenation: Aldehydes, ketones, and
carboxylic acid derivatives 103
3.1.5 Hydrogenation of nitrogen-containing groups: NO,
NN, CN, and CN groups 108
3.1.5.1 Hydrogenation of the nitro group 108
3.1.5.2 Hydrogenation of nitriles 112
3.1.5.3 Hydrogenation of imines 114
3.1.5.4 Hydrogenation of azides 117
3.1.6 Chemo- and regioselective hydrogenation of compounds
with multiple hydrogenation sensitive groups 118
3.1.6.1 Selective CC bond hydrogenation of
α,β-unsaturated carbonyl compounds 118
3.1.6.2 Selective CO reduction of α,β-unsaturated
carbonyl compounds 119
3.1.6.3 Complete hydrogenation of multiple functional
groups using the same catalytic system 123
3.1.7 Heterogeneous catalytic hydrogenations by
nonconventional activation methods 123
3.1.7.1 Microwave-assisted hydrogenations 123
3.1.7.2 Ultrasound-assisted hydrogenations 126
3.1.8 Conclusions and outlook 130
References 130
3.2 Heterogeneous catalytic hydrogenolysis

of organic compounds
3.2.2 CC bonds 158
3.2.3 CO bonds 167
3.2.4 CN bonds 177
3.2.5 C-halogen bonds—Dehalogenation 186
3.2.6 NN and NO bonds 190
3.2.7 CS bonds 195
3.2.8 Hydrogenolysis of C-other elements (Si, metals) bonds 198
3.2.9 Hydrogenolysis of biomass-related compounds 199
3.2.9.1 Hydrogenolysis of biomass-derived
oxygen-containing heterocycles 199
3.2.9.2 Hydrogenolysis of biomass-derived other
oxygen-containing compounds 199
References 204
Contents vii
3.3 Heterogeneous catalytic oxidations

3.3.2 Epoxidation reactions 228
3.3.3 Dihydroxylation reactions 235
3.3.3.1 Dihydroxylations with osmium 235
3.3.3.2 Dihydroxylations with metals other than osmium 240
3.3.4 Wacker-type oxidation reactions 241
3.3.5 Oxidative cleavage of hydrocarbons 243
3.3.5.1 Cleavage to generate aldehydes and ketones 244
3.3.5.2 Cleavage to generate carboxylic acids and esters 248
3.3.5.3 Other oxidative cleavage reactions 250
3.3.6 Oxidation of CO and CN bonds 251
3.3.6.1 Oxidation of CO bonds 251
3.3.6.2 Oxidation of CN bonds 260
3.3.7 Dehydrogenation and aromatization of CC and CX bonds 263
References 269
3.4 Metathesis by heterogeneous catalysts

3.4.2 Cross-metathesis 280
3.4.3 Ring-closing metathesis 288
3.4.4 Ring-opening metathesis 301
3.4.5 Alkyne metathesis 302
3.4.6 Heterogeneous catalytic asymmetric metathesis 303
3.4.7 Metathesis applied to bioderived alkenes 305
References 310
3.5 Friedel-Crafts and related reactions catalyzed

by solid acids
3.5.2 Alkylation, hydroxyalkylation 318
3.5.2.1 Alkylations with hydrocarbons 318
3.5.2.2 Alkylations with alcohols, ethers, aldehydes,
and ketones 326
3.5.2.3 Alkylations with alkyl halides 338
3.5.2.4 Hydroxyalkylations 341
3.5.2.5 Intramolecular transalkylations—Rearrangements 343
3.5.3 Acylation 344
3.5.3.1 Acylations with carboxylic acids 345
3.5.3.2 Acylations with activated carboxylic acid
derivatives 348
3.5.3.3 Intramolecular transacylations—Rearrangements 355
3.5.4 Friedel-Crafts cycliacyalkylations 356
3.5.5 Halogenation 357
viii Contents
3.5.6 Nitration 360

3.5.7 Sulfonation 364
References 365
3.6 Cross-coupling reactions for environmentally

benign synthesis
3.6.2 The Heck coupling 380
3.6.2.1 Heck reactions using a heterogeneous
catalyst in solution 380
3.6.2.2 Solvent-free Heck reactions 389
3.6.2.3 Heck reactions without palladium 392
3.6.3 The Suzuki coupling 393
3.6.3.1 Palladium-catalyzed heterogeneous
Suzuki coupling reactions 393
3.6.3.2 Palladium-free heterogeneous catalytic
Suzuki coupling reactions 405
3.6.4 The Hiyama coupling 407
3.6.5 The Negishi coupling 411
3.6.6 The Kumada coupling 414
3.6.7 The Sonogashira coupling 415
3.6.8 The Tsuji-Trost allylation 424
3.6.9 Coupling reactions not involving a CC bond formation 426
3.6.9.1 CN bond-forming reactions 426
3.6.9.2 CO bond-forming reactions 429
3.6.9.3 CS bond-forming reactions 430
References 432
3.7 Multicomponent reactions

3.7.2 Carbonyl-based multicomponent reactions 444
3.7.2.1 Formation of 6-membered rings with
multicomponent reactions 444
3.7.2.2 Formation of 5-membered rings with
multicomponent reactions 453
3.7.2.3 Formation of aliphatic bonds 459
3.7.3 Isocyanide-based reactions 464
3.7.3.1 Isocyanide-based MCRs for the preparation
of 5-membered rings 466
3.7.3.2 Isocyanide-based MCRs for the preparation of
5- and 6-membered heterocycles 469
3.7.3.3 Aliphatic bond formation 475
References 480
Contents ix
3.8 Ring transformations by heterogeneous catalysis

3.8.2 Cyclization 492
3.8.2.1 Intermolecular cyclization reactions 492
3.8.2.2 Intramolecular cyclization reactions 508
3.8.3 Ring opening reactions 517
3.8.3.1 Ring opening of small heterocycles 517
3.8.3.2 Ring opening polymerization 525
3.8.3.3 Other types of ring opening reactions 529
References 530
3.9 Heterogeneous catalytic rearrangements and other

transformations
3.9.1 Rearrangements 543
3.9.1.1 Beckmann rearrangement 543
3.9.1.2 Fries rearrangement 548
3.9.1.3 Epoxide rearrangements 549
3.9.1.4 Ferrier rearrangement 551
3.9.1.5 Johnson-Claisen rearrangement 552
3.9.1.6 The ortho-Claisen-rearrangement 552
3.9.1.7 Benzylimine-benzaldimine rearrangement 553
3.9.1.8 Pinacol rearrangement 554
3.9.1.9 Baeyer-Villiger oxidation 554
3.9.2 Aldol and related reactions 556
3.9.2.1 The aldol reaction 556
3.9.2.2 Mukaiyama reaction 558
3.9.3 Condensations 558
3.9.3.1 Schiff-base formation 558
3.9.3.2 Knoevenagel condensation 563
3.9.3.3 Pechmann condensation 566
3.9.3.4 Aldol condensation 568
3.9.4 Hydrolysis 573
3.9.4.1 Hydrolysis of cellulose 573
3.9.5 Introduction and removal of protecting groups 574
3.9.6 Hydroformylations 577
References 580
3.10 Asymmetric synthesis by solid catalysts

3.10.2 Oxidation reactions 594
3.10.2.1 Epoxidation 594
3.10.2.2 Dihydroxylation 596
3.10.2.3 Other oxidations 598
x Contents
3.10.3 Hydrogenation 599

3.10.3.1 Reduction of carbonyl compounds 600
3.10.3.2 Reduction of C=C double bonds 614
3.10.4 Aldol-reaction and related chemistry 618
3.10.4.1 Aldol reactions 619
3.10.4.2 Michael additions 624
3.10.4.3 Henry reactions 629
3.10.5 Multicomponent and various other reactions 630
3.10.5.1 Multicomponent reactions 630
3.10.5.2 Cascade and tandem reactions 632
3.10.5.3 Other reactions 634
References 640
Index 655
Preface
The commencement of the idea and concept of this book has been on my
mind (BT) for quite some time. As a graduate student, I worked in the over-
lapping area of organic chemistry and heterogeneous catalysts, and one of the
most comprehensive books that surveyed this research field was Augustine’s
Heterogeneous Catalysis for the Synthetic Chemist. Although it has been an
invaluable resource for a generation of scientists, this book has been published
a quarter of century ago (in 1996) and a new edition never came. Since then, ex-
tensive developments occurred in heterogeneous catalysis including its broad-
ening applications in synthetic and industrial chemistry. With this book, we
intended to follow the footsteps of Professor Augustine and provide a useful
resource for those who work in organic synthesis and use heterogeneous cata-
lytic methods, and also those who are synthetic chemists but new to the applica-
tion of solid catalysts in their work. The book is intended for a broad audience
including researchers working in industry and academia. It is aimed to deliver
a synthesis-oriented heterogeneous catalytic text that also takes the principles
of Green Chemistry into account. Although heterogeneous catalysis began its
contribution to the development of environmentally benign synthetic processes
well over a century ago, the formulation of the conscious Green Chemistry prin-
ciples did not occur until the mid-1990s. Thus, interestingly, the time period our
work surveys (1996–2021) witnessed the intertwist of heterogeneous catalysis
and Green Chemistry. The main goal of the work was to show an as broad as
possible snapshot of synthetic heterogeneous catalysis in the review period and
consider the surveyed protocols keeping in mind the contemporary aspects of
Green Chemistry. The book includes three distinct parts: the first part describes
the historical aspects of heterogeneous catalysis and its becoming a vital part of
green synthesis developments. It also covers the basic definitions of catalysis,
especially those that are focused not only on catalysis but also its heteroge-
neous applications. The next part gives an overview of solid catalysts, including
metal catalysts and nonmetallic alternatives, such as metal oxides, synthetic,
and natural aluminosilicates, polymer-based solid acids and bases, and several
emerging types of catalytic materials, such as nanoparticles, metal-organic
frameworks, or covalent-organic frameworks. The centerpiece of the most ex-
tensive part of the book is heterogeneous catalysis in practical synthesis. This
third part describes the relevant examples of the most common processes where
heterogeneous catalysis is applied: hydrogenation, hydrogenolysis, oxidation,
xi
xii Preface
metathesis, cross-coupling reactions, Friedel-Crafts, and multicomponent reac-

tions just to name a few, all of them are common in organic synthesis. These
subchapters are in-depth reviews on these topics. However, we must admit that
the material available in the literature is overwhelming, thus we focused on
providing a broad picture with representative examples, rather than attempt-
ing to write comprehensive chapters on these individual methods. Each would
fill a separate book on its own. We hope that the book will serve as a primary
resource for those who are new to heterogeneous catalytic synthesis and those
who intend to branch out and discover other topics that are related to their own
research fields.
Finally, we thank our colleagues, editors at Elsevier, for contributing to this
unique endeavor: Anneka Hess who helped us through the proposal phase of
the book and Sruthi Satheesh, who handled the galley proofs. Although, we had
several editorial project managers throughout the project, we are particularly
grateful to Emily Thomson, our final Editorial Project Manager for her help in
ushering the work to completion.
Béla Török
Christian Schäfer
Anne Kokel
Chapter 1
Heterogeneous catalysis for

organic synthesis: Historical
background and fundamentals
1.1. Introduction and historical background
The phenomenon of catalysis itself has been around in the form of fermenta-
tion (i.e., bio-catalysis) for thousands of years. The earliest written report on a
catalytic reaction was published in 1552 by Cordus, who carried out the dehy-
dration of alcohol to ether.1 The roots of modern catalysis originate from over
two hundred years ago when Elizabeth Fulhame described the concept of ca-
talysis in her 1794 essay regarding her experiments on oxidation-reduction, sug-
gesting that a small amount of water was required for the reaction to occur.2, 3
There were several others who later observed and reported catalytic reactions,
such as Parmentier, Kirchhoff, or Döbereiner, who focused on the hydrolysis of
starch, and also described the decomposition of potassium chlorate catalyzed
by manganese dioxide.4–6 There have been many more who contributed to the
developments. One of the most important ones was when the term catalysis
was coined by the Swedish chemist, Berzelius, in 1835.7 The significant break-
through that gave a major push to the development of heterogeneous catalysis
occurred at the end of the 19th century when Paul Sabatier carried out his ex-
periments regarding catalytic hydrogenation on Ni/kieselguhr.8 This discovery,
with his other contributions, earned Sabatier the Nobel Prize in Chemistry in
1912.9 In addition to developing catalytic hydrogenation, which became a new
field of organic synthesis, he also made several fundamental observations, such
as that the particle size of Pt significantly changed its activity/reaction rates, that
became a common knowledge in heterogeneous catalysis. By the early 1900
similar observations were made regarding other metals or, in general, other
catalytic substances.10 Sabatier’s experiments with metal catalysts, especially
with Ni, generated considerable interest in the field and shortly new applica-
tions, such as the development of the Raney Ni catalyst, revolutionized metal
catalysis.11–13
Just like Sabatier was the pioneer of heterogeneous metal catalysis, Vladimir
Ipatieff earned the same distinction for his studies using nonmetal or solid acid
catalysts (γ-alumina) in the early 1900s.14 The two scientists worked in parallel
Heterogeneous Catalysis in Sustainable Synthesis. https://doi.org/10.1016/B978-0-12-817825-6.00014-8

Copyright © 2022 Elsevier Inc. All rights reserved. 1
2 Heterogeneous catalysis in sustainable synthesis
and spearheaded the development of the two main directions of heterogeneous

catalysis independently. Among Ipatieff’s many contributions, he studied the
dehydration of alcohols to alkenes (e.g., ethanol to ethylene), butadiene syn-
thesis, development of catalysts for hydrogenation, the discovery of oligo-
merization, paraffin alkylation, and acid-catalyzed aromatic alkylation. To be
successful he had to develop a special technique using high pressure in steel
autoclaves, a major tool that he introduced to heterogeneous catalysis. Unlike
Sabatier, Ipatieff’s focus was more on commercial applications. As a milestone
in his achievements he has developed the process that produced high octane
(about 100 octane number) gasoline that was used by the British Air Force dur-
ing WWII and aided them to succeed in the aerial battle over Great Britain.15, 16
Following Ipatieff’s introduction of γ-alumina as a catalyst, the field underwent
an explosion-like development, new acidic solids were developed and applied
as heterogeneous acid catalysts.
The earlier mentioned practical developments also initiated extensive re-
search at the mechanistic side of catalysis, particularly in finding explanations
for the observed phenomena. Early efforts by Duclaux, Moissan, or Ostwald17
were followed by other researchers, many of whom focused on heterogeneous
catalysis and the surface phenomena occurring on catalysts. Starting with the
measurement of solid surfaces, such as the Brunauer-Emmett-Teller (BET) sur-
face area,18 several explanations were reported to elucidate surface phenomena,
including the Langmuir-Hinshelwood,19, 20 Eley-Rideal,21 or Horiuti-Polanyi
mechanisms.22 Later, in the 1960s, these investigations led to the development
of a new field, commonly referred to as surface science,23 pioneered by Ertl24
and Somorjai.25 Since then, heterogeneous catalysis research became a wide-
spread field within the overlapping areas of chemistry, chemical engineering,
and surface science. Contemporary developments added material science to this
company, as many new materials, such as carbon nanostructures (nanotubes,
graphene, graphene oxide, etc.), metal-organic frameworks, covalent organic
frameworks, synthetic zeolites, or clays, that hold significant promise in catalyst
development have been prepared. The history and development of catalysis, in-
cluding heterogeneous catalysis, has attracted the attention of many educators,
science historians, and active researchers as well, and have been extensively
reviewed.26–31 The reader is advised to consult with these accounts for more
details.
Catalytic processes are major contributors to the green chemistry move-
ment, including sustainable synthesis, renewable fuel production, or environ-
mental protection, e.g., automotive applications. Catalytic processes can replace
the use of nonrenewable, low atom economy reagents, significantly decreasing
the environmental impact of the production of pharmaceuticals or fine chemi-
cals. Catalysis also contributes to the fulfillment of several principles of green
chemistry and green engineering.32, 33
Based on the importance of these methods, they have been frequently re-
viewed. There are many seminal books34–40 and major accounts41–43 that time
Heterogeneous catalysis for organic synthesis Chapter | 1 3
to time provided extensive background regarding these processes. One of these

books, Augustine’s Heterogeneous Catalysis for the Synthetic Chemist,44 was
focused on the application side of heterogeneous catalysis, with particular at-
tention to processes that are related to organic synthesis. Although it is an excel-
lent summary of the progress until its publication in 1996 it has been published
25 years ago and several processes, such as metathesis or cross-coupling reac-
tions, are not covered in it. Our goal in this book was to give an up-to-date de-
scription about heterogeneous catalytic processes used for the synthesis of fine
chemicals and pharmaceuticals, and provide representative illustrations of the
contemporary advances made in the application of these methods in environ-
mentally benign and sustainable synthesis.
The following parts of this chapter describe the fundamentals of catalysis
with several terms and definitions that are necessary to understand the forth-
coming chapters.
1.2. Catalysis
Catalysis, whether in its homogeneous or heterogeneous form, has been a major
contributor to green chemistry in general, and to sustainable synthesis in partic-
ular. Catalytic processes make the traditional nonrenewable, low atom economy,
wasteful protocols obsolete and provide green alternatives to often century-old
protocols. The use of catalysis supports the fulfillment of the generic Green
Chemistry principles in more than one way; it contributes to several points as
listed here with the condensed descriptions: 1 (prevent waste), 2 (maximize
atom economy), 5 (limit auxiliary substances), 6 (energy efficiency), 8 (reduce
derivatives), 9 (catalysis), and 12 (safer chemistry) from the twelve points of
Green Chemistry.32, 33 In addition to Green Chemistry principles, heterogeneous
catalysis contributes to the improvement of the engineering aspects of chemical
processes as well, according to similar principles of Green Engineering. For
example, principles 2 (waste prevention), 3 (design for separation), 4 (maximize
efficiency), 8 (minimize excess), and 10 (integrate material and energy flows)
are all improved by the application of heterogeneous catalysis.45 In order to pro-
vide a clear introduction for those who are unfamiliar with the terms of cataly-
sis, particularly those of heterogeneous catalysis, in the following subchapters
we describe the basic definitions and fundamentals of this field.
1.2.1 Fundamentals and basic definitions

1.2.1.1 Catalyst and catalytic cycle
A catalyst is a compound or material that enables a chemical process to occur,
without being changed by the end of the process. It must be a natural or syn-
thetic substance; light, heat, or other forms of energy (e.g., microwave irradia-
tion, ultrasounds, etc.), cannot be considered catalysts. After the first reaction
is completed, the catalyst returns to the beginning of the process and initiates
product
desorption,
catalyst
S
reformation
P
Catalyst mass transport
and adsorption
S
P Catalyst Catalyst
product mass transport

Catalyst
formation and adsorption
R S
FIG. 1 A generic scheme of a catalytic cycle with the elementary steps.
a new reaction. These reactions are called catalytic cycles (Fig. 1). It must be
noted, however, that this is the ideal picture. Many catalysts eventually undergo
an irreversible change due to unintended and undesirable phenomena. These
could be due to the reaction conditions, heat, active component leaching out of
a reactor, and many others.
The major role of a catalyst is to alter the original noncatalytic reaction
pathway into a series of lower energy demanding processes, called elementary
steps. While doing this, by changing the reaction mechanism, the catalyst often
increases the rate of the reactions as well. The elementary steps and their com-
bination to a catalytic cycle are illustrated in Fig. 1.
Catalysts come in many different forms, some are single atoms46, 47 or small
compounds such as acids or bases,48 some are larger such as metal complexes49,
50
or even supramolecular assemblies including enzymes or metal-organic
frameworks,51–53 others are elements in different forms.54 Catalytic materials
are commonly distinguished based on their solubility, whether they are soluble
in the reaction medium (homogeneous catalysis) or they are largely insoluble
solids (heterogeneous catalysts). In this book we will focus on the application
of heterogeneous catalysis, thus the emphasis in this chapter will be on the solid
catalytic materials.
1.2.1.2 Activation energy

In the course of a chemical reaction, chemical bonds are cleaved and new bonds
made. As all chemical bonds possess an energy content to keep the atoms to-
gether, that energy needs to be provided to cleave a bond and initiate a reaction.
The energy that is required to initiate a reaction is called the activation energy
Activation
energy
EA,UC
Uncatalyzed reaction: A+B C+D EA,UC
Catalyzed Reaction: A+B I1 EA,1

EA,2
EA,3
EA,1 I1 I2 EA,2
Free energy
I2 I2 C+D EA,3
I1
A+B
I - intermediate
∆G
C+D
Reaction Coordinate
FIG. 2 Illustration of the energy profile of a hypothetical catalytic and noncatalytic reaction.
(EA). Typically, the activation energy of a noncatalytic reaction is significantly

higher than that of a catalytic reaction. The catalyst alters the reaction mecha-
nism to separate elementary steps that require significantly lower activation en-
ergy as illustrated in Fig. 2.
In addition to explaining the major role a catalyst plays in a chemical pro-
cess, Fig. 2 also points out that the application of a catalyst does not modify the
basic thermodynamic features of the process. The overall energy of the sub-
strates and the final products will not be altered by the presence of a catalyst,
thus catalysis is a kinetic phenomenon. Typical catalysts increase the rate by
three orders of magnitude; biocatalysts, however, are able to produce 1020 times
rate increase. The kinetic nature of the catalytic action also means that if a pro-
cess is an equilibrium reaction the use of a catalyst allows to achieve the equi-
librium faster, but the equilibrium constant remains the same.
1.2.1.3 Other definitions

In addition to the earlier mentioned basic definitions, there are several other
important terms that describe the efficiency and selectivity of catalysts.
Reaction rate. The reaction rate in the case of catalytic reactions is often
described by the turnover frequency (TOF). When a catalyst is contributing to a
reaction it is released after one catalytic cycle and returns to initiate another one.
When the number of catalytic cycles are normalized for one catalytic unit, such
as an active site or an active metal complex, the number of cycles run is called
turnover number (number of reactions/active center). When the number of turn-
overs is also normalized for a time unit (TON/time = TOF) one can characterize
the rate of the reaction.
Lifetime. As mentioned already, ideally the catalyst should remain unaltered

after a catalytic cycle; however, in real-life experiments catalytic substances
undergo changes that include deactivation. Some of the changes are chemical
(reduction, oxidation, functionalization, etc.) while others are physical (particle
size increase or decrease); nonetheless, they will result in undesirable changes
in activity and/or selectivity. The factor of how long a catalyst can function
without major changes in its performance is the catalyst’s lifetime. This is often
expressed by the turnover number (TON) up to the point when the performance
starts declining.
Catalyst poisons. The specific features of a catalyst can be fundamentally
and negatively altered by certain changes the catalyst undergoes during a reac-
tion. When these changes are caused by chemical agents then we talk about
catalyst poisoning and the agent is a catalyst poison. These compounds not only
bind very strongly, often irreversibly, to the catalyst, but they also bind to the
active center that will become partially or completely inactive. The strong ad-
sorption means that a minute amount of these compounds can alter the activity
significantly, which highlights the need for high purity starting materials and
solvents. For example, organosulfur compounds deactivate most noble metal
catalysts, thus all sulfur-containing impurities must be removed from the start-
ing material. This is a common problem not only in heterogeneous catalytic
synthesis but also in the automotive industry as well, as most reactants and fuels
of petrochemical origin could contain sulfur. Catalyst poisoning can be acciden-
tal, natural, or intentional. In the first case, the poison enters the catalytic system
accidentally, for example from the atmosphere or via a contaminated solvent
and shuts it down. This is often the case with sulfur- or nitrogen-containing
compounds. In the second case, the catalyst poison is gradually deposited or
building up on the surface of the catalyst throughout the reaction, such as the
formation of surface carbonaceous deposits, that is typical for solid catalysts,
for example supported metals or zeolites.55 The third case is when the catalyst
is intentionally and partially poisoned as a part of the design process, in order
to modify its activity and/or selectivity. By the selective poisoning of a catalyst,
its activity and selectivity can be fine-tuned and undesirable side or successive
reactions can be blocked, and in parallel, the yield of the target product can be
improved. A typical example is the Lindlar catalyst (Pd/CaCO3 is partially poi-
soned with Pb(OAc)2 and quinoline) that can selectively hydrogenate alkynes
to alkenes (Fig. 3).56
FIG. 3 The Lindlar catalyst and its use for the partial hydrogenation of alkynes to alkenes.
Chemical promoters. Additives can also play the opposite role and signifi-
cantly improve the activity and/or selectivity of an otherwise imperfect catalytic
material. These additives are called promoters. Chemical promoters enhance the
activity and selectivity of catalysts by altering the electron density/distribution
on the surface of the catalyst. The typical example of chemical promoters is mo-
lybdenum that is used in improving the catalyst of ammonia synthesis. In this
process the main catalyst is iron and a small amount of molybdenum is used as
a chemical promoter.57 Another example is the methanol synthesis from syngas
where the most common catalyst is Cu-ZnO that is made better by chromium
oxide (Cr2O3) as a promoter.58 Other materials are used as structural promoters
as they improve formulation, general mechanical properties, and stability of
catalysts.59 Structural promoters can prevent sintering (the formation of large
particles that would decrease the active surface of the catalyst) and maintain the
particle size of the catalysts.60
Catalyst reuse, regeneration, and recycling. Although catalyst deactivation,
whether by poisoning or other physical changes, is an undesirable phenomenon,
it is part of the laboratory and industrial practice. Due to the often expensive na-
ture of catalysts, the process chemistry protocols for batch systems commonly
attempt to reuse the catalyst after one batch is completed.61 Sometimes cata-
lysts can be reused in several cycles without meaningful drop in their perfor-
mance; however, in many other cases, significant deactivation is observed even
after one run. When that occurs, the potential regeneration of the catalyst is
investigated. Reactivation is commonly carried out by periodical physical (heat,
surface cleaning by ultrasounds, etc.) or chemical (oxidation, reduction, etc.)
treatment to restore the original activity.62 However, despite all efforts, at some
point catalysts reach the end of their lifetime. Due to the often expensive rare
metals used as catalysts the so-called spent catalysts are also recycled, which,
in this context, means that the spent catalysts are collected and returned to in-
dustrial recycling facilities, where using a variety of methods the noble metals
can be separated from the support material and recycled back to their bulk metal
form, which then can reenter the catalyst production pipeline. The catalyst end-
of-lifetime recycling is particularly desirable, it is economic, and also envi-
ronmentally conscious, as it spares the waste deposition facilities/landfills and
ultimately the water supply (through ground water) from the toxic heavy metal
contamination.63, 64 These processes are extended beyond the catalysts used in
the chemical industry to automotive catalysts as well. This is a particularly im-
portant issue due to the large volume of automotive exhaust catalysts used.65
Selectivity. Describes the catalyst’s ability to carry out a chemical process
to produce the major expected product in high excess compared to all other by-
products. Selectivity is a general term that includes several specific subcatego-
ries (Fig. 4). An earlier book by Davis and Suib provided a detailed discussion
of this issue, here we only discuss the most common terms.66
Having a substrate that includes more than one functional group the com-
pound could undergo parallel and or subsequent reactions. Chemoselectivity
FIG. 4 Representative examples for different forms of selectivity.
describes how well the catalyst can facilitate the exclusive transformation of
only one functional group while all others remain untouched. When the out-
come of the reaction results in the formation of at least two different constitu-
tional isomers we talk about regioselectivity. There are different examples for
this subcategory. For example, in a typical catalytic bromination of substituted
benzene derivatives with activating substituents, the ortho- (or 2-) and para-
(or 4-) brominated products can form. In another example, the reaction could
occur on the same functional groups in a compound, e.g., the hydrogenation of
either of the CC double bonds in dienes in different positions. In the case of
asymmetric catalysis the reaction produces chiral compounds; enantioselectiv-
ity will describe the ratio of the two enantiomers with descriptive factors such as
enantiomeric excess (ee) or enantiomeric ratio (er). If a reaction is carried out on
a prochiral functional group in a starting material that already possesses a chiral
center, the products are called diastereomers and their ratio is described by the
diastereoselectivity. Although some catalysts exhibit high activity and selectiv-
ity at the same time, high activity catalysts often do not discriminate between
different functional groups or the location of the same functional group, hence
they will exhibit low selectivity. Along the same line, low activity catalysts can
often distinguish between reacting groups based on minor differences and will
show high selectivity. Thus activity and selectivity are generally in an inverse
relationship.
Type of catalysis. Catalytic processes are characterized based on the phase
of the catalyst in the reaction medium, mostly on their solubility in the sol-
vents. Traditionally, they are placed into three main groups, which are homo-
geneous, heterogeneous, and phase transfer catalysts. The distinction between
homogeneous and heterogeneous catalysis is obvious; if the catalyst is soluble,
then homogeneous, if not, heterogeneous is the case. Phase transfer catalysis is
somewhere in between and is neither of the earlier two; the catalyst’s function
is to ensure mass transport through the phase boundary of the two solvents in
the system.
Catalysts. Catalytic materials include a broad range of materials from simple
mineral acids, and soluble metal complexes, bulk or supported metals, metal ox-
ides, natural or synthetic aluminosilicates to highly organized synthetic materi-
als such as metal-organic frameworks or biocatalysts. Here, we will not discuss
catalysts further as Chapter 2 is dedicated to the description of catalysts, with
exclusive highlight on heterogeneous catalysts, given the focus of this book.
1.2.2 Heterogeneous catalysis

By definition, in a heterogeneous catalytic process, the catalyst and the reaction
mixture are present in different phases. The most common example, especially
for laboratory applications, is when the catalyst is solid and the reaction mixture
is in a solvent (solid/liquid (S/L) reactions). Although these systems are popular
in industrial applications as well, the solid/gas (S/G) reactions are perhaps even
more prevalent in industry, especially in large-scale operations such as those in
the petrochemical industry (e.g., isomerization, cracking) or the oxidation of
sulfur to SO3 during the production of sulfuric acid. There are special applica-
tions, both at laboratory and industrial scales, when all three phases, solid-liquid
and gas (S/L/G), are involved in a reaction. Examples include the widely used
hydrogenation or hydroformylation reactions.
Heterogeneous catalytic processes possess several advantages. One of the
most commonly mentioned benefit is that the catalysts are solid and can easily
be separated from the reaction medium, whether it is a liquid or gas. This aids
in the removal of the catalyst from the product and facilitates easy recovery and
reactivation if needed, promoting catalyst recycling and thus could decrease the
environmental impact and improve the sustainability of a process. Solid cata-
lysts are commonly not moisture or oxygen sensitive, and thus have longer shelf
life and stability than the sensitive metal complexes.
However, heterogeneous catalysts also have their own drawbacks. While
in homogeneous catalysis every dissolved catalytic species is considered an
a ctive center, regarding solid catalysts, a considerable part of the material is

buried under the surface where the reactions occur. This phenomenon decreases
the number of available active centers, which decreases the activity (per unit
weight). Another common issue is the mass-transport limitation, which refers
to the necessity of the substrates and reacting partners to be transferred to the
surface of the catalyst for the reaction to occur. This phenomenon is particu-
larly of concern when three-phase systems, such as hydrogenations, are applied.
Another serious issue is the use of special preparation techniques, particularly
for industrial catalysts. Although every step of a catalyst’s preparation has its
own importance, the process is often considered an art form. Since the prepara-
tion conditions have strong influence on the characteristics and thus the perfor-
mance of the catalyst, minor alterations in the synthetic process could result in
notable changes in performance.
1.2.2.1 Catalytic surfaces

As in heterogeneous catalysis all reactions occur on the surface of the cata-
lyst, whether it is the outer surface or the internal surface of porous materials;
the surfaces possess a role of primary importance in this field. The chemical
and physical nature of the surface will essentially determine the mechanism
of surface interactions and ultimately lead to the product formation. Studying
reactant-surface interactions is an important field that attracted significant at-
tention over the past several decades even before the establishment of surface
science as a specific area of research.
1.2.2.2 Physical and chemical adsorption

Independently of the catalyst itself, the interaction of the catalyst’s surface
with the substrate(s) is of utmost importance in heterogeneous catalysis. A sub-
strate must interact with the surface to initiate any transformation. Adsorption
is the process through which the catalysts form a surface complex with the
substrate(s), which is the first step of every heterogeneous catalytic process.
Once the surface reaction is complete, the product undergoes desorption.67 In an
effective process, the adsorption capability of the substrate is much greater than
that of the product, thus ensuring that once the reaction is complete the substrate
can replace the product on the catalyst’s surface. Any compound that is to par-
ticipate in such a process must be able to adsorb on the surface. The process of
adsorption can occur by physisorption when simple, and usually weak physical
bonds develop between the surface and the compound. Such weak interactions
occur between, e.g., nonpolar compound and surfaces, such as the nitrogen ad-
sorption on surfaces that enable the determination of the physical surface area
of a catalyst, commonly known as the BET surface (vide supra).18 Different and
much stronger interaction drives chemisorption, when the substrate-surface in-
teraction is due to chemical forces, such as acid-base, nucleophilic-electrophilic
interactions that are commonly based on the electronic processes. For example,
many hydrogenation processes begin with the adsorption of a CX double

bond where the electron-rich double bonds make contact with the partially elec-
tron deficient metal surface. While the adsorption of the substrate(s) must oc-
cur through an interaction of considerable strength, it must remain a reversible
process. If the adsorption is irreversible then the compounds would stay on the
catalyst’s surface for indefinite time, blocking the sites from further substrate
molecules, thus deactivating the catalysts. Essentially, irreversible adsorption is
a characteristic of catalyst poisons.
1.2.2.3 The active site of solid catalysts

The concept of the active sites of catalysts was put forth by Taylor in the
1920s.68 Essentially the active site is a group of atoms that catalyzes a reac-
tion. Taylor suggested that these active sites are in a relatively small number
compared to the number of the atoms in the bulk of the catalysts.69 Modern
surface science measurements confirmed Taylor’s original hypothesis, namely
that a catalyst is a largely inactive surface with comparatively few active spots.70
It is also known that these active sites come in many different shapes, such as
single or multiatom sites, surface clusters, kinks, terraces, steps, and most of
these come with additional defects when commonly one or more atoms are
vacant.71 The active sites should have appropriate adsorptive capability and sub-
strate adsorption would follow the Sabatier principle; the substrate needs to
be able to adsorb and desorb as the product from the active site. In addition to
the adsorption strength, later it has been suggested that active sites can cata-
lyze structure-sensitive (otherwise called demanding) and structure-insensitive
(facile) reactions.72 Structure-sensitive reactions are dependent on the geometry
and/or crystallographic orientation of the active site, while structure-insensitive
reactions occur independently of the shape/form of the active site. This initiated
broad-ranging studies in heterogeneous metal catalysis when different metal
single crystals and atomically precise nanoclusters are applied to mimic dif-
ferent active sites.73–75 Later, mechanistic investigations for reactions carried
out on supported metal catalysts used single crystal studies for comparative
analyses.
The active site has a somewhat different nature in solid acid-base catalysts,
such as metal oxides, zeolites, or clays. Instead of focusing on special geometric
formations on the surface of the metal, here the active site is commonly identi-
fied as a Brønsted or Lewis acid or base site.76–79
1.2.2.4 Anchoring effects

There are a broad range of examples when one component of a commonly bi-
functional catalyst serves as a specific anchoring moiety for the substrate and
through that interaction ensures that the other component of the catalyst can
execute the actual reaction. The anchoring can occur through a variety of inter-
actions, such as acid-base, hydrogen bonding, or simple van der Waals forces.
FIG. 5 Anchoring effect of the Lewis acid centers of K-10 montmorillonite that ensures the che-
moselective adsorption of the carbonyl group of cinnamaldehyde and the selective formation of
cinnamyl alcohol (>99% selectivity) in the hydrogenation.
One of the most common examples is the chemoselective hydrogenation of α,β-

unsaturated carbonyl compounds, which is a process of practical importance in
the fragrance industry.80 The hydrogenation of these substrates on generic metal
catalysts commonly occurs on the CC bond before the CO bond would
undergo reduction. Using a special support with reasonably strong Lewis acid
centers would selectively anchor the more electron-rich carbonyl group and en-
sure that the hydrogenation of this group would proceed selectively (up to 99%)
leaving the CC bond intact (Fig. 5).81
1.2.2.5 Experimental variables

As mentioned before, heterogeneous catalytic transformations occur in a liq-
uid or gaseous reaction mixture while the catalyst is a solid material. In most
processes of synthetic importance, the reaction medium is a liquid, thus here
we focus on liquid-phase reactions. Therefore the role of the solvents in these
reactions is of utmost relevance. The solvent could possess several roles in a
heterogeneous catalytic reaction. Its primary role is to dissolve the substrate
and ensure that the substrate can be transported to the surface of the catalyst
where the reaction would occur. If the reaction is a three-phase system (e.g.,
hydrogenation with a solid catalyst/liquid solvent/gaseous hydrogen) then the
solvent should be able to dissolve the gas as well, although with proper agitation
the metal particles can adsorb the hydrogen at the liquid/gas phase border as
well. The solvent does not have to dissolve the substrate completely, a reason-
able solubility can guarantee an efficient process. However, it is expected that
the product is soluble in the solvent, otherwise the product will remain on the
surface of the catalyst after a complete cycle and will block the active centers.
In addition to dissolving the substrate(s), the solvent could have other important
contributions to the success of a catalytic reaction. For example, it can act as
an agent that modifies one of the reaction participants. For example, in the Pt-
catalyzed cinchona alkaloid-modified heterogeneous catalytic hydrogenations
of α-ketoesters, acetic acid was found to be the best solvent. The broadly ac-
cepted explanation is that the acid protonates the basic quinuclidine nitrogen
of the alkaloid and enables it to form a complex with the carbonyl group of
the ketoester.82 The solvent itself can also serve to trap an intermediate or a
product to inhibit successive reactions that may decrease the yield or selectivity.
Although these examples indicate that the solvent may participate in the reac-
tion, it should not strongly adsorb on the catalyst’s surface, otherwise, due to its
large excess it could block the adsorption of the substrate(s).
The application of nontraditional activation methods, particularly
microwave-assisted organic synthesis, enabled the preparation of a broad variety
of compounds under solvent-free conditions. The specific microwave absorbing
ability of the support K-10 montmorillonite and similar catalysts ensured ef-
fective internal heating of the system and a simple protocol provided several
N-heterocyclic compounds, such as pyrroles,83–85 quinolines,86, 87 pyrazoles,88–90
β-carbolines,91, 92 benzodiazepines,93, 94 and multicyclic products95 in high
yields, and in short (few minutes) reaction times.
The physical and chemical properties of the catalyst are also important ex-
perimental variables. The support (if supported catalyst), the particle size, and
the pore volume/size/diameter are all vital in the design of a successful protocol.
The catalysts are discussed in detail later in the book, and the reader is referred
to Chapter 2 regarding more information.
Many catalytic reactions are carried out in a system that includes at least
one gas. In these reactions the pressure of the system often plays a crucial role
in determining reaction rates, yields, and selectivities.96 Many of these reac-
tions are carried out under high-pressure conditions, while others work better
in low-pressure environment. The role of the pressure is often determined by
a competition regarding adsorption on the catalyst’s surface. For example, in
many hydrogenation reactions the substrate has an equal or lower adsorption
capability than the reactant hydrogen; in such cases too high hydrogen pres-
sure would sweep the reactant off the surface and the effect of the pressure on
the conversion/yield is described by a maximum curve (Langmuir-Hinshelwood
mechanism).97 The effect of the pressure is also dependent on the type of reac-
tion that occurs. Hydrogenation reactions prefer higher pressures, while dehy-
drogenation (or reactions that result in the loss of a gaseous product) rather
proceed well at lower pressures. As a special case, some reactions are carried
out in solvents that are gases at room temperature (e.g., ethane or CO2), but
would turn to supercritical fluids under certain conditions. In these reactions an
appropriate pressure and temperature should be applied to maintain the super-
critical state of the medium. Heterogeneous catalysis in supercritical fluids at-
tracted significant attention and have been extensively reviewed,98–100 including
applications regarding biobased technologies, such as biodiesel production.101
Nearly every chemical reaction, heterogeneous catalytic ones included, re-
quires activation at some level. The activation energy for a reaction is commonly
provided by increasing the temperature, which has a profound effect on the rate
of reactions, heterogeneous catalytic ones included. The traditional convective
heating is often ineffective and slow, and due to the uneven heating profile the
temperature gradient within a system could result in undesirable side reactions.

A recent book provides an overview on nontraditional activation methods, in-
cluding microwave and ultrasound irradiation; photo-, electro-, and mechano-
chemistry; and high hydrostatic pressure.102 In addition, several reviews also
summarize specific areas of this field related to heterogeneous catalysis, such
as microwave-assisted organic synthesis,42, 103, 104 sonochemistry,105–107 pho-
tochemistry,108–110 electrochemistry,111–113 mechanochemistry,114–116 and high
hydrostatic pressure.117–119 Although the efficacy of these methods has been
broadly illustrated, one must not forget that not all of them work through gen-
erating internal heating and thus elevated temperatures. Ultrasounds, photo and
electrochemistry, and high hydrostatic pressure initiate reactions by different
mechanisms. The earlier referenced book and reviews provide detailed descrip-
tion of the mode of action of these activation methods.
1.2.2.6 Catalytic reactors

Heterogeneous catalytic reactions are generally carried out in two different re-
actor systems: batch reactors and flow reactors.120 Depending on the actual pro-
cess both systems possess their own benefits as well as disadvantages.
Batch reactors are highly popular in laboratory-level syntheses, and certain
industrial processes, such as many catalytic hydrogenations, are carried out in a
batch reactor.121 These reactors are finite volume systems that can be operated in
an open or closed format. Depending on their use the reactors are made of a va-
riety of materials, such as glass (mostly laboratory applications), stainless steel,
with or without a Teflon liner, or monel (for high acidity reaction mixtures) just
to name a few. When the reactor is applied in a closed format, the user may have
the opportunity to operate under pressurized conditions, in which case the pres-
sure can vary from 1 bar to several hundred bars.122, 123 Most of the pressurized
systems are applied for reactions when at least one component is a gas, such as
hydrogenation or hydroformylation. Low-pressure (e.g., atmospheric) systems
can be connected to a gas burette, and the user would be able to measure the
consumed gaseous reactant, e.g., hydrogen, and thus these systems are quite
useful for mechanistic and kinetic studies. These systems can also be applied in
the reverse process; when a reaction releases a gas as product, the gas burette
can measure the produced gas amount. High-pressure reactors are connected to
gas tanks that supply the gases.
In all batch reactors agitation is a crucial issue. Many heterogeneous cata-
lytic applications qualify as three-phase systems, with the catalyst being solid
in a solvent with an additional gas. Only effective agitation can ensure that the
mass transport limitations are properly addressed. Laboratory size systems can
efficiently work with an internal magnetic spin bar, and an external magnetic
stirrer, that can also serve as an external heating unit. The larger pilot plant
or industrial units are stirred with external motor-operated turbines of various
designs.44
Major advantages include the relatively simple design and handling; how-
ever, the separation and the potential recycling of the catalyst may present chal-
lenges. In addition, the potentially uneven heat profile of the reactor may cause
overheating at the heating elements (usually the wall) and could result in unde-
sired by-product formation.
The flow reactors represent the other major type.121 Many catalytic reactions
can be carried out in a continuous process by the application of flow reactors.
Although the chemical industry used flow systems for a long time, especially
for large-scale processes, now, laboratory-scale flow chemistry became highly
popular.124 In general, a flow reactor is based on a pump or set of pumps that
will move the reactant mixture through a fixed or fluid bed reactor that is de-
signed to block the catalyst’s way out so it stays in place and at the end the prod-
uct mixture is amassed in a collector. Flow systems can operate in several ways
using liquid or gaseous mobile phase. In special applications (e.g., hydrogena-
tion) the substrate is carried by a liquid mobile phase and the reactant hydrogen
is added via a special valve system, thus even three-phase reactions can be ap-
plied. Several older and current designs are described in the literature.125, 126
Flow systems have several major advantages. One of the most important
ones is that these reactors allow continuous production of chemicals.127 In ad-
dition, the well-defined catalytic bed makes catalyst recycling and recovery
relatively simple. For the modern laboratory-scale flow reactors the catalyst is
supplied in the form of cartridges that can be easily replaced and moved to re-
generation. The main disadvantage is that the potentially short residence time
the reactants spend in the reactor may result in lower than expected conversion.
1.3. Conclusions and outlook

This introductory chapter summarized the brief history of catalysis and also
described the most important characteristics of catalytic reactions, primarily fo-
cusing on heterogeneous catalysis, which is the main focus of this book. Many
different terms and phenomena have been described with the goal of providing
a short introduction to nonexperts into the realm of heterogeneous catalysis and
make the terminology used in the upcoming chapters clear.
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You walk up and through the cosy apartments, push back a folding
glass door, and step out upon a balcony of marble.
How still it all is! Only the plash of the water about the bows of the
gondolas, and the little waves snapping at the water-steps. Even the
groups of people around the small iron tables below, partly hidden by
the bloom of oleanders, talk in half-heard whispers.
You look about you,—the stillness filling your soul, the soft air
embracing you,—out over the blossoms of the oleanders, across the
shimmering water, beyond the beautiful dome of the Salute, glowing
like a huge pearl in the clear evening light. No, it is not the Venice of
your childhood; not the dream of your youth. It is softer, more
mellow, more restful, more exquisite in its harmonies.
Suddenly a strain of music breaks upon your ear—a soft, low strain.
Nearer it comes, nearer. You lean forward over the marble rail to
catch its meaning. Far away across the surface of the beautiful sea
floats a tiny boat. Every swing of the oar leaves in its wake a
quivering thread of gold. Now it rounds the great red buoy, and is lost
behind the sails of a lazy lugger drifting with the tide. Then the whole
broad water rings with the melody. In another instant it is beneath
you—the singer standing, holding his hat for your pennies; the
chorus seated, with upturned, expectant faces.
Into the empty hat you pour all your store of small coins, your eyes
full of tears.
GONDOLA DAYS
HAT first morning in Venice! It is the summer, of course—
never the winter. This beautiful bride of the sea is loveliest
when bright skies bend tenderly over her, when white mists
fall softly around her, and the lagoons about her feet are
sheets of burnished silver: when the red oleanders thrust their
blossoms exultingly above the low, crumbling walls: when the black
hoods of winter felsi are laid by at the traghetti, and gondolas flaunt
their white awnings: when the melon-boats, with lifeless sails, drift
lazily by, and the shrill cry of the fruit vender floats over the water:
when the air is steeped, permeated, soaked through and through
with floods of sunlight—quivering, brilliant, radiant; sunlight that
blazes from out a sky of pearl and opal and sapphire; sunlight that
drenches every old palace with liquid amber, kissing every moulding
awake, and soothing every shadow to sleep; sunlight that caresses
and does not scorch, that dazzles and does not blind, that illumines,
irradiates, makes glorious, every sail and tower and dome, from the
instant the great god of the east shakes the dripping waters of the
Adriatic from his face until he sinks behind the purple hills of Padua.
These mornings, then! How your heart warms and your blood tingles
when you remember that first one in Venice—your first day in a
gondola!
You recall that you were leaning upon your balcony overlooking the
garden when you caught sight of your gondolier; the gondolier whom
Joseph, prince among porters, had engaged for you the night of your
arrival.
On that first morning you were just out of your bed. In fact, you had
hardly been in it all night. You had fallen asleep in a whirl of
contending emotions. Half a dozen times you had been up and out
on this balcony, suddenly aroused by the passing of some music-
boat filling the night with a melody that seemed a thousand fold more
enchanting because of your sudden awakening,—the radiant moon,
and the glistening water beneath. I say you were out again upon this
same balcony overlooking the oleanders, the magnolias, and the
palms. You heard the tinkling of spoons in the cups below, and knew
that some earlier riser was taking his coffee in the dense shrubbery;
but it made no impression upon you. Your eye was fixed on the
beautiful dome of the Salute opposite; on the bronze goddess of the
Dogana waving her veil in the soft air; on the group of lighters
moored to the quay, their red and yellow sails aglow; on the noble
tower of San Giorgio, sharp-cut against the glory of the east.
Now you catch a waving hand and the lifting of a cap on the gravel
walk below. “At what hour will the Signore want the gondola?”
You remember the face, brown and sunny, the eyes laughing, the
curve of the black mustache, and how the wavy short hair curled
about his neck and struggled out from under his cap. He has on
another suit, newly starched and snow-white; a loose shirt, a wide
collar trimmed with blue, and duck trousers. Around his waist is a
wide blue sash, the ends hanging to his knees. About his throat is a
loose silk scarf—so loose that you note the broad, manly chest, the
muscles of the neck half concealed by the cross-barred boating-shirt
covering the brown skin.
There is a cheeriness, a breeziness, a spring about this young fellow
that inspires you. As you look down into his face you feel that he is
part of the air, of the sunshine, of the perfume of the oleanders. He
belongs to everything about him, and everything belongs to him. His
costume, his manner, the very way he holds his hat, show you at a
glance that while for the time being he is your servant, he is, in many
things deeply coveted by you, greatly your master. If you had his
chest and his forearm, his sunny temper, his perfect digestion and
contentment, you could easily spare one half of your world’s
belongings in payment. When you have lived a month with him and
have caught the spirit of the man, you will forget all about these
several relations of servant and master. The six francs a day that you
pay him will seem only your own contribution to the support of the
gondola; his share being his services. When you have spent half the
night at the Lido, he swimming at your side, or have rowed all the
way to Torcello, or have heard early mass at San Rosario, away up
the Giudecca, he kneeling before you, his hat on the cool pavement
next your own, you will begin to lose sight even of the francs, and
want to own gondola and all yourself, that you may make him guest
and thus discharge somewhat the ever-increasing obligation of
hospitality under which he places you. Soon you will begin to realize
that despite your belongings—wealth to this gondolier beyond his
wildest dreams—he in reality is the richer of the two. He has
inherited all this glory of palace, sea, and sky, from the day of his
birth, and can live in it every hour in the year, with no fast-ebbing
letter-of-credit nor near-approaching sailing day to sadden his soul or
poison the cup of his pleasure. When your fatal day comes and your
trunk is packed, he will stand at the water-stairs of the station, hat in
hand, the tears in his eyes, and when one of the demons of the
master-spirit of the age—Hurry—has tightened its grip upon you and
you are whirled out and across the great iron bridge, and you begin
once more the life that now you loathe, even before you have
reached Mestre—if your gondolier is like my own gondolier, Espero
—my Espero Gorgoni, whom I love—you would find him on his
knees in the church next the station, whispering a prayer for your
safe journey across the sea, and spending one of your miserable
francs for some blessed candles to burn until you reached home.
But you have not answered your gondolier, who stands with
upturned eyes on the graveled walk below.
“At what hour will the Signore want the gondola?”
You awake from your reverie. Now! as soon as you swallow your
coffee. Ten minutes later you bear your weight on Giorgio’s bent
elbow and step into his boat.
It is like nothing else of its kind your feet have ever touched—so
yielding and yet so firm; so shallow and yet so stanch; so light, so
buoyant, and so welcoming to peace and rest and comfort.
How daintily it sits the water! How like a knowing swan it bends its
head, the iron blade of the bow, and glides out upon the bosom of
the Grand Canal! You stop for a moment, noting the long, narrow
body, blue-black and silver in the morning light, as graceful in its
curves as a bird; the white awning amidships draped at sides and
back, the softly-yielding, morocco-covered seat, all cushions and silk
fringes, and the silken cords curbing quaint lions of polished brass.
Beyond and aft stands your gondolier, with easy, graceful swing
bending to his oar. You stoop down, part the curtains, and sink into
the cushions. Suddenly an air of dignified importance steals over
you. Never in your whole life have you been so magnificently carried
about. Four-in-hands, commodores’ gigs, landaus in triumphant
processions with white horses and plumes, seem tame and
commonplace. Here is a whole barge, galleon, Bucentaur, all to
yourself; noiseless, alert, subservient to your airiest whim, obedient
to the lightest touch. You float between earth and sky. You feel like a
potentate out for an airing, housed like a Rajah, served like
Cleopatra, and rowed like a Doge. You command space and
dominate the elements.
THE GATELESS POSTS OF THE PIAZZETTA

But Giorgio is leaning on his oar, millions of diamonds dripping from
its blade.
“Where now, Signore?”
Anywhere, so he keeps in the sunlight. To the Piazza, perhaps, and
then around San Giorgio with its red tower and noble façade, and
later, when the shadows lengthen, away down to the Public Garden,
and home again in the twilight by way of the Giudecca.
This gondola-landing of the Piazza, the most important of the cab-
stands in Venice, is the stepping-stone—a wet and ooze-covered
stone—to the heart of the city. Really the heart, for the very life of
every canal, campo, and street, courses through it in unending flow
all the livelong day and night, from the earliest blush of dawn to the
earliest blush of dawn again; no one ever seems to go to bed in
Venice. Along and near the edge of this landing stand the richest
examples of Venetian architecture. First, the Royal Gardens of the
king’s palace, with its balustrade of marble and broad flight of water-
steps; then the Library, with its cresting of statues, white against the
sky; then the two noble columns, the gateless posts of the Piazzetta,
bearing Saint Theodore and the Lion of Venice; and beyond, past the
edge of San Marco, the clock tower and the three great flag-staffs;
then the Palace of the Doges, that masterwork of the fifteenth
century; then the Prison, with a glimpse of the Bridge of Sighs,
caught in mid-air; then the great cimeter-sweep of the Riva, its point
lost in the fringe of trees shading the Public Garden; and then, over
all, as you look up, the noble Campanile, the wonderful bell-tower of
San Marco, unadorned, simple, majestic—up, up, into the still air, its
gilded angel, life-size, with outstretched wings flashing in the
morning sun, a mere dot of gold against the blue.
Before you touch the lower steps of the water-stairs, your eye falls
upon an old man with bared head. He holds a long staff studded with
bad coins, having a hook at one end. With this in one hand he
steadies your gondola, with the other he holds out his hat. He is an
aged gondolier, too old now to row. He knows you, the poor fellow,
and he knows your kind. How many such enthusiasts has he helped
to alight! And he knows Giorgio too, and remembers when, like him,
he bent his oar with the best. You drop a penny into his wrinkled
hand, catch his grateful thanks, and join the throng. The arcades
under the Library are full of people smoking and sipping coffee. How
delicious the aroma and the pungent smell of tobacco! In the shadow
of the Doges’ Palace groups idle and talk—a little denser in spots
where some artist has his easel up, or some pretty, dainty child is
feeding the pigeons.
A moment more and you are in the Piazza of San Marco; the grand
piazza of the doges, with its thousands of square feet of white
pavement blazing in the sun, framed on three sides by marble
palaces, dominated by the noblest campanile on the globe, and
enriched, glorified, made inexpressibly precious and unique by that
jewel in marble, in porphyry, in verd antique and bronze, that despair
of architects of to-day, that delight of the artists of all time—the most
sacred, the Church of San Marco.
In and out this great quadrangle whirl the pigeons, the pigeons of
Dandolo, up into the soft clouds, the light flashing from their throats;
sifting down in showers on gilded cross and rounded dome; clinging
to intricate carvings, over and under the gold-crowned heads of
saints in stone and bronze; across the baking plaza in flurries of gray
and black; resting like a swarm of flies, only to startle, mass, and
swirl again. Pets of the state, these birds, since the siege of Candia,
when the great Admiral Dandolo’s chief bearer of dispatches, the
ancestor of one of these same white-throated doves, brought the
good news to Venice the day the admiral’s victorious banner was
thrown to the breeze, and the Grand Council, sitting in state, first
learned the tidings from the soft plumage of its wings.
At one end, fronting the church, stand the three great flag-poles, the
same you saw at the landing, socketed in bronze, exquisitely
modeled and chased, bearing the banners of Candia, Cyprus, and
the Morea—kingdoms conquered by the state—all three in a row,
presenting arms to the power that overthrew them, and forever
dipping their colors to the glory of its past.
Here, too, in this noble square, under your very feet, what
solemnities, what historic fêtes, what conspiracies! Here for
centuries has been held the priestly pageant of Corpus Christi,
aflame with lanterns and flambeaux. Here eleven centuries ago blind
old Dandolo received the Crusader chiefs of France. Here the
splendid nuptials of Francesco Foscari were celebrated by a
tournament, witnessed by thirty thousand people, and lasting ten
days. Here the conspiracies of Tiepolo and Faliero were crushed—
Venetian against Venetian the only time in a thousand years. And
here Italy suffered her crowning indignity, the occupation by the
French under the newly-fledged warrior who unlimbered his cannon
at the door of the holy church, pushed the four bronze horses from
their pedestals over the sacred entrance—the horses of Constantine,
wrought by Lysippus the Greek,—despoiled the noble church of its
silver lamps, robbed the ancient column of its winged lion, and then,
after a campaign unprecedented in its brilliancy, unexampled in the
humiliation and degradation it entailed upon a people who for ten
centuries had known no power outside of Venice, planted in the
centre of this same noble square, with an irony as bitter as it was
cruel, the “Tree of Liberty,” at which was burned, on the 4th of June,
1797, the insignia of the ancient republic.
And yet, notwithstanding all her vicissitudes, the Venice of to-day is
still the Venice of her glorious past, the Venice of Dandolo, Foscari,
and Faliero. The actors are long since dead, but the stage-setting is
the same; the same sun, the same air, the same sky over all. The
beautiful dome of the Salute still dominates the Grand Canal. The
great plaza is still perfect in all its proportions and in all that made up
its beauty and splendor. The Campanile still raises its head,
glistening in the morning light. High over all still flash and swoop the
pigeons of Venice—the pigeons of Dandolo—now black as cinders,
now flakes of gold in the yellow light. The doors of the sacred church
are still open; the people pass in and out. Under the marble arcades,
where the soldiers of the army of France stacked their arms, to-day
sit hundreds of free Venetians, with their wives and sweethearts,
sipping their ices and coffee; the great orchestra, the king’s band,
filling the air with its music.
When you ask what magician has wrought this change, let the old
guide answer as once he answered me when, crossing the Piazza
and uncovering his head, he pointed to a stone and said, in his soft
Italian:—
“Here, Signore,—just here, where the great Napoleon burnt our flag,
—the noble republic of our fathers, under our good King and his
royal spouse, was born anew.”
But you cannot stay. You will return and study the Piazza to-morrow;
not now. The air intoxicates you. The sunlight is in your blood; your
cheeks burn; you look out and over the Grand Canal—molten silver
in the shimmer of the morning. Below, near the Public Garden,
beyond San Giorgio, like a cluster of butterflies, hovers a fleet of
Chioggia fishing-boats, becalmed in the channel. Off the Riva, near
Danieli’s, lies the Trieste steamer, just arrived, a swarm of gondolas
and barcos about her landing-ladders; the yellow smoke of her
funnel drifting lazily. Farther away, on the golden ball of the Dogana,
the bronze Goddess of the Wind poises light as air, her face aflame,
her whirling sail bent with the passing breeze.
You resolve to stop no more; only to float, loll on your cushions,
watch the gulls circle, and the slow sweep of the oars of the luggers.
You would throw open—wide open—the great swinging gates of
your soul. You not only would enjoy, you would absorb, drink in, fill
yourself to the brim.
For hours you drift about. There is plenty of time to-morrow for the
churches and palaces and caffès. To-day you want only the salt air in
your face, the splash and gurgle of the water at the bow, and the low
song that Giorgio sings to himself as he bends to his blade.
Soon you dart into a cool canal, skirt along an old wall, water stained
and worn, and rest at a low step. Giorgio springs out, twists a cord
around an iron ring, and disappears through an archway framing a
garden abloom with flowering vines.
It is high noon. Now for your midday luncheon!
You have had all sorts of breakfasts offered you in your wanderings:
On white-winged yachts, with the decks scoured clean, the brass
glistening, the awning overhead. In the wilderness, lying on balsam
boughs, the smell of the bacon and crisping trout filling the bark
slant, the blue smoke wreathing the tall pines. In the gardens of
Sunny Spain—one you remember at Granada, hugging the great
wall of the Alhambra—you see the table now with its heap of fruit
and flowers, and can hear the guitar of the gypsy behind the
pomegranate. Along the shore of the beautiful bay of Matanzas,
where the hidalgo who had watched you paint swept down in his
volante and carried you off to his oranges and omelette. At St.
Cloud, along the Seine, with the noiseless waiter in the seedy dress
suit and necktie of the night before. But the filet and melon! Yes, you
would go again. I say you have had all sorts of breakfasts out of
doors in your time, but never yet in a gondola.
A few minutes later Giorgio pushes aside the vines. He carries a
basket covered with a white cloth. This he lays at your feet on the
floor of the boat. You catch sight of the top of a siphon and a flagon
of wine: do not hurry, wait till he serves it. But not here, where
anybody might come; farther down, where the oleanders hang over
the wall, their blossoms in the water, and where the air blows cool
between the overhanging palaces.
Later Giorgio draws all the curtains except the side next the
oleanders, steps aft and fetches a board, which he rests on the little
side seats in front of your lounging-cushions. On this board he
spreads the cloth, and then the seltzer and Chianti, the big glass of
powdered ice and the little hard Venetian rolls. (By the bye, do you
know that there is only one form of primitive roll, the world over?)
Then come the cheese, the Gorgonzola—active, alert Gorgonzola,
all green spots—wrapped in a leaf; a rough-jacketed melon, with
some figs and peaches. Last of all, away down in the bottom of the
basket, there is a dish of macaroni garnished with peppers. You do
not want any meat. If you did you would not get it. Some time when
you are out on the canal, or up the Giudecca, you might get a fish
freshly broiled from a passing cook-boat serving the watermen—a
sort of floating kitchen for those who are too poor for a fire of their
own—but never meat.
Giorgio serves you as daintily as would a woman; unfolding the
cheese, splitting the rolls, parting the melon into crescents, flecking
off each seed with his knife: and last, the coffee from the little copper
coffee-pot, and the thin cakes of sugar, in the thick, unbreakable,
dumpy little cups.
There are no courses in this repast. You light a cigarette with your
first mouthful and smoke straight through: it is that kind of a
breakfast.
Then you spread yourself over space, flat on your back, the smoke
curling out through the half-drawn curtains. Soon your gondolier
gathers up the fragments, half a melon and the rest,—there is
always enough for two,—moves aft, and you hear the clink of the
glass and the swish of the siphon. Later you note the closely-eaten
crescents floating by, and the empty leaf. Giorgio was hungry too.
But the garden!—there is time for that. You soon discover that it is
unlike any other you know. There are no flower-beds and gravel
walks, and no brick fountains with the scantily dressed cast-iron boy
struggling with the green-painted dolphin, the water spurting from its
open mouth. There is water, of course, but it is down a deep well
with a great coping of marble, encircled by exquisite carvings and
mellow with mould; and there are low trellises of grapes, and a
tangle of climbing roses half concealing a weather-stained Cupid
with a broken arm. And there is an old-fashioned sun-dial, and sweet
smelling box cut into fantastic shapes, and a nest of an arbor so
thickly matted with leaves and interlaced branches that you think of
your Dulcinea at once. And there are marble benches and stone
steps, and at the farther end an old rusty gate through which Giorgio
brought the luncheon.
It is all so new to you, and so cool and restful! For the first time you
begin to realize that you are breathing the air of a City of Silence. No
hum of busy loom, no tramp of horse or rumble of wheel, no jar or
shock; only the voices that come over the water, and the plash of the
ripples as you pass. But the day is waning; into the sunlight once
more.
Giorgio is fast asleep; his arm across his face, his great broad chest
bared to the sky.
“Si, Signore!”
He is up in an instant, rubbing the sleep from his eyes, catching his
oar as he springs.
You glide in and out again, under marble bridges thronged with
people; along quays lined with boats; by caffè, church, and palace,
and so on to the broad water of the Public Garden.
But you do not land; some other day for that. You want the row back
up the canal, with the glory of the setting sun in your face. Suddenly,
as you turn, the sun is shut out: it is the great warship Stromboli,
lying at anchor off the garden wall; huge, solid as a fort, fine-lined as
a yacht, with exquisite detail of rail, mast, yard-arms, and gun
mountings, the light flashing from her polished brasses.
In a moment you are under her stern, and beyond, skirting the old
shipyard with the curious arch,—the one Whistler etched,—sheering
to avoid the little steamers puffing with modern pride, their noses
high in air at the gondolas; past the long quay of the Riva, where the
torpedo-boats lie tethered in a row, like swift horses eager for a
dash; past the fruit-boats dropping their sails for a short cut to the
market next the Rialto; past the long, low, ugly bath-house anchored
off the Dogana; past the wonderful, the matchless, the never-to-be-
unloved or forgotten, the most blessed, the Santa Maria della Salute.
THE ONE WHISTLER ETCHED

Oh! this drift back, square in the face of the royal sun, attended by all
the pomp and glory of a departing day! What shall be said of this
reveling, rioting, dominant god of the west, clothed in purple and fine
gold; strewing his path with rose-leaves thrown broadcast on azure
fields; rolling on beds of violet; saturated, steeped, drunken with
color; every steeple, tower, and dome ablaze; the whole world on tip-
toe, kissing its hands good-night!
Giorgio loves it, too. His cap is off, lying on the narrow deck; his
cravat loosened, his white shirt, as he turns up the Giudecca,
flashing like burning gold.
Somehow you cannot sit and take your ease in the fullness of all this
beauty and grandeur. You spring to your feet. You must see behind
and on both sides, your eye roving eagerly away out to the lagoon
beyond the great flour-mill and the gardens.
Suddenly a delicate violet light falls about you; the lines of palaces
grow purple; the water is dulled to a soft gray, broken by long,
undulating waves of blue; the hulls of the fishing-boats become inky
black, their listless sails deepening in the falling shadows. Only the
little cupola high up on the dome of the Redentore still burns pink
and gold. Then it fades and is gone. The day is done!
ALONG THE RIVA
HE afternoon hours are always the best. In the morning the
great sweep of dazzling pavement is a blaze of white light,
spotted with moving dots of color. These dots carry gay-
colored parasols and fans, or shield their eyes with aprons,
hugging, as they scurry along, the half-shadows of a bridge-rail or
caffè awning. Here and there, farther down along the Riva, are larger
dots—fruit-sellers crouching under huge umbrellas, or groups of
gondoliers under improvised awnings of sailcloth and boat oars.
Once in a while one of these water-cabmen darts out from his shelter
like an old spider, waylays a bright fly as she hurries past, and
carries her off bodily to his gondola. Should she escape he crawls
back again lazily and is merged once more in the larger dot. In the
noonday glare even these disappear; the fruit-sellers seeking some
shaded calle, the gondoliers the cool coverings of their boats.
Now that the Sun God has chosen to hide his face behind the trees
of the King’s Garden, this blaze of white is toned to a cool gray. Only
San Giorgio’s tower across the Grand Canal is aflame, and that but
half way down its bright red length. The people, too, who have been
all day behind closed blinds and doors, are astir. The awnings of the
caffès are thrown back and the windows of the balconies opened.
The waiters bring out little tables, arranging the chairs in rows like
those in a concert hall. The boatmen who have been asleep under
cool bridges, curled up on the decks of their boats, stretch
themselves awake, rubbing their eyes. The churches swing back
their huge doors—even the red curtains of the Chiesa della Pietà are
caught to one side, so that you can see the sickly yellow glow of the
candles far back on the altars and smell the incense as you pass.
Soon the current from away up near the Piazza begins to flow down
towards the Public Garden, which lies at the end of this Grand
Promenade of Venice. Priests come, and students; sailors on a half
day’s leave; stevedores from the salt warehouses; fishermen;
peddlers, with knick-knacks and sweetmeats; throngs from the
hotels; and slender, graceful Venetians, out for their afternoon stroll
in twos and threes, with high combs and gay shawls, worn as a
Spanish Donna would her mantilla—bewitching creatures in cool
muslin dresses and wide sashes of silk, with restless butterfly fans,
and restless, wicked eyes too, that flash and coax as they saunter
along.
Watch those officers wheel and turn. See how they laugh when they
meet. What confidences under mustachios and fans! Half an hour
from now you will find the four at Florian’s, as happy over a little
cherry juice and water as if it were the dryest of all the Extras. Later
on, away out beyond San Giorgio, four cigarettes could light for you
their happy faces, the low plash of their gondolier’s oar keeping time
to the soft notes of a guitar.
Yes, one must know the Riva in the afternoon. I know it every hour in
the day; though I love it most in the cool of its shadows. And I know
every caffè, church, and palace along its whole length, from the Molo
to the garden. And I know the bridges, too; best of all the one below
the Arsenal, the Veneta Marina, and the one you cross before
reaching the little church that stands aside as if to let you pass, and
the queer-shaped Piazzetta beyond, with the flag-pole and marble
balustrade. And I know that old wine-shop where the chairs and
tables are drawn close up to the very bridge itself, its awnings half
over the last step.
My own gondolier, Espero—bless his sunny face!—knows the owner
of this shop and has known her for years; a great, superb creature,
with eyes that flash and smoulder under heaps of tangled black hair.
He first presented me to this grand duchess of the Riva years ago,
when I wanted a dish of macaroni browned on a shallow plate.
Whenever I turn in now out of the heat for a glass of crushed ice and
orange juice, she mentions the fact and points with pride to the old
earthen platter. It is nearly burnt through with my many toastings.
But the bridge is my delight; the arch underneath is so cool, and I
have darted under it so often for luncheon and half an hour’s siesta.
On these occasions the old burnt-bottomed dish is brought to my
gondola sizzling hot, with coffee and rolls, and sometimes a bit of
broiled fish as an extra touch.
This bridge has always been the open-air club-room of the entire
neighborhood,—everybody who has any lounging to do is a life
member. All day long its habitués hang over it, gazing listlessly out
upon the lagoon; singly, in bunches, in swarms when the fish-boats
round in from Chioggia, or a new P. and O. steamer arrives. Its hand-
rail of marble is polished smooth by the arms and legs and blue
overalls of two centuries.
There is also a very dear friend of mine living near this bridge, whom
you might as well know before I take another step along the Riva. He
is attached to my suite. I have a large following quite of his kind,
scattered all over Venice. As I am on my way, in this chapter, to the
Public Garden, and can never get past this his favorite haunt without
his cheer and laugh to greet me; so I cannot, if I would, avoid
bringing him in now, knowing full well that he would bring himself in
and unannounced whenever it should please his Excellency so to
do. He is a happy-hearted, devil-may-care young fellow, who haunts
this particular vicinity, and who has his bed and board wherever, at
the moment, he may happen to be. The bed problem never troubles
him; a bit of sailcloth under the shadow of the hand-rail will do, or a
straw mat behind the angle of a wall, or even what shade I can spare
from my own white umbrella, with the hard marble flags for feathers.
The item of board is a trifle, yet only a trifle, more serious. It may be
a fragment of polenta, or a couple of figs, or only a drink from the
copper bucket of some passing girl. Quantity, quality, and time of
serving are immaterial to him. There will be something to eat before
night, and it always comes. One of the pleasures of the
neighborhood is to share with him a bite.
This beggar, tramp, lasagnone—ragged, barefooted, and
sunbrowned, would send a flutter through the hearts of a matinée full
of pretty girls, could he step to the footlights just as he is, and with
his superb baritone voice ring out one of his own native songs. Lying
as he does now under my umbrella, his broad chest burnt almost
black, the curls glistening about his forehead, his well-trimmed
mustache curving around a mouth half open, shading a row of teeth
white as milk, his Leporello hat thrown aside, a broad red sash
girding his waist, the fine muscles of his thighs filling his overalls,
these same pretty girls might perhaps only draw their skirts aside as
they passed: environment plays such curious tricks.
This friend of mine, this royal pauper, Luigi, never in the recollection
of any mortal man or woman was known to do a stroke of work. He
lives somewhere up a crooked canal, with an old mother who adores
him—as, in fact, does every other woman he knows, young or old—
and whose needle keeps together the rags that only accentuate
more clearly the superb lines of his figure. And yet one cannot call
him a burden on society. On the contrary, Luigi has especial duties
which he never neglects. Every morning at sunrise he is out on the
bridge watching the Chioggia boats as they beat up past the Garden
trying to make the red buoy in the channel behind San Giorgio, and
enlarging on their seagoing qualities to an admiring group of
bystanders. At noon he is plumped down in the midst of a bevy of
wives and girls, flat on the pavement, his back against a doorway in
some courtyard. The wives mend and patch, the girls string beads,
and the children play around on the marble flagging, Luigi
monopolizing all the talk and conducting all the gayety, the whole
coterie listening. He makes love, and chaffs, and sings, and weaves
romances, until the inquisitive sun peeps into the patio; then he is up
and out on the bridge again, and so down the Riva, with the grace of
an Apollo and the air of a thoroughbred.
When I think of all the sour tempers in the world, all the people with
weak backs and chests and limbs, all the dyspeptics, all the bad
livers and worse hearts, all the mean people and the sordid, all those
who pose as philanthropists, professing to ooze sunshine and
happiness from their very pores; all the down-trodden and the
economical ones; all those on half pay and no work, and those on
full pay and too little—and then look at this magnificent condensation
of bone, muscle, and sinew; this Greek god of a tramp, unselfish,
good-tempered, sunny-hearted, wanting nothing, having everything,
envying nobody, happy as a lark, one continuous song all the day
long; ready to catch a line, to mind a child, to carry a pail of water for
any old woman, from the fountain in the Campo near by to the top of
any house, no matter how high—when, I say, I think of this prince of
good fellows leading his Adam-before-the-fall sort of existence, I
seriously consider the advisability of my pensioning him for the
remainder of his life on one lira a day, a fabulous sum to him, merely
to be sure that nothing in the future will ever spoil his temper and so
rob me of the ecstasy of knowing and of being always able to find
one supremely happy human creature on this earth.
But, as I have said, I am on my way to the Public Garden. Everybody
else is going too. Step to the marble balustrade of this three-
cornered Piazzetta and see if the prows of the gondolas are not all
pointed that way. I am afoot, have left the Riva and am strolling down
the Via Garibaldi, the widest street in Venice. There are no palaces
here, only a double row of shops, their upper windows and balconies
festooned with drying clothes, their doors choked with piles of fruit
and merchandise. A little farther down is a marble bridge, and then
the arching trees of the biggest and breeziest sweep of green in all
Venice—the Giardini Pubblici—many acres in extent, bounded by a
great wall surmounted by a marble balustrade more than a mile in
length, and thickly planted with sycamores and flowering shrubs. Its
water front commands the best view of the glory of a Venetian
sunset.
This garden, for Venice, is really a very modern kind of public
garden, after all. It was built in the beginning of the present century,
about 1810, when the young Corsican directed one Giovanni Antonio
Selva to demolish a group of monasteries incumbering the ground
and from their débris to construct the foundations of this noble park,
with its sea-wall, landings, and triumphal gate.
Whenever I stretch myself out under the grateful shade of these
splendid trees, I always forgive the Corsican for robbing San Marco
of its bronze horses and for riding his own up the incline of the
Campanile, and even for leveling the monasteries.
And the Venetians of to-day are grateful too, however much their
ancestors may have reviled the conqueror for his vandalism. All over
its graveled walks you will find them lolling on the benches, grouped
about the pretty caffès, taking their coffee or eating ices; leaning by
the hour over the balustrade and watching the boats and little
steamers. The children romp and play, the candy man and the
sellers of sweet cakes ply their trade, and the vender with cool drinks
stands over his curious four-legged tray, studded with bits of brass
and old coins, and calls out his several mixtures. The officers are
here, too, twisting their mustachios and fingering their cigarettes; fine
ladies saunter along, preceded by their babies, half smothered in
lace and borne on pillows in the arms of Italian peasants with red
cap-ribbons touching the ground; and barefooted, frowzy-headed
girls from the rookeries behind the Arsenal idle about, four or five
abreast, their arms locked, mocking the sailors and filling the air with
laughter.
Then there are a menagerie, or rather some wire-fenced paddocks
filled with kangaroos and rabbits, and an aviary of birds, and a big
casino where the band plays, and where for half a lira, some ten
cents, you can see a variety performance without the variety, and
hear these light-hearted people laugh to their heart’s content.
And last of all, away down at one end, near the wall fronting the
church of San Giuseppe, there lives in miserable solitude the horse
—the only horse in Venice. He is not always the same horse. A few
years ago, when I first knew him, he was a forlorn, unkempt, lonely-
looking quadruped of a dark brown color, and with a threadbare tail.
When I saw him last, within the year, he was a hand higher, white,
and wore a caudal appendage with a pronounced bang. Still he is
the same horse—Venice never affords but one. When not at work
(he gathered leaves in the old days; now I am ashamed to say he
operates a lawn-mower as well), he leans his poor old tired head
listlessly over the rail, refusing the cakes the children offer him. At
these times he will ruminate by the hour over his unhappy lot. When
the winter comes, and there are no more leaves to rake, no gravel to
haul, nor grass to mow, they lead him down to the gate opening on
the little side canal and push him aboard a flat scow, and so on up
the Grand Canal and across the lagoon to Mestre. As he passes
along, looking helplessly from side to side, the gondoliers revile him
and the children jeer at him, and those on the little steamboats pelt
him with peach pits, cigar ends, and bits of broken coal. Poor old
Rosinante, there is no page in the history of Venice which your
ancestors helped glorify!
There are two landings along the front of the garden,—one below the
west corner, up a narrow canal, and the other midway of the long
sea-wall, where all the gondolas load and unload. You know this last
landing at once. Ziem has painted it over and over again for a score
of years or more, and this master of color is still at it. With him it is a
strip of brilliant red, a background of autumn foliage, and a creamy
flight of steps running down to a sea of deepest ultramarine. There is
generally a mass of fishing-boats, too, in brilliant colorings, moored
to the wall, and a black gondola for a centre dark.
When you row up to this landing to-day, you are surprised to find it
all sunshine and glitter. The trees are fresh and crisp, the marble is
dazzling white, and the water sparkling and limpid with gray-green
tints. But please do not criticise Ziem. You do not see it his way, but
that is not his fault. Venice is a hundred different Venices to as many
different painters. If it were not so, you would not be here to-day, nor
love it as you do. Besides, when you think it all over, you will admit
that Ziem, of all living painters, has best rendered its sensuous,
color-soaked side. And yet, when you land you wonder why the
colorist did not bring his easel closer and give you a nearer view of
this superb water-landing, with the crowds of gayly dressed people,
swarms of gondolas, officers, fine ladies, boatmen, and the hundred
other phases of Venetian life.
But I hear Espero’s voice out on the broad water. Now I catch the
sunlight on his white shirt and blue sash. He is standing erect, his
whole body swaying with that long, graceful, sweeping stroke which
is the envy of the young gondoliers and the despair of the old;
Espero, as you know, has been twice winner in the gondola races.
He sees my signal, runs his bow close in, and the next instant we
are swinging back up the Grand Canal, skirting the old boatyard and
the edge of the Piazzetta. A puff of smoke from the man-of-war
ahead, and the roll of the sunset gun booms over the water. Before
the echoes have fairly died away, a long sinuous snake of
employees—there are some seven thousand of them—crawls from
out the arsenal gates, curves over the arsenal bridge, and heads up

Heterogeneous Catalysis in Sustainable Synthesis Advances in Green and Sustainable Chemistry 1St Edition Bela Torok Full Chapter

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Heterogeneous Catalysis in Sustainable

Synthesis (Advances in Green and

For information on all Elsevier publications

Publisher: Susan Dennis

1. Heterogeneous catalysis for organic synthesis:

2. Solid catalysts for environmentally benign synthesis

3. Application of heterogeneous catalysis in the

3.2 Heterogeneous catalytic hydrogenolysis

3.3 Heterogeneous catalytic oxidations

3.4 Metathesis by heterogeneous catalysts

3.5 Friedel-Crafts and related reactions catalyzed

3.5.6 Nitration 360

3.6 Cross-coupling reactions for environmentally

3.7 Multicomponent reactions

3.8 Ring transformations by heterogeneous catalysis

3.9 Heterogeneous catalytic rearrangements and other

3.10 Asymmetric synthesis by solid catalysts

3.10.3 Hydrogenation 599

metathesis, cross-coupling reactions, Friedel-Crafts, and multicomponent reac-

Heterogeneous catalysis for

Heterogeneous Catalysis in Sustainable Synthesis. https://doi.org/10.1016/B978-0-12-817825-6.00014-8

and spearheaded the development of the two main directions of heterogeneous

to time provided extensive background regarding these processes. One of these

1.2.1 Fundamentals and basic definitions

product mass transport

FIG. 1 A generic scheme of a catalytic cycle with the elementary steps.

1.2.1.2 Activation energy

Catalyzed Reaction: A+B I1 EA,1

(EA). Typically, the activation energy of a noncatalytic reaction is significantly

1.2.1.3 Other definitions

Lifetime. As mentioned already, ideally the catalyst should remain unaltered

FIG. 4 Representative examples for different forms of selectivity.

1.2.2 Heterogeneous catalysis

a­ ctive center, regarding solid catalysts, a considerable part of the material is

1.2.2.1 Catalytic surfaces

1.2.2.2 Physical and chemical adsorption

many hydrogenation processes begin with the adsorption of a CX double

1.2.2.3 The active site of solid catalysts

1.2.2.4 Anchoring effects

One of the most common examples is the chemoselective hydrogenation of α,β-

1.2.2.5 Experimental variables

temperature gradient within a system could result in undesirable side reactions.

1.2.2.6 Catalytic reactors

1.3. Conclusions and outlook

6. Döbereiner, J. W. Versuche Über die Gährung. Schweiger J. 1816, 20, 213–214.

THE GATELESS POSTS OF THE PIAZZETTA

THE ONE WHISTLER ETCHED

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a ctive center, regarding solid catalysts, a considerable part of the material is