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Materials Science in Photocatalysis
Materials Science
in Photocatalysis

Edited by
Elisa I. Garcı́a-López
Professor, Department of Biological Chemical and Pharmaceutical Sciences and Technologies
(STEBICEF), University of Palermo, Palermo, Italy

Leonardo Palmisano
“Schiavello-Grillone” Photocatalysis Group, Department of Engineering, University of Palermo,
Palermo, Italy
Elsevier
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Contributors
Numbers in parentheses indicate the pages on which the authors’
contributions begin.
Zahra Abbasi (235), Department of Chemistry, Faculty of
Science, Shahid Chamran University of Ahvaz, Ahvaz,
Iran
Sambandam Anandan (283), Department of Chemistry,
National Institute of Technology, Trichy, India
Masakazu Anpo (171), Department of Applied Chemistry,
Graduate School of Engineering, Osaka Prefecture Uni-
versity, Sakai, Osaka, Japan
K Aswani Raj (505), Department of Chemistry, IIT
Dharwad, Dharwad, Karnataka, India
Ana Bahamonde (83), Environmental Catalystis Engi-
neering Group, Institute of Catalysis and Petrochem-
istry, Madrid, Spain
F. Baldassarre (603), Biological and Environmental
Sciences Department & UdR INSTM of Lecce, University
of Salento; Institute of Nanotechnology, CNR
NANOTEC, National Research Council, Lecce, Italy
Giuseppe Barbieri (523), Department of Environmental
and Chemical Engineering, The University of Calabria,
Rende CS, Italy
Zuzana Barbieriková (125), Institute of Physical Chem-
istry and Chemical Physics, Faculty of Chemical and
Food Technology, Slovak University of Technology
in Bratislava, Bratislava, Slovak Republic
E. Bernardini (357), Chemistry Department, Torino
University, Torino, Italy
C.L. Bianchi (649), Department of Chemistry, Università
degli Studi di Milano, Milano, Italy
Vittorio Boffa (385), Aalborg University, Center for
Membrane Technology, Aalborg, Denmark
C. Bogatu (371), Center for Renewable Energy System and
Recycling, Transilvania University of Brasov, Braşov,
Romania
Fabrı́cio Eduardo Bortot Coelho (385), Chemistry
Department, Torino University, Torino, Italy; Aalborg
University, Center for Membrane Technology, Aalborg,
Denmark
Vlasta Brezová (125), Institute of Physical Chemistry and
Chemical Physics, Faculty of Chemical and Food Tech-
nology, Slovak University of Technology in Bratislava,
Bratislava, Slovak Republic
Adele Brunetti (523), Institute on Membrane Technology
(ITM-CNR), National Research Council c/o The
University of Calabria, Rende CS, Italy
V. Capucci (649), IrisCeramica Group, Fiorano M.se, Italy
Erik Cerrato (221), Department of Chemistry and NIS
Centre, University of Torino, Torino, Italy
G. Cerrato (649), Department of Chemistry, Università
degli Studi di Torino, Torino, Italy
Federico Cesano (385), Chemistry Department; NIS Inter-
departmental Centre, Torino University, Torino, Italy
G. Ciccarella (603), Biological and Environmental
Sciences Department & UdR INSTM of Lecce,
University of Salento; Institute of Nanotechnology,
CNR NANOTEC, National Research Council, Lecce,
Italy
Juan C. Colmenares (575), Institute of Physical Chem-
istry, Polish Academy of Sciences, Warsaw, Poland
Jose C. Conesa (267), Institute of Catalysis and Petrochem-
istry, CSIC, Madrid, Spain
Juan M. Coronado (139), Institute of Catalysis and Petro-
chemistry, CSIC, Madrid, Spain
M. Covei (371), Center for Renewable Energy System and
Recycling, Transilvania University of Brasov, Braşov,
Romania
F. Deganello (357), Institute for the Study of Nanostruc-
tured Materials (ISMN)—Italian National Research
Council (CNR), Palermo, Italy
Francesco Di Franco (115), Dipartimento di Ingegneria,
Università degli Studi di Palermo, Palermo, Italy
R. Djellabi (649), Department of Chemistry, Università
degli Studi di Milano, Milano, Italy
xv
xvi Contributors
A. Duta (371), Center for Renewable Energy System and
Recycling, Transilvania University of Brasov, Braşov,
Romania
Dana Dvoranová (125), Institute of Physical Chemistry
and Chemical Physics, Faculty of Chemical and Food
Technology, Slovak University of Technology in
Bratislava, Bratislava, Slovak Republic
Gabriela Dyrda (183), Institute of Chemistry, University
of Opole, Opole, Poland
Maya Endo-Kimura (421), Institute for Catalysis (ICAT),
Hokkaido University, Sapporo, Japan
D. Fabbri (357), Chemistry Department, Torino
University, Torino, Italy
Irina M. Factori (341), Human and Natural Sciences Center,
Federal University of ABC—UFABC, Santo Andre, SP,
Brazil
Marisol Faraldos (83), Environmental Catalystis Engi-
neering Group, Institute of Catalysis and Petrochem-
istry, Madrid, Spain
Junting Feng (485), State Key Laboratory of Chemical
Resource Engineering, Beijing University of Chemical
Technology, Beijing, China
Pablo S. Fernández (341), Chemistry Institute, State
University of Campinas—UNICAMP, Campinas, SP,
Brazil
Marcos Fernández-Garcı́a (409), Institute of Catalysis
and Petrochemistry, CSIC, Madrid, Spain
Belen Ferrer (543), Chemistry Department, Universitat
Politècnica de València, Valencia, Spain
Paolo Fornasiero (485), Chemistry Department, INSTM
and ICCOM-CNR Trieste Research Unit, University
of Trieste, Trieste, Italy
Fernando Fresno (139), Photoactivated Processes Unit,
Institute IMDEA Energy, Madrid, Spain
R. Galli (649), DiSTAS-Department for Sustainable Food
Process, Università Cattolica del Sacro Cuore, Piacenza,
Italy
Hermenegildo Garcı́a (543), Instituto Universitario de
Tecnologı́a Quı́mica, CSIC-UPV, Universitat Poli-
tècnica de València, Valencia, Spain
Elisa I. Garcı́a-López (3, 13, 37, 235, 319), Department
of Biological, Chemical and Pharmaceutical Sciences
and Technologies (STEBICEF), University of Palermo,
Palermo, Italy
Dimitrios A. Giannakoudakis (575), Institute of Physical
Chemistry, Polish Academy of Sciences, Warsaw,
Poland
D.B. Hernandez-Uresti (211), Autonomous University of
Nuevo León, Physical-Mathematical Sciences Faculty,
Cd. Universitaria, San Nicolás de los Garza, NL,
Mexico
Sam Hseien-Y. Hsu (575), School of Energy and
Environment, Hong Kong, China
Shin-Ting Hwang (283), Department of Environmental
Engineering and Science, Feng Chia University,
Taichung, Taiwan
Ana Iglesias-Juez (139), Institute of Catalysis and Petro-
chemistry, CSIC, Madrid, Spain
Lakshmanan Karuppasamy (283), Department of Envi-
ronmental Engineering and Science, Feng Chia
University, Taichung, Taiwan
Marcin Kobielusz (95), Faculty of Chemistry, Jagiellonian
University, Kraków, Poland
Ewa Kowalska (421), Institute for Catalysis (ICAT);
Graduate School of Environmental Science, Hokkaido
University, Sapporo, Japan
Anna Kubacka (409), Institute of Catalysis and Petro-
chemistry, CSIC, Madrid, Spain
Joanna Kuncewicz (95), Faculty of Chemistry, Jagiel-
lonian University, Kraków, Poland
Maria Kuznetsova (341), Human and Natural Sciences
Center, Federal University of ABC—UFABC, Santo
Andre, SP, Brazil
Xianjun Lang (561), Sauvage Center for Molecular Sci-
ences, College of Chemistry and Molecular Sciences,
Wuhan University, Wuhan, China
Enzo Laurenti (589), Chemistry Department, Torino
University, Torino, Italy
Xia Li (561), Sauvage Center for Molecular Sciences,
College of Chemistry and Molecular Sciences, Wuhan
University, Wuhan, China
Leonarda F. Liotta (13), Institute for the Study of Nano-
structured Materials, Palermo, Italy
Wojciech Macyk (95), Faculty of Chemistry, Jagiellonian
University, Kraków, Poland
Giuliana Magnacca (357, 385, 589), Chemistry Department;
NIS Interdepartmental Centre, Torino University, Torino,
Italy
Giuseppe Marcı̀ (13, 37, 319), Department of Engineering,
University of Palermo, Palermo, Italy
Michele Mazzanti (301), Department of Chemical,
Pharmaceutical and Agricultural Sciences, University
of Ferrara, Ferrara, Italy
Giuseppe Mele (183), Department of Engineering for
Innovation, University of Salento, Lecce, Italy
Arianna Melillo (543), Chemistry Department, Universitat
Politècnica de València, Valencia, Spain

Marco Minella (449), Department of Chemistry and
NIS—Nanostructured Interfaces and Surfaces Inte-
rdepartmental Centre, University of Turin, Turin,
Italy
Claudio Minero (449), Department of Chemistry and
NIS—Nanostructured Interfaces and Surfaces Interde-
partmental Centre, University of Turin, Turin, Italy
Alessandra Molinari (301), Department of Chemical,
Pharmaceutical and Agricultural Sciences, University
of Ferrara, Ferrara, Italy
Nikolaos G. Moustakas (255), Leibinz Institute for
Catalysis (LIKAT), Rostock, Germany
Vaishakh Nair (575), National Institute of Technology
Karnataka, Mangalore, India
Sergio Navalón (543), Chemistry Department, Universitat
Politècnica de València, Valencia, Spain
Bunsho Ohtani (159), Institute for Catalysis, Hokkaido
University, Sapporo, Japan
Sibila A.A. Oliveira (341), Human and Natural Sciences
Center, Federal University of ABC—UFABC, Santo
Andre, SP, Brazil
L. Operti (649), Department of Chemistry, Università degli
Studi di Torino, Torino, Italy
Maria Cristina Paganini (221), Department of Chemistry
and NIS Centre, University of Torino, Torino, Italy
L. Palmisano (3), Engineering Department, University of
Palermo, Palermo, Italy
D. Perniu (371), Center for Renewable Energy System and
Recycling, Transilvania University of Brasov, Braşov,
Romania
Albin Pintar (397), Laboratory for Environmental Sci-
ences and Engineering, Department of Inorganic Chem-
istry and Technology, National Institute of Chemistry,
Ljubljana, Slovenia
Jovana R. Prekodravac (575), Vinca Institute of Nuclear
Sciences—National Institute of the Republic of
Serbia, University of Belgrade Belgrade, Belgrade,
Serbia
Alessandra Bianco Prevot (357, 589), Chemistry
Department, Torino University, Torino, Italy
Tharishinny Raja-Mogan (421), Institute for Catalysis
(ICAT); Graduate School of Environmental Science,
Hokkaido University, Sapporo, Japan
M Rajeswara Rao (505), Department of Chemistry, IIT
Dharwad, Dharwad, Karnataka, India
Bárbara S. Rodrigues (341), Human and Natural Sciences
Center, Federal University of ABC—UFABC, Santo
Andre, SP, Brazil
Contributors xvii
Ilenia Rossetti (63), Chemical Plants and Industrial Chem-
istry Group, Department of Chemistry, Università degli
Studi di Milano and INSTM Unit Milano Università,
Milan, Italy
D. Sánchez-Martı́nez (211), Autonomous University of
Nuevo León, Civil Engineering Faculty— Ecomaterials
and Energy Department, Cd. Universitaria, San Nicolás
de los Garza, NL, Mexico
Monica Santamaria (115), Dipartimento di Ingegneria,
Università degli Studi di Palermo, Palermo, Italy
Patricia V.B. Santiago (341), Chemistry Institute, State
University of Campinas—UNICAMP, Campinas, SP,
Brazil
Rudolf Słota (183), Institute of Chemistry, University of
Opole, Opole, Poland
Fabrizio Sordello (449), Department of Chemistry and
NIS—Nanostructured Interfaces and Surfaces Interde-
partmental Centre, University of Turin, Turin, Italy
Juliana S. Souza (341), Human and Natural Sciences
Center, Federal University of ABC—UFABC, Santo
Andre, SP, Brazil
G. Spigno (649), DiSTAS-Department for Sustainable
Food Process, Università Cattolica del Sacro Cuore,
Piacenza, Italy
Taymaz Tabari (95), Faculty of Chemistry, Jagiellonian
University, Kraków, Poland
Mai Takashima (159), Institute for Catalysis, Hokkaido
University, Sapporo, Japan
Masato Takeuchi (171), Department of Applied Chem-
istry, Graduate School of Engineering, Osaka Prefecture
University, Sakai, Osaka, Japan
Maria Luisa Testa (589), Institute for the Study of Nano-
structured Materials, Italian National Research Council,
Palermo, Italy
Álvaro Tolosana-Moranchel (83), Nanotechnology and
Integrated BioEngineering Centre, School of Engi-
neering, Ulster University, Belfast, Northern Ireland,
United Kingdom
Mateusz Trochowski (95), Faculty of Chemistry, Jagiel-
lonian University, Kraków, Poland
Maria Laura Tummino (357, 589), Chemistry Department,
Torino University, Torino, Italy
Kunlei Wang (421), Institute for Catalysis (ICAT),
Hokkaido University, Sapporo, Japan; Northwest Research
Institute, Co. Ltd. of C.R.E.C., Lanzhou, P.R. China
Qian Wang (485), State Key Laboratory of Chemical
Resource Engineering, Beijing University of Chemical
Technology, Beijing, China; Chemistry Department,
xviii Contributors
INSTM and ICCOM-CNR Trieste Research Unit, Uni-
versity of Trieste, Trieste, Italy
Zhishun Wei (421), School of Materials and Chemical Engi-
neering, Hubei University of Technology, Wuhan, China
Jerry J. Wu (283), Department of Environmental Engineering
and Science, Feng Chia University, Taichung, Taiwan
Andrea Zaffora (115), Dipartimento di Ingegneria, Uni-
versità degli Studi di Palermo, Palermo, Italy
Gregor Žerjav (397), Laboratory for Environmental Sci-
ences and Engineering, Department of Inorganic Chem-
istry and Technology, National Institute of Chemistry,
Ljubljana, Slovenia
Shuaizhi Zheng (421), Key Laboratory of Low Dimen-
sional Materials and Application Technology of Min-
istry of Education, School of Materials Science and
Engineering, Xiangtan University, Xiangtan, China
Preface

Materials science has become an extremely broad and multidisciplinary field of research and the emerging technologies
where it is applied in the recent years have been astonishingly increasing. Photocatalysis, as a branch of catalysis, has been
one of these technologic fields, where the study of the materials science resulted particularly important. This book attempts
to cover the main aspects in the very broad field of materials science addressed to materials applied in heterogeneous photo-
catalytic process of various nature. A very wide class of photocatalytic materials have been treated here in an attempt of
cover both the main basic aspects to approach the study of photocatalytic materials and also examples of solid photoca-
talysts, their features and applications, without, of course, being exhaustive due to the plethora of materials and aspects
which would be treated in such an effort.
This book reports information on several types of materials used in heterogeneous photocatalysis both from a theoretical
and an applicative point of view. We hope that the 6 sections comprising 37 chapters will provide a fairly broad overview
for readers interested in this fascinating field of research. In addition to very popular bare and mixed metal oxides and
sulfides such as TiO2, ZnO, WO3, MoS2, other more complex and innovative materials are proposed such as metal-organic
structures, graphene and graphene oxide, magnetic materials, plasmonic nanoparticles, and 2D materials among others. The
reader will be able to evaluate the advantages and disadvantages of using the various materials, taking into account not only
their cost but also their (photo)stability, toxicity, and ease of preparation. Moreover, readers can find in the book different
types of examples of photocatalytic reactions of oxidation and reduction carried out in liquid–solid and in gas–solid systems
where the different heterogeneous photocatalysts would be suitable. The various materials presented have been tested,
among other reactions, for pollutants degradation, chemical transformations including CO2 activation, organic synthesis
and applications of biomimetic photocatalytic systems, fungal abatement in photocatalytic surfaces. We would like to
underline that the authors have tried to deal with the topics so that the reader who wishes to deepen them can find the
necessary literature among the numerous references cited in each chapter. We believe that a book that summarizes concepts
and topics from a certain field that can then be further explored in the scientific literature is particularly useful for young
researchers and PhD students, as well as for experienced researchers who are about to start research in that field. Finally, we
want to thank all the colleagues and friends who enthusiastically joined us in writing the book, and a last but not least thanks
goes to Elsevier and the staff who accompanied us with great professionalism and patience during this rewarding adventure.

Elisa I. Garcı́a-López and Leonardo Palmisano

Every great advance in science has issued from a new audacity of imagination
John Dewey, 1929

xix
Chapter 1

Fundamentals of photocatalysis: The role

of the photocatalysts in heterogeneous
photo-assisted reactions
Elisa I. Garcı́a-Lópeza and L. Palmisanob
a
Department of Biological, Chemical and Pharmaceutical Sciences and Technologies (STEBICEF), University of Palermo, Palermo, Italy, b Engineering
Department, University of Palermo, Palermo, Italy

1 Introduction
The contemporary world is facing energy shortages and environmental problems, which hinder the evolution of human
civilization giving rise to various types of crises. The huge consumption of energy and environmental pollution from tra-
ditional industrial processes, along with the increasing need for synthetic chemicals to satisfy current requirements, are
urgent issues to be addressed for the development of new foundations for a sustainable future. These critical challenges
need solutions that require an important upgrade in energy sources and the conception of new generation processes and
manufacturing technologies. Researchers, over the past few decades, have been studying several methods to understand
how to overcome these problems. In this context, heterogeneous photocatalysis appears as one of the useful technologies
to help these urgent efforts, and it can contribute to managing the conversion of solar energy into chemical energy in a
sustainable way.
This introductory chapter discusses some essential characteristics of heterogeneous photocatalysis by making connec-
tions with thermal catalysis. We hope that their analysis together with the explanation of some key concepts leads to better
understanding the contents of the chapters in this book. In particular, the chapter highlights the importance of the features
and parameters of solid photocatalysts.

2 Basic principles of photocatalysis

When the term photocatalysis first appeared in scientific literature, photochemists focused on the aspects related to specific
processes accelerated by light. For their part, researchers active in catalysis highlighted the catalytic aspects, focusing their
attention on the characterization techniques typical of thermal catalysis and on the reaction processes and mechanisms that
can occur on the surface of solid particles, minimizing the importance of light for triggering and continuing the reaction.
Both approaches should be combined to fully understand the photochemical and catalytic aspects of a heterogeneous photo-
catalytic reaction. There has always been complete agreement in the scientific community regarding the concepts and def-
initions of catalysis [1], whereas agreement on these same aspects of photocatalysis has been reached only in the last years
[2–4]. The term photocatalysis first appeared in literature as early as 1911 [5], but only Baly et al., for the first time in 1921,
studied the phenomenon in which light accelerated a catalytic reaction [6]. The pioneering papers in which photocatalysis
was defined as the process in which the combination of light and a solid catalyst was able to influence a reaction were
published in 1964 by Doerffler and Hauffe [7, 8]. From then on, sporadic examples of photocatalytic reactions have been
reported up until the work of Honda et al. on the photoelectrolysis of water and the photoelectrocatalytic reduction of carbon
dioxide using titanium dioxide (TiO2) [9].
An acceleration of research on heterogeneous photo-assisted catalysis occurred from 1972, when Fujishima and Honda
published a work on UV light-induced water splitting using a TiO2 photoanode, although in principle this work fits better in
the field of photo-electrocatalysis [10]. Since then, considerable efforts have been made not only to understand the fun-
damentals of heterogeneous photocatalysis, but also to apply this technology to solving several environmental problems,
using both artificial energy and sunlight. The removal of viruses and bacteria, the elimination of polluting substances, the

Materials Science in Photocatalysis. https://doi.org/10.1016/B978-0-12-821859-4.00004-0

Copyright © 2021 Elsevier Inc. All rights reserved. 3
4 SECTION A Introduction

production of hydrogen, the performing of green organic syntheses, and the reduction of carbon dioxide are among some of
the potential applications of heterogeneous photocatalysis.
In the 1990s, heterogeneous photocatalysis was considered among the “advanced oxidation technologies” and was
mainly applied to the degradation of very toxic and nonbiodegradable species both in the vapor and liquid phase [11–13].
However, more recently photocatalytic reactions have been directed toward the formation of compounds with high added
value under mild experimental conditions, although in water, the green solvent par excellence, it is difficult to obtain high
selectivity and the solubility of most organic molecules is low [14]. After the document by Fujishima and Honda, a great
number of articles have been published concerning the heterogeneous field of photocatalysis. In this situation, the proposals
of terms and definitions to correctly articulate the photocatalytic investigations seem to be important tools [15–18]. However,
a definitive “Glossary of terms used in photocatalysis and radiation catalysis” (IUPAC recommendations) was published with
a final agreement in 2011 [19], although it should be considered that the rapid evolution of science could suggest updates and
changes to terms and definitions found in that document. The definition of photocatalysis was accepted as the “change in the
rate of a chemical reaction or its initiation under the action of ultraviolet, visible, or infrared radiation in the presence of a
substance, the photocatalyst, that absorbs light and is involved in the chemical transformation of the reaction partners.” The
definition of photocatalyst was established as: “substance able to produce, by absorption of ultraviolet, visible, or infrared
radiation, chemical transformations of the reaction partners, repeatedly coming with them into intermediate chemical inter-
actions and regenerating its chemical composition after each cycle of such interactions.” This last definition was very much
related to that of the catalyst. Heterogeneous catalysts are solids or mixtures of solids that cause or accelerate a chemical
reaction without being modified. Heterogeneous catalysts can be metals, oxides, metal salts, sulfides, zeolites, and perov-
skites. Heterogeneous photocatalysts are solid semiconductors that act catalytically under light radiation.
In a heterogeneous photocatalytic process, the solid photocatalyst is excited by a light radiation with suitable energy. In
this process, an electron in the valence band (VB) of the semiconductor is excited by the photo-irradiation toward the empty
conduction band (CB) of the solid, which is separated by a band gap from the VB. The electron in the VB, being promoted,
leaves a positive hole in the VB. The photo-generated electrons and holes (e
/h+) are responsible for the reduction and
oxidation reactions, respectively, occurring at the surface of the photocatalyst. Indeed, species adsorbed on the surface
of a photocatalyst would be either reduced or oxidized. The material is, in practice, a heterogeneous catalyst, albeit it
is active only when it absorbs photons with a suitable energy generating the (e
/h+) couple. The photocatalyst, like the
catalyst, remains chemically unchanged during and after the reaction, and accelerates a chemical reaction participating
in the mechanism of the reaction but not in the overall chemical process.
A heterogeneous photocatalytic reaction can be followed, and its occurrence can be ascertained by (1) measuring the
consumption of the starting substrates, (2) determining the reaction products once the irradiation has started, and (3) ver-
ifying the actual role of the solid as a catalyst by checking if its properties have been modified during the photoreaction.
The relationship between photocatalysis and catalysis was addressed by Childs and Ollis, who questioned the actual
nature of the photocatalyst and how to correctly compare the activity of the different photocatalytic materials [20].
A catalytic reaction can be divided into the following steps: (1) diffusion of the reactants from the fluid phase to the
catalyst surface, (2) adsorption of the reagent(s), (3) reaction occurring in the adsorbed phase, (4) desorption of the product
(s), and (5) its (their) transfer to the bulk of the fluid phase [21]. The steps that should be considered in a heterogeneous
photocatalytic process are similar, but (2) and (3) seem quite different from those expected in thermal catalysis. This is
because in a photocatalytic process the reactants are generally only physically adsorbed on the surface because the reaction
is carried out at low temperature. After adsorption, several reactions and physical processes activated by light occur,
including possible photo-adsorption and photo-desorption stages. On the contrary, in a catalytic process the adsorption
can itself be considered a thermally activated chemical reaction, and it generally involves a chemisorption where at least
one reactant is destabilized and gives rise to the desired product(s) [22].
Heating is not necessary for the photonic activation of a solid photocatalyst, but it is required in catalysis to activate the
chemisorption of the reactant on the surface of the catalyst, its transformation, and its subsequent desorption.
The main difference between a catalyst and a photocatalyst is that in thermal heterogeneous catalysis the solid is ready
to perform its function, while in photocatalysis it must be “activated” by light generating hole-electron pairs before being
considered a photocatalyst. Furthermore, the activity of the photocatalyst is maintained only by the continuous absorption
of light.
It is worth noting here that the photo-adsorption is a process due to the light absorption by the solid surface according to
the following mechanism [23]:
S + hn ! S∗ (1)
 Fundamentals of photocatalysis Chapter 1 5

S∗ ! S (2)
S∗ + R ! Rads (3)
where S is the photo-adsorption center onto the photocatalytic surface, S* is the active state of the photo-adsorption center,
R is the reactant molecule in the fluid phase, and Rads is the photo-adsorbed substrate onto the active site of the solid
photocatalyst.
The physical steps reported in (1)–(3) represent the initial steps in a catalytic photo-assisted reaction, that is, the radi-
ation absorption by the solid photocatalyst (1) and (2) and the successive adsorption of the substrate (3). The irradiation of
the solid surface modifies the properties of the photocatalyst surface [24, 25]. One can mention, for example, the hydro-
philic/hydrophobic nature of the surface of the semiconductors, which become more hydrophilic (smaller contact angle)
when irradiated and gradually go back to a more hydrophobic state when left in the dark or exposed to visible light [26]. In
particular, modification of the properties of the surface is reversible and the surface returns to its original state in the
absence of irradiation.
After the activation of the photocatalyst due to absorption of light of suitable energy, the photocatalytic process takes
place in some pure physical or chemical stages. In fact, as described previously for the catalytic cycle, the reactant(s) must
reach the external surface of the photocatalyst, spread in the pores, photo-adsorb, and photoreact and therefore the product
(s) must be desorbed. The main stages occurring in a photocatalytic process on the “activated-by-light” semiconductor
particle surface are (1) the diffusion of reactant(s) to the photocatalyst surface through the boundary layer, (2) diffusion
of reactant(s) from the reacting system into the pores of the photocatalyst, (3) photo-adsorption of reactant(s) on the pore
surface, (4) photo-oxidation and photo-reduction reactions, (5) photo-desorption of the reaction product(s) from the pore
surface, (6) diffusion of the product(s) out of the pores, and (7) diffusion of the products(s) away from the surface of the
photocatalyst through the boundary layer.
The diffusion processes may be easily affected by modifying the fluid dynamics of the system, while adsorption and
desorption of the reagents inside of the pores and from the pores could be addressed by the textural properties of the solid
photocatalyst, mainly the size and shape of the pores.
The adsorption and desorption induced by light phenomena, whose extent depends on the type of species involved, are
difficult to be quantified. The measurements of light absorption by the solid photocatalyst in dark conditions are only indic-
ative of what would occur in the presence of light. This is an important issue for explaining the overall mechanism of a
photocatalytic reaction. In addition, photo-adsorption and photo-desorption effects overlap with the disappearance or the
appearance of the species due to the reaction steps, influencing their measured concentration values in the gaseous fluids or
in the bulk of the liquid. Consequently, it is difficult to evaluate the extent of physical adsorption under irradiation due to the
concurrent disappearance of reagent(s) during the photocatalytic reaction.
As reported in Fig. 1, the photocatalyst, in this scheme exemplified by a TiO2 particle, absorbs a photon generating an
electron/hole couple (step 1) that recombines (step 2) or gives rise to oxidation and reduction reactions (steps 3 and 4) on the
surface or very close to it. The reagent(s) present on the fluid can adsorb more or less strongly depending on their chemical-
physical properties in relation to the surface of the catalyst. The impinging light produces electron-hole pairs if the ther-
modynamics constraints are fulfilled. Holes can be trapped by donor species as water molecules forming hydroxyl radicals
(∙OH). Contemporaneously, electrons reduce acceptor molecules as O2, which also can produce hydroxyl or hydroperoxide
radicals. These oxidant species formed in both oxidant and reductive paths attack generally unselectively the reagent(s)

Ox
6 1
e- 4
Ti
Red 1
2 1

Ti Ox 2
CO2 + H2O
5
h+ 3
HO 7
Red 2

FIG. 1 Steps of heterogeneous photocatalysis in a TiO2 particle. (Adapted from C.B. Mendive, D. Hansmann, T. Bredow, D. Bahnemann, New Insights
into the mechanism of TiO2 photocatalysis: thermal processes beyond the electron–hole creation, J. Phys. Chem. C 115 (2011), 19676, with permission of
the American Chemical Society.)
6 SECTION A Introduction

transforming it into intermediates and into the final products by means of various consecutive steps, which are resumed in
step 5. The surface of the photocatalyst itself can trap electrons and holes, and Ti(IV) and/or Ti-OH sites, for instance in the
case of TiO2 surface, can respectively play this role (steps 6 and 7).
The features of a good photocatalyst include chemical and biological inertness, stability toward light irradiation
(absence of photo-corrosion), easy and cheap production, and being harmless to the environment and living beings.
The most attractive photocatalyst should be activated by natural solar light. Among all the semiconductors tested, the most
popular has been TiO2. The majority of photocatalysts are inorganic solid materials, generally oxides that exist in various
crystalline phases. Nevertheless, sulfides, metal salts, zeolites, and perovskites have also been used. More recently, some
organic semiconductors such as boron nitride (BN) or carbon nitride solid (C3N4) have been studied as well. The subsequent
chapters propose a wide range of examples.
A heterogeneous photocatalyst should be a semiconductor possessing a crystalline structure. The absence of crystal-
linity prevents the solid to be used as photocatalyst. Indeed, only a crystalline semiconductor may absorb radiation of
suitable energy (equal to or greater than the bandgap) generating efficient electron-hole pairs. The light absorption and
the formation of photoproduced couples only occur in the spatially ordered atoms of a crystal, in which the radiation
can enter in resonance. Amorphous phases absorb radiation, but the separation of electrons and holes that are responsible
for surface redox processes is impossible. The crystalline morphology of the photocatalyst significantly influences the
optical, chemical, and topographical characteristics of its surface, and consequently its activity. The ability to guarantee
an optimization of these factors is the key to obtaining highly performing photocatalysts [27].
An interesting further aspect has been highlighted by some authors who report that 3D networks can be formed by some
nanoparticles of metal oxides, which can work as photocatalysts. In the 3D network the particles are not ordered randomly,
but their atomic planes are aligned in a precise way so that their contact can allow the transfer of the e
/h+ pairs, reducing
greatly the interfacial trapping processes. This effect is called “antenna effect” [28].
Electrons and gaps can move to/on the surface and be trapped. The presence of a “cooperative network” in place of
individual photocatalyst particles improves the photocatalytic activity of the entire system.
Many reactions can be performed both catalytically and photocatalytically, but the two mechanisms are generally dif-
ferent [2, 13, 29]. The catalytic and photocatalytic processes can also occur simultaneously [30].
We have seen that the photocatalyst should (photo)adsorb two types of reactants, one to be oxidized and the other to be
reduced, in order to assure the electroneutrality of the photocatalytic cycle. A photocatalytic reaction can produce partial
and total oxidation reactions or give rise to a synthesis, depending on the negative or positive sign, respectively, of the
variation of Gibbs free energy (DG) of the reaction.
The photoinduced electron-hole carriers’ mobility, to react with the species adsorbed on the solid photocatalyst surface,
mainly depends on two factors: the band energy positions of the semiconductor and the redox potential of the adsorbates.
The higher energy level of the valence band (HOMO) determines the hole-oxidizing ability, whereas the lower energy level
of the conduction band (LUMO) stands for the electron reduction potential. These two values measure the possibility of the
photocatalyst to promote oxidations and reductions, respectively. An oxidation reaction is more favored the more positive
the position of the VB, while a reduction reaction is more favored the more negative the position of the CB. In Fig. 2 the
band positions for some semiconductors used often in heterogeneous photocatalysis are reported together with the reduction
potentials of H2O to O2 and H+ to H2.

FIG. 2 Band positions and Photocatalysts possessing strong

potential applications of some reduction abilities. Useful for CO2
typical photocatalysts (at pH 7 in No · OH or O2 -· reduction and/or H2 evolution
aqueous solutions). ZnS
SiC
-3 TaON C3 N4 Cu2 O
Potential vs. NHE [V]

TiO2 SrTiO TiO2 TaN5 CdS Si Bi2 S3

-2 BiVO4 Rutile
3
Anatase
ZnO
WO3 SnO2
-1 Fe2 O3
2H+/H2 (-0.41V)
0
H2 O/O2 (+0.82V)
+1
+2
+3
Photocatalysts useful for
at pH7 Photocatalysts possessing strong overall water splitting
oxidation abilities. Useful to
oxidise pollutants (by means of · OH)
 Fundamentals of photocatalysis Chapter 1 7

From a thermodynamic point of view, the reduction of the oxidized species of an adsorbed couple whose redox potential
is more positive than the flat band potential of the CB is allowed, whereas the reduced species of a couple whose redox
potential is more negative than the flat band potential of the VB can be oxidized. Fig. 2 depicts this situation, where three
families of photocatalysts are illustrated in red, blue, and green. The red group includes those semiconductors possessing a
very oxidant VB, and thus in the aqueous suspension they assure the formation of holes and therefore OH radicals (also
O2
∙ and H2O2), which induce oxidation reactions. The formation of OH radicals occurs because the potential of the VB is
more positive than that of the OH radical formation (see Fig. 2). The green group includes those photocatalysts with more
negative CB positions; the photo-generated electrons produced under illumination of these materials have a strong
reduction ability, and H2 evolution from H2O and/or CO2 reduction are possible. In other words, they can photo-reduce
CO2 and give rise to water photo-splitting from a thermodynamic point of view. It should be remembered, however, that
the actual occurrence of these mentioned processes is connected to many factors that influence the theoretical thermody-
namic values shown in Fig. 2. For example, the presence of interband states between VBs and CBs hinders the photoca-
talytic reaction because these states favor electron-hole recombination; the lifetime of the photo-produced pairs decreases,
preventing them from reaching the surface of the photocatalyst where the redox reaction takes place.
From a kinetic point of view, the efficiency of the photocatalyst is maximum when the rate of the e
/h+ deactivation
process (i.e., their recombination in the bulk or on the surface) is lower than that of these photo-produced pairs with the
adsorbed substrates.
The chemical reaction, involving the photo-adsorbed substrates is the most important step. As mentioned, heteroge-
neous photocatalysis can drive thermodynamically uphill reactions, for example, the splitting of water and reduction of
CO2. Notably, differently to what occurs in catalysis, a photocatalytic process can come about also for reactions with
DG > 0 that, under catalytic conditions, cannot occur to a significant extent unless energy is supplied. In the case of photo-
catalytic reactions, this energy is provided in the form of photons, as in the case of natural photosynthesis driven by sunlight.
As mentioned, the efficiency of a heterogeneous photocatalytic reaction depends on many chemical and physical prop-
erties of the photocatalyst, for example, the presence of acid and basic sites, zero charge point, hydroxylation degree of the
surface, specific surface area, shape and size of the particles, crystallinity, and porosity. An optimal combination of dif-
ferent properties such as activity, selectivity toward products with high added value, preparation with a nonpolluting
method and ease of regeneration, long lifetime, nontoxicity, and low cost is also important. The relative weight of these
properties is different, depending on the type of photocatalytic reaction to be performed and on the system (gas-solid or
liquid-solid), photoreactor, and set-up chosen. Also, when designing a photocatalyst it may be necessary to find a com-
promise between the different properties. The different synthetic methods could concern some properties compared to
others, thus favoring the required performances.
It could be useful to remind here the most significant parameters used to assess the performance of a heterogeneous
photocatalytic system, as defined by IUPAC [19]. All of them depend on the characteristics of the photocatalyst together
with those of the set-up system used. Four parameters can be defined: quantum yield (F), photonic efficiency (x), turnover
frequency (TOF), and turnover number (TON) [19].
The F is calculated as the number of product species formed in a photocatalytic process or, alternatively, the number of
molecules of a reacted reagent (defined events, according to IUPAC), divided by the number of photons at a certain wave-
length, absorbed by the system. This quantity has a well-quantified value only when the reaction conditions are also estab-
lished, and it is necessary to know the quantity of photons absorbed by the solid photocatalyst. To simplify the
quantification of the parameter, we can only consider the impinging radiation on the system before absorption. The x
is commonly used in heterogeneous photocatalysis instead of F. Its definition is similar to that of F, but a specified wave-
length range is considered instead of a certain wavelength. The TOF is the number of photoinduced transformations
(product formed or reactant consumed), per catalytic site and per period of time. In heterogeneous photocatalysis, the
number of active sites on the surface of the photocatalyst is often unknown, and the TOF value is determined by considering
the surface area, although the comparison of the obtained values for photocatalysts prepared by using different methods is
questionable.
The TON is the number of times that the photochemical transformation goes through a photocatalytic cycle. This
parameter is widely used in catalysis, but is quite descriptive for a photocatalytic process because the irradiation conditions
influence the reaction rate and, for the reaction to occur, incident photons of adequate energy must be absorbed by the
semiconductor, which usually consists of polycrystalline porous nanoparticles. Therefore, it is necessary to carefully
measure the extent of the absorption of photons [31]. An open debate on the experimental methodologies that should
be used to obtain these parameters is still ongoing [32].
Determination of the kinetics in photocatalytic reactions also requires careful determination of the radiation intensity
field within the reactor. In fact, it has been experimentally confirmed that the intensity of light determines the reaction rate
8 SECTION A Introduction

[33] because the absorption of the photons by the photocatalyst is, as previously mentioned, the main stage in a photoca-
talytic process. In this context, it can be emphasized that the results of photo-reactivity depend not only on the geometry and
size of the reactor but also on some characteristics of the photocatalyst such as particle size, morphology, and illumination
modes [34].
Since photocatalytic reactions occur on the surface [35], the driving forces are expressed on the basis of (1) the surface
concentration of the charge carriers, which are a function of the absorbed light and (2) the surface concentration of the
species to be oxidized and reduced.
The dependence of the reaction rate, r, on the intensity of light can be represented with a power law. For low light
intensity, the dependence of the rate on the photon flow is linear. This confirms the photo-induced nature of the activation
of the catalytic process, with the participation of photo-induced electric e
/h+ charges in the reaction mechanism. However,
above a certain value (ca. 250 W/m2) the reaction rate becomes proportional to the square root because the formation rate of
the e/h+ pairs exceed the reaction rate, and their recombination is favored. The optimal use of light power corresponds to the
domain in which r is proportional to the radiant flux [36].
Generally, the initial reaction rate, r0, increases with the concentration of the substrate and the kinetics can be considered
pseudo-first order, tending to the limit value of order zero [36, 37]. This behavior can be interpreted by the Langmuir-
Hinshelwood (LH) model considering that the species to be reduced and oxidized are adsorbed on the surface of the
photocatalyst at different sites. Notably, other models in addition to the LH one have been used to study the kinetics of
the photocatalytic reactions, but it is not aim of this chapter to present them.
The LH model, according to which the reaction must involve surface sites induced by light absorption and by the
presence of photo-adsorbed species, contemplates two essential parameters: the surface kinetic constant and the equi-
librium adsorption constant, which refers to photo-adsorption/photo-desorption equilibrium phenomena. It is important
to underline that both of these may be determined by the fitting applied to photo-reactivity data [38, 39] and depend
on the local radiation intensity and on the characteristics of the photocatalyst.
The high-performance applications of the photocatalytic reaction are linked to the possibility that the photocatalyst is
made up of several crystalline phases of the same compound or that it is a composite made up of different materials whose
contact creates a heterojunction, which plays a key role by improving the separation of the photoproduced pairs increasing
their lifetime. In that case it is even more difficult than in the case of a single catalyst to rationalize the phenomena of photo-
adsorption/photo-desorption, due to the presence of different types of surfaces with different features. Notably, the size of
the crystallites, the specific surface area, and the porosity are crucial parameters to guarantee good accessibility to the
species to be adsorbed and reacted on the surface; in particular, the high-surface materials provide a great interface for
any type of photocatalytic reaction with high-performance applications.

3 Conclusions
Heterogeneous photocatalysis has emerged as a technology that can help solve some urgent energy and environmental
problems. This chapter discussed how the choice of materials generally used as catalysts can influence the efficiency
of photocatalytic reactions; more details can be found by reading the various chapters of this book. Among the main advan-
tages of a photocatalytic process are the mild experimental conditions in which the reactions are carried out, often at atmo-
spheric pressure and at room temperature using cheap and nontoxic solid photocatalysts, and the potential exploitation of
sunlight. The main parameters that influence the photocatalytic performance are in close relationship with the character-
istics of the material used as a photocatalyst. An accessible interface with the appropriate functionality plays a vital role in
the whole process. Many materials have traditionally been used as heterogeneous photocatalysts, such as bare and loaded/
doped inorganic semiconductors, glasses, fabrics, polymers, and various types of composites that often include or are sup-
ported on stoichiometric and nonstoichiometric oxides. In addition, many new innovative strategies have been designed in
recent decades, as reported in the coming chapters of this book.

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Chapter 2

Preparation of photocatalysts by chemical

methodologies
Elisa I. Garcı́a-Lópeza, Leonarda F. Liottab, and Giuseppe Marcı̀c
a
Department of Biological, Chemical and Pharmaceutical Sciences and Technologies (STEBICEF), University of Palermo, Palermo, Italy b Institute for
the Study of Nanostructured Materials, Palermo, Italy c Department of Engineering, University of Palermo, Palermo, Italy

1 Introduction
The increasing energy demand caused by population growth, the extensive utilization of fossil fuels, and the fast devel-
opment of industry have resulted in a serious energy crisis and have caused massive environmental pollution. Photocata-
lysis is considered one of the most potent techniques to solve energy and environmental issues by the use of abundant,
omnipresent, and free solar irradiation. Heterogeneous photocatalysts allow light energy to be transformed into chemical
energy useful for environmental remediation processes or energy production. The essence of the heterogeneous photoca-
talytic process is the solid photocatalyst. Many inorganic semiconductors have been widely investigated as photocatalysts.
From already 40 years, by the understanding of the photocatalytic processes, many kinds of photocatalysts have been
studied among them TiO2 soon emerged as one of the most interesting, along with other metal oxides and sulfides. Several
alternative materials as nitrides, phosphates, non-metal and organic photocatalysts as this book will present in the fol-
lowing, have been developed. An enormous variety of chemicals have been used for the preparation of these and other
(photo)catalysts and forsooth, photocatalytic materials can be prepared by many different routes, also because a plethora
of solids can be conceived as photocatalysts, as exemplified in this text itself. Indeed, in the following chapters, a profusion
of materials will be described as valid photocatalysts for a variety of applications.
In the wide scenario of the preparation of (photo)catalysts, some general elementary steps should be always accom-
plished. According to Hutchings and Vedrine, these operations are based on two fundamentals: (a) a detailed knowledge
of the scientific laws governing chemical and physical transformations, which are based on the fundamentals of inorganic
and/or solid-state chemistry, and (b) the empirical observation related to the carefully preserved know-how [1]. Many
industries are highly secretive concerning the preparation methodologies conceived for the materials to be used as
(photo)catalysts because they can be subjected to patents and this could be one reason for a certain paucity in affording
definitive and general studies in the field. This perception has been in part eradicated under the several scientific publi-
cations devoted to the field. Detailed preparation studies have been undertaken to establish general rules related to the
(photo)catalytic reaction to be attained. Many preparation methods are disclosed in the patent literature, and also frequently
are difficult to replicate for the lack of details in the methodologies or because of differences in the purity of reagents.
The efficiency of heterogeneous photocatalysts is determined by many chemical and physical features: i.e., the nature of
the material, shape of the particles, crystallinity degree, crystallite size point of zero charge, acidic and basic centers onto
the surface, specific surface area, and porosity, the surface-to-volume ratio among others. Specifically, a photocatalyst is a
semiconductor and among the above-mentioned parameters that influence semiconductor efficiency, in addition to the ther-
modynamic and kinetic constraints of the light-related processes, those playing a major role are crystallinity and surface
area. Crystallinity determines the charge separation/recombination rate and charge mobility, while high surface area is
necessary for efficient interfacial charge transfer processes beyond the particle domain. The surface area is an essential
requirement as long as reactants should be accessible to a maximum number of active sites. However, it is worth mentioning
that a very high SSA could lead to non-selective heterogeneous (photo)catalysts because, for instance, this material would
be easily able to over-oxidize the desired product. On the contrary, in an alternative reaction, the optimum (photo)catalyst
would require a high surface area. Consequently, we need to consider the optimum texture required for the solid by taking
into account the reaction that will be carried out.

Materials Science in Photocatalysis. https://doi.org/10.1016/B978-0-12-821859-4.00006-4

Copyright © 2021 Elsevier Inc. All rights reserved. 13
14 SECTION B Fundamentals of preparation and characterization of photocatalytic materials

Moreover, other important features to consider in the designing of a (photo)catalyst is to possess the appropriate texture
attrition resistance, adequate shape, and texture for the application and suitable pore structure.
Generally speaking, all of the physico-chemical features of the photocatalytic material would be combined to obtain an
efficient catalyst possessing the optimum combination to obtain the better activity and selectivity, to be easily regenerated,
durable, nontoxic, economic, and sustainable in terms of preparation methodology and lifetime. Often all the requirements
appear to contrast and the best compromise must be fulfilled during the photocatalyst conception and attainment. For this
aim, different preparation methodologies and techniques allow addressing the required performances.
There are many methods of nanostructures preparation, which can be divided into two approaches: “top-down” and
“bottom-up” methods [2]. The first one is based on the splitting of the bulk, macroscopic materials to nanoparticles. Crum-
bling, ball milling, and different kinds of lithography are “top-down” methodologies. Much better results, giving materials
with fewer defects and narrower size/shape distribution of grains provide the “bottom-up” methodologies, based on nano-
crystallites growth by the formation of nanostructures “atom by atom.” This self-assembling process gives rise to the aggre-
gation until the obtaining of nanoparticles. The “bottom-up” approaches are based mainly on chemical synthesis as, for
example, precipitation, decomposition of organic precursors, synthesis under hydrothermal conditions, hydrolysis and sub-
sequent condensation of reactants, surface redox exchange but also physical procedures as sputtering in a vacuum, con-
densation in liquid or gaseous phase among others.
A scheme of “bottom-up” and “top-down” approaches to obtain photocatalytic nanoparticles is reported in Fig. 1.
The development of new fabrication and processing technologies, along with a fundamental understanding of the rela-
tionship between the structure and properties of the powders continuously generates a variety of possibilities to produce
photocatalysts not only as powders but also as films, composites, and coatings.
The preparation methodologies of (photo)catalysts would be divided into two groups: (i) chemical and (ii) physical
methods, as schematized in Fig. 1. The strategies of the physical methods are based on a top to down approach, starting
from a bulk material that generates the final (photo)catalyst. Conversely, chemical methodologies are bottom-up
approaches, aiming to assemble molecules to form a final solid, showing the advantage of tailoring the solid to address
the suitable size, composition, and structure, appropriate for the target application. Moreover, chemical methods require
low temperatures and less energy than the physical procedures resulting in more economical and sustainable [2].
In this chapter, we will discuss some general principles concerning the methods for the preparation of heterogeneous
photocatalysts utilizing the chemical methodologies reported in Fig. 2.
A survey of the main chemical approaches for the preparation of (photo)catalysts will be reported in the following
paragraphs, along with some brief examples of photocatalysts prepared according to the described methodology.

Assembly from
Atoms/Molecules

Size Reduction
to nano-scale
for Assembly

TOP-DOWN BOTTOM-UP
FIG. 1 Scheme of two approaches to obtain nanoparticles that could be used as photocatalysts.
 Preparation of photocatalysts by chemical methodologies Chapter 2 15

FIG. 2 Chemical and physical methodologies for the preparation

Preparation of bulk (photo)catalysts of bulk photocatalysts.

Physical procedures Chemical methodologies

Pyrolysis
Precipitation/co-precipitation
Sputtering
Sol-gel
Ball-milling
Laser ablation Hydrothermal/Solvothermal
Electron-beam evaporation Microemulsion
Electrospraying Solid-state reactions
Electrochemical Solution combustion synthesis
Microwaves/Electromagnetic field

The main objective in the preparation of a photocatalyst is to produce (and be able to reproduce) a solid which can be
used as a stable, active, and selective catalyst offering high surface area, good porosity, and suitable mechanical strength.
The properties of a good catalyst, extended to the good photocatalysts is divided into two categories: (1) properties
which determine directly catalytic activity and selectivity, such as bulk and surface chemical composition, local micro-
structure, and phase composition; and (2) properties which ensure their successful implementation in the catalytic process,
as mechanical stability, porosity, shape, and size of catalyst particles. These needs generally require a compromise to
produce a material that meets the contradictory demands imposed by industrial processes. We will focus in this chapter
on the first category.
Classically, three types of catalyst, and hence photocatalysts, can be distinguished: (i) bulk catalysts; (ii) impregnated
catalysts; (iii) mixed-agglomerated powders.
Bulk catalysts are the most classical solids used as photocatalysts; supports are prepared by similar procedures. Impreg-
nated catalysts are usually obtained from preformed supports by impregnation with the active phase. Various substrates
have been used as heterogeneous supports including oxides, glass, fabric, or polymers. The mixed-agglomerated catalysts
comprise those materials obtained by mixing the active substances with powdered support or a support precursor and then
agglomerating the mixture [3].
In this scenario, two general strategies will be discussed in this Chapter, i.e., precipitation and impregnation. These can
be divided into various categories that will be described in the following. We will illustrate the main operations to obtain
bulk solids to use as photocatalysts and also as supports, then we will consider the preparation of supported catalysts.
The main unit operations applied for the preparation of (photo)catalysts involve the following procedures: (i) A pre-
cipitation step or an alternative process to obtain a solid (sol–gel, hydrothermal, solid–solid reaction, among others);
(ii) filtration, (iii) washing; (iv) grinding and (v) calcination. The scheme reported in Fig. 3 represents the steps that
could be followed. The preparation of a supporting material can foresee one or more further steps. Supported catalysts
are prepared for a large variety of reasons such as obtaining bifunctional catalysts, improve some features as the dis-
persion of the active phase, mechanical resistance, or induced active phase-support interaction to further improve the
(photo)catalyst activity.

2 Synthesis of photocatalysts as powders by chemical methodologies: An overview

2.1 Precipitation and co-precipitation
Precipitation is a widely employed method to obtain either single or mixed heterogeneous photocatalysts [3–5]. The main
advantage of the precipitation process is the possibility of creating pure and homogenous materials in one-pot, but the major
disadvantages are the necessity to separate the solid phase after precipitation and the generation of large volumes of salt-
containing solutions. In this process, a solid phase is formed from a solution and this precipitated solid is the precursor of the
final catalyst. The formation of the precipitate occurs by the addition of an agent which could change the pH, or by the
modification of the temperature or evaporation of the solvent. The precipitation of the solid occurs by achieving the super-
saturation conditions [5]. The parameters which turn the solution to the supersaturation conditions are concentration, tem-
perature, and pH, as shown in Fig. 4. Commonly, one proceeds usually by precipitation from a solution by adding another
solution to reach the necessary pH to obtain the solid. Generally, the supersaturation can be reached by: (i) increasing the
concentration through solvent evaporation, (ii) lowering the temperature or (iii) by changing the pH. Achieving the
16 SECTION B Fundamentals of preparation and characterization of photocatalytic materials

Precursor
Precipitation
(Sol-gel, hydrothermal, etc…)

Precipitate
Aging, wash, filtering
Aging,
sprydrying Filtered cake

Dried solid precursor

Shaping Calcination

Solid precursor Photocatalyst

Calcination Shaping

Final solid Photocatalyst

FIG. 3 Scheme of the steps in the preparation of a precipitated photocatalyst.

FIG. 4 Supersaturation dependence on concentration, T, and pH. Adapted with permission from C. Perego, P. Villa, Catalyst preparation methods, Catal.
Today 34 (1997) 281–305. Copyright by Elsevier.

supersaturation, the system turns unstable and the precipitation of the solid occurs as a consequence of a small perturbation.
The solid then is formed by the nucleation of small elementary particles and their further agglomeration.
The formation of clusters, which spontaneously grow by the subsequent addition of monomers is the first stage of the
nucleation process. The clusters reaching a critical size continue to grow. These primary particles begin to form a shared
structure, the aggregates. The size of the crystals obtained depends on the ratio of the rate of nucleation to that of the crystal
growth. The greater this ratio is, the smaller will be the crystallites and vice versa. If the rate of nucleation is faster than the
rate of growth, numerous very small particles are formed and the obtained solid tend to be amorphous.
The most common catalysts and photocatalysts prepared by precipitation are oxides and salts. The precursors are mainly
metallic salts or hydroxides. The precursors are preferably chosen among salts possessing the metal cation accompanied by
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hypochondriasis, intellectual feebleness, and insanity. Two forms of
hereditary alcoholism have been recognized: First, that in which the
disease or defect of the parent is transmitted to the offspring; and
second, that in which the disease or defect is not directly transmitted
to the offspring, but a morbid tendency which manifests itself in
diseases or defects of a different kind.49
49 1. Heredite de similitude, Alcoolisme hereditaire homotype; 2. Heredite de
transformation, Alcoolisme hereditaire heterotype.

1. The appetite for strong drink is frequently transmitted from parents

to the children, just as other traits of the mind or body. Sometimes it
develops early, sometimes late in life; as a rule, however, this
hereditary propensity shows itself at an early age, and is apt to be
intensified at the time of puberty and the menopause. Objections
have been urged against the theory of hereditary alcoholism. Among
these the strongest is perhaps that the taste for drink in the offspring
of alcoholic subjects is the result rather of opportunity and example
than of heredity. The frequency with which alcoholic tendencies
develop themselves in children reared and educated away from their
parents, and the number of cases in which these tendencies show
themselves only at an advanced period of life, long after the
influence of example in childhood has ceased, sufficiently disprove
this assumption. The hereditary influence does not, however,
invariably manifest itself in the desire for drink. On the contrary, not
rarely it consists in feebleness of nervous constitution, characterized
by irritability, want of mental repose, or a restless or vicious
disposition which demands constant excitement. Hence such
individuals, although intellectually well developed, are often scarcely
more than moral imbeciles, in whom the passion for drink may be
replaced by the opium habit, addiction to gaming and to other vices,
and whose career is shaped largely by an inordinate and insatiable
craving for excitement of all kinds. Hereditary alcoholism follows the
laws of heredity in general. The tendency may be transmitted directly
from one generation to another, or may skip one or more
generations, taking in the intermediate periods some different form.
2. The second variety is that in which the symptoms of chronic
alcoholism are manifested in the offspring in the absence of the
direct action of alcohol; that is to say, not the taste for alcohol, but
the results of the gratification of that taste are transmitted, just as
epileptic or hysterical patients may transmit to their offspring epilepsy
or hysteria; thus it is not rare to encounter in the descendants of
alcoholic parents perverted sensation, both general and special,
hyperæsthesia, anæsthesia, flying neuralgias which do not always
follow the course of particular nerves, but frequently affect in a
general way the head or the members or manifest themselves as
visceral neuralgias. These persons are much troubled with headache
from slight causes and with migraine. Nor are disturbances of vision
rare, nor vertigo. Insomnia is also frequent in such individuals, and
augments the other symptoms. Digestive troubles also frequently
occur, notwithstanding a regular and perfectly temperate life. Such
persons are often subject to hallucinations of sight and hearing, and
are liable to have delirium in trifling illnesses.

The second form of hereditary alcoholism manifests itself in a wholly

different manner. The descendants, without a special appetite for
strong drink, and in the absence of the special morbid manifestations
above described, are singularly liable to mental and nervous
diseases of various kinds. Among these convulsions and epilepsy
are especially frequent; hysteria and various forms of insanity also
occur. In this group of cases we find every degree of arrest of
intellectual development, from mere feeble-mindedness to complete
idiocy. As manifestations of the influence of alcoholism upon the
offspring may be cited certain moral peculiarities otherwise
inexplicable, such as are seen in children who at a very tender age
show themselves vindictive, passionate, and cruel, to whom the
sufferings of others afford pleasure, who torment their companions
and torture their pets, and show precocious vicious tendencies of all
kinds. Later in life these persons become lazy, intolerant of
discipline, vagabonds, unstable of character, without the power of
application and without moral sense. Given to drink, defiant of law,
they constitute the great body of tramps, paupers, and criminals. The
children of alcoholic subjects are often feeble and puny, pale, badly
nourished, and curiously subject to morbid influences.

IV. Dipsomania.

Dipsomania, which has also been described under the term

oinomania, is rather a form of insanity than of alcoholic disease. The
characteristic symptoms are, however, in the greater number of
instances, due to indulgence in alcohol. The subjects of this affection
usually belong to families in which insanity, and especially this
particular form of insanity, is hereditary.

There are two forms of dipsomania—the essential and the

symptomatic. Of these, the latter is the more frequent. Its
consideration requires in this connection very few words. It manifests
itself by an irresistible desire on the part of many insane people for
alcohol. It occurs both in the prodromic and in the fully-established
periods of insanity. It is especially common in various forms of mania
and in the prodromic periods of general paralysis. The dominating
influence in essential dipsomania is heredity. Occasional causes
may bring on particular attacks, but their influence is secondary.
Dipsomania cannot be looked upon as a distinct recurrent affection
in an otherwise healthy person. At some period in their lives, and
often long before the occurrence of characteristic paroxysms,
dipsomaniacs show peculiarities indicating defects of mental
organization. Certain symptoms of dipsomania are often mistaken for
its cause. Thus, dyspepsia is more frequently an effect than a cause
of the alcoholic excesses. The despondency, irritability, restlessness,
hysterical manifestations, and insomnia which precede the attack are
not the cause of it: they are its earliest symptoms.

The affection usually begins insidiously and is progressive. As a rule,

although not always, it begins in early adult life. The manifestations
of this disease are essentially intermittent and paroxysmal, but the
impulse to drink must be regarded as a symptom which may be
replaced by other irresistible desires of an impulsive kind, such as
lead to the commission and repetition of various crimes, as the
gratification of other depraved appetites, robbery, or even homicide.
The paroxysms are at first of short duration, and are followed by
return to the previous regular and decent manner of life. They
become, however, by degrees, more violent and more prolonged. At
first lasting for a few days or a week, by and by they extend to
periods of a month or six weeks, the attack wearing itself out, and
recurring with a periodicity sometimes variable and sometimes
constant. In the intervals of these attacks for a considerable time the
patients very often lead sober, chaste, and useful lives. At length,
however, evidences of permanent mental trouble are manifested,
and the case settles into confirmed insanity. The attack is usually
preceded by evidences of mental derangement; the patient becomes
restless and irritable; sleep is irregular and unrefreshing; he
complains of general malaise, and is anxious, troubled by vague
apprehensions. He presently abandons his usual occupations and
gives himself up to disordered impulses, among which alcoholic
excesses are the most frequent and the most easily gratified.
Sometimes the patient passes his time at taverns drinking with all
comers; at others he shuts himself up in a chamber and gratifies his
desire for drink to the most extreme degree alone. Dipsomaniacs not
rarely leave their homes and associates without warning or
explanation, and pass the period of the paroxysm among associates
of the most disreputable character. The desire for drink is gratified at
all costs, and not infrequently they return to their friends without
money and without sufficient clothing, most of it having been sold or
pawned in order to purchase drink. The paroxysm is succeeded by a
period of more or less marked mental depression, during which the
patient not rarely voluntarily seeks admission to some asylum.

The true nature of dipsomania is frequently overlooked. As a

symptom of hereditary insanity it is in striking contrast with the
habitual propensity to drink which occurs in the ordinary alcoholic
subject. The latter seeks occasions to drink. He renews his excesses
not intermittently, but habitually. If in consequence of disgrace or
misfortune or under strong moral suasion he is for a time
abstemious, it is only to renew and to continue his indulgence upon
the first favorable occasion. On the contrary, the true dipsomaniac
recognizes his malady and struggles against it. Even more: for a
time he shows much skill in concealing it. He avoids occasions to
drink, and, reproaching himself for his mad and unreasonable desire,
seeks by every means to overcome his impulse to it. The ordinary
drunkard may become insane because he drinks; the dipsomaniac
drinks because he is insane.50
50 Magnan, Le Progrès médical, 1884.

Dipsomaniacs are apt to manifest precocious or retarded intellectual

development. They are from infancy or childhood especially prone to
convulsive or other paroxysmal nervous phenomena. They are often
choreic, often hysterical. This association with instability of the
nervous system is related to the fact that dipsomania is more
common in women than in men.

DIAGNOSIS.—1. Acute Alcoholism.—The diagnosis of the ordinary

form of acute alcoholism, with the exception of alcoholic coma,
requires no consideration. The diagnosis of alcoholic coma from
profound coma due to other conditions is, in the absence of the
previous history of the case, always attended with difficulty, and is in
certain cases quite impossible. It is therefore of great practical
importance to obtain the history where it is possible to do so. The
odor of alcohol upon the breath is of less positive diagnostic value
than would at first thought appear. In the first place, sympathetic
bystanders may have poured alcoholic drinks down the throat of one
found unconscious, or, in the second place, individuals who have
taken a certain amount of drink may be, and not unfrequently are,
seized with apoplexy in consequence of the excitement thereby
induced. The more common conditions with which alcoholic coma is
confounded are apoplexy from cerebral hemorrhage and narcotic
poisoning, especially opium-poisoning. To these may also be added
uræmic coma and, under exceptional circumstances, sunstroke. In
all these cases the circumstances under which the individual has
been found are of diagnostic importance.

In alcoholic coma the pupils are more commonly dilated than

contracted, the heart's action feeble, the respiration shallow, the
muscular relaxation symmetrical, and the temperature low. There is
a strong odor of alcohol upon the breath.

In apoplexy from cerebral hemorrhage the condition of the pupils will

depend upon the location of the clot. They may be moderately
dilated, firmly contracted, or unequal. The enfeeblement of the
heart's action is, as a rule, less marked than in profound alcoholic
coma. The pulse may be small or full and slow or irregular. It is
usually slow and full. The respiration is often, although not invariably,
slow and stertorous. Not uncommonly, the eyes and also the head
deviate from the paralyzed side. If the coma be not absolute, the
muscular relaxation is unilateral. The temperature is at first slightly
below the normal, but less, as a rule, than in alcoholic coma; after
several hours it rises to or above the normal.

In complete opium narcosis the insensibility is profound; the heart's

action is slow or rapid, but feeble; the respirations slow and shallow
or quiet or stertorous; the face at first flushed, afterward pallid and
cyanosed; the pupils minutely contracted or dilated as death
approaches; and the muscular relaxation complete, with abolition of
reflex movements. In cases of doubt it is important to use the
stomach-pump.

Uræmic coma is apt to be preceded by or alternate with convulsions.

The pupils are more commonly slightly contracted than dilated, but
are without diagnostic significance. The temperature is not elevated;
it may even be low. The face may be pallid, pasty, and puffy, and
there may be general anasarca if the nephritis be parenchymatous.
On the other hand, in interstitial nephritis there is hypertrophy of the
heart, without evidence of valvular disease, and some degree of
puffiness of the lower extremities. In doubtful cases the urine should
be drawn by a catheter and subjected to chemical and microscopical
examination.51 Diabetic coma occurs suddenly without convulsions.
This condition may be suspected when the emaciation is extreme or
upon the recognition of sugar in the urine.
51 The following is the method recommended by Green (Medical Chemistry,
Philadelphia, 1880) for the detection of alcohol in the urine: If its reaction be acid, the
urine is exactly neutralized by potassium acid carbonate. It is then distilled on a water-
bath in a flask or retort connected with a condensing apparatus. When about one-
sixth of the liquid has passed over the distillate will, if alcohol be present, present the
following characteristics: first, the peculiar alcoholic odor; second, a specific gravity
lower than water; third, upon being mixed with dilute sulphuric acid and treated with a
few drops of potassium bichromate solution the liquid becomes green, owing to the
separation of chromic oxide; the odor of aldehyde may at the same time be observed.
This reaction is not characteristic, but may serve to confirm other tests. Fourth, if
dilute alcohol be shaken with an excess of solid and dry potassium carbonate in a
test-tube, the greater part of the water will be appropriated by the potassium
carbonate, and two layers of liquid will be formed. The alcohol constitutes the upper
layer, and if sufficiently concentrated will burn upon the application of a flame. Finally,
a small trace of alcohol may be separated from the urine without difficulty after the
ingestion of alcoholic liquids by means of a good fractionating apparatus. Less than 1
per cent. of alcohol cannot be detected.

Sunstroke is characterized by dyspnœa, gasping respiration,

jactitation, and intense heat of the skin. The pulse varies. It may be
full and labored or feeble and frequent. The face is usually flushed.
The pupils, at first contracted, are afterward dilated. The coma is apt
to be interrupted by transient local or general convulsions.

It is impossible to lay down any rules by which the maniacal form of

acute alcoholism may be at once diagnosticated from acute mania
from other causes. For the characteristics of the convulsive form of
acute alcoholism and those forms which occur in persons of
unsound mind the reader is referred to the descriptions of those
conditions. The diagnosis of acute poisoning by alcohol in lethal
doses can only be established during life by investigation of the
history of the case.

II. Chronic Alcoholism.—The lesions of chronic alcoholism, as has

already been pointed out, are not in themselves peculiar to that
condition. Many of them occur with more or less frequency in morbid
states not induced by alcohol. It is their association and progressive
character which gives to chronic alcoholism its individuality. The
occasional prominence of certain symptoms or groups of symptoms
may thus in particular cases lead to some confusion of diagnosis,
especially where the history is unknown or the habits of the
individual are concealed. In the greater number of cases, however,
the association of symptoms is such as to render the diagnosis, even
in the absence of a direct history, a comparatively easy one.

Chronic alcoholism is a condition rather than a disease—a condition

characterized by varying lesions of the viscera and nervous system,
by profound disturbances of nutrition, and by grave mental and moral
derangements. This fact being recognized, the cardinal error of
diagnosis to be guarded against is that of overlooking the condition
upon which the disease itself with which we have to do depends or is
associated. Congestion, inflammation, sclerosis, and steatosis affect
the various organs of the body and produce their characteristic
symptoms. Profound and lasting disturbances of nutrition demand
our attention. Psychical derangements of all grades, from mere
moodiness to confirmed and hopeless insanity, take place. These
affections must be diagnosticated for themselves here as elsewhere
in clinical medicine. The recognition of the underlying condition can,
however, alone supply the key to their true pathology.

Delirium tremens is occasionally diagnosticated with difficulty from

some forms of insanity not caused by drink. Here transitory and fixed
delusions, not mere terrors and hallucinations, are of importance, not
less than the absence of the varied and complex associations of
symptoms which are characteristic of alcoholism. The delirium of the
acute infectious diseases may be mistaken for delirium tremens.
Pneumonia, typhoid fever, and the exanthemata occasionally begin
with delirium resembling in some respects delirium tremens. Here
the history of the case, the pyrexia, and the general condition of the
patient are sufficient to establish the diagnosis if the danger of error
be borne in mind.
III. Hereditary Alcoholism.—The diagnosis of this condition can only
be established by careful investigation of the family history and
systematic study of the stages of progression by which the morbid
condition presented by the patient has been reached.

IV. Dipsomania.—The diagnostic points are the hereditary

transmission of this or other forms of insanity—the mental instability
of the patient in early life and in the intervals of the paroxysms, the
intermittent or cyclical recurrence of the attack, the morbid impulses
of a different kind associated with the impulse to drink, and the
struggle of the patient against his recurring impulses to
uncontrollable excesses.

PROGNOSIS.—The prognosis in acute alcoholism of the ordinary form

is favorable, so far as the immediate attack is in question. The
prognosis in rapidly-developing, overwhelming coma from enormous
doses of alcohol is in the highest degree unfavorable. Acute coma
from moderate doses usually passes off in the course of some
hours. It occasionally, however, terminates in fatal pneumonia.

The prognosis in delirium tremens of the ordinary form is favorable. It

becomes, however, more and more grave with each recurring attack.
Delirium tremens in patients suffering from advanced disease of the
heart, lungs, liver, or kidneys, or complicated by acute diseases of
these organs, is apt to prove fatal.

The prognosis of chronic alcoholism is gloomy. If the lesions be not

advanced, permanent discontinuance of alcoholic habits may be
followed by restoration of health, but, unfortunately, the
discontinuance is too often merely temporary, the habit being too
strong to be permanently broken off.

The prognosis in hereditary alcoholism is unfavorable, both as

regards the alcoholic habit and as regards the development of
serious diseases of the nervous system under adverse
circumstances, even in the absence of the direct action of alcohol.
The prognosis in dipsomania is unfavorable. The paroxysm may
recur many times without apparent serious result; the patient in the
course of some days or weeks recovers, abandons his evil courses,
and resumes his usual occupations. After a time, however, the
insanity of which the dipsomania is the recurring manifestation
declares itself as a more or less permanent state. The outbreaks
become more frequent and more prolonged, the mental condition in
the intervals progressively more morbid, until the patient lapses by
degrees into confirmed insanity.

The prognosis in all forms of alcoholism, both acute and chronic, is

rendered in a high degree uncertain by the psychical disorders which
characterize so many of its phases. In consequence of some of
these conditions the patient loses at once his appreciation of bodily
dangers and his power to avoid them; by reason of others, to escape
imaginary evils he plunges into real ones; and finally some of them
are of such a nature that they impel him to the blind and unreasoning
commission of the most grievous crimes, including suicide and
homicide.52
52 “I believe that more suicides and combined suicides and homicides result in this
country from alcoholism in its early stages than from any other cause whatsoever” (T.
S. Clouston, Clinical Lectures on Mental Diseases, Am. ed., 1884).

TREATMENT.—The prophylaxis of alcoholism has regard to

communities at large and to individuals. The prevention of the evils
of excess by the control of the sale of drink constitutes one of the
more important objects of state medicine. At the same time, the
traffic in alcohol is curiously evasive of legal enactments. The
difficulties attending the enforcement of sumptuary laws are well
known. Restrictive laws concerning the making and sale of alcoholic
drinks, while partaking of the nature of sumptuary laws are of more
comprehensive character, being obnoxious to powerful commercial
interests and to the sense of personal liberty of large numbers of
persons of all classes. As a result of organized opposition and
individual violation they are to a great extent inoperative as regards
the prevention of alcoholism.
Aside from the question of revenue from taxation, the practical
influence of law is in this matter somewhat limited, being confined
chiefly to the prevention of the sale of liquors to minors and persons
already intoxicated, and to ineffectual attempts in certain countries to
regulate the quality of the drink sold. The penalties for personal
drunkenness which does not lead to overt acts are, as a rule, wholly
inadequate to restrain it. The best results upon anything like an
extended scale have been obtained by the co-operative action of
philanthropic individuals in endeavoring to influence the moral tone,
especially among workingmen, to diminish temptations, and to
provide for leisure hours, in the absence of drink, reasonable
amusements and occupation to occupy the time ordinarily spent in
taverns and similar places.

The decrease in the consumption of alcoholic drinks in the United

States within recent years is doubtless due in part to increasing
popular knowledge concerning the dangers of alcoholic excess and
to the growth of a more wholesome public sentiment. It is, however,
in part also due to poor wages among workingmen.

As regards the individual, prophylaxis against alcoholism consists

either in total abstinence from, or in the most guarded indulgence in,
alcoholic beverages. It is unfortunate that individuals whose moral
and physical organization is such as renders them most liable to
suffer from the consequences of alcohol are by that very fact most
prone to its temptations, and hence contribute largely to the subjects
of alcoholism. These individuals are found among the ignorant, the
very poor, and especially among neurotic subjects of all classes of
society. Due consideration of this fact cannot fail to establish the
responsibility of those fortunately not belonging to these classes, in
two respects: first, that of example; and second, that of personal
restraint from the standpoint of heredity. The influence of heredity
among races addicted to alcohol has not yet attracted the attention it
deserves. It is probable that much of the tolerance for alcohol
exhibited by individuals, families, or even nations, is to be accounted
for by heredity. Still more probable is it that most of the evils and
crimes that befall alcohol-drinking communities and individuals are
due directly or indirectly to the abuse of this agent. No argument
against the indulgence in narcotics can be more potent than that
derived from a consideration of the laws of heredity.

I. The Treatment of Acute Alcoholism.—The medical treatment of

mere drunkenness requires no consideration. The rapid elimination
of alcohol, and the transient nature of its pathological effects in
excesses which are not repeated or prolonged, explain the
spontaneous recovery, which is usually sufficiently prompt and
permanent. The physical suffering and mental distress following
unaccustomed excesses are of salutary influence. Under certain
circumstances a powerful effort of the will is sufficient to control, at all
events for a time, the more moderate effects of alcohol. A similar
result follows the use of cold douches, the Turkish bath, and full
doses of certain preparations of ammonium, particularly the officinal
solution of the acetate of ammonium. In alcoholic stupor of an acute
kind the patient may be left to himself, care being taken that the
clothing is loosened and that the position is such as to prevent local
paralysis from the nerve-pressure. Alcoholic coma, if of moderate
intensity, may be managed in the same way. Profound alcoholic
coma requires, however, more energetic measures. Frictions,
artificial warmth, stimulating enemata, as of turpentine or of hot salt
and water, an ounce to the pint, hypodermic injections of strychnia or
atrophia in minute doses and occasionally repeated, inhalations of
ammonia, and occasional cold affusions, followed by brisk frictions
with warm flannel and faradism of the respiratory muscles, may be
needed to tide over the threatened fatal collapse. The stomach
should be at once washed out with hot coffee.

In the convulsive form of acute alcoholism chloral in twenty-grain

doses, repeated at intervals until sixty grains have been given,
usually serves to arrest, or at all events to moderate, the paroxysm.
It may be administered by the mouth or in double doses by the
rectum. If chloral be inadmissible by reason of weakness of the
circulation, paraldehyde may be substituted in doses of from half a
drachm to one drachm, repeated at intervals of from one to two
hours until quietude is produced. Where the convulsive paroxysms
are of great violence it may be necessary to control them by the
cautious administration of ether by inhalation.

The mania of acute alcoholism calls for energetic management. To

avert injury to the patient himself or to those about him he must be
confined, if practicable, in a suitable apartment in a hospital; if not, in
his own house and carefully watched. Here, as a rule, paraldehyde,
chloral, or large doses of the bromides constitute our most efficient
means of medication.

In all forms of acute alcoholism it is a rule admitting of no exception

to at once withhold alcohol in every form and all doses. If, under
exceptional circumstances, great nervous depression or flagging
circulation seems to call for the use of alcohol in small amounts, it is
far better to substitute other drugs. The frequently repeated
administration of hot beef-tea or rich broths in small doses, with
capsicum and the use of the various preparations of ammonia, or
small doses of opium with or without quinia and digitalis, proves
useful in proportion to the skill and discrimination with which they are
selected and repeated. It is a good plan to commence the treatment
with an active purge.

In the acute collapse following excessive doses—lethal doses—the

stomach is to be immediately emptied by the tube or pump and
washed out with warm coffee. In the absence of the stomach-tube
emesis may be provoked by the use of mustard or sulphate of zinc
or by hypodermic injection of apomorphia. The patient must be
placed in the recumbent posture and surrounded with hot blankets.
The cold douche may be occasionally applied to the head and face,
and the muscles of respiration may be excited to action by faradism.
Artificial respiration and friction of the extremities may also be
required. Inhalations of ammonia may be used. The flagging heart
may be stimulated by occasionally tapping the præcordia with a hot
spoon—Corrgan's hammer. Hypodermic injections of digitalis may
also be employed. Overwhelming doses of alcohol, leading promptly
to collapse, usually prove fatal despite all treatment.
II. The Treatment of Chronic Alcoholism.—Whatever may be the
prominence of particular symptoms or groups of symptoms, whether
they indicate derangement of the viscera, of the nervous system, or
of the mind, whatever their combination, the fundamental therapeutic
indication in chronic alcoholism is the withdrawal of the poison. The
condition is directly due to the continuous action of a single toxic
principle: its relief when practicable, its cure when possible, are only
to be obtained by the discontinuance of that poison. This is a matter
of great, often of insurmountable, difficulty. The obstacles are always
rather moral than physical. Occasional or constant temptation, the
iron force of habit, the malaise, the faintness, the craving of the
nervous system, and, worse than all, the enfeebled intellectual and
moral tone of the confirmed drunkard, stand in the way. Even after
success seems to have been attained, and the patient, rejoicing in
improved physical health and in the regained companionship and
consideration of his family and friends, feels that he is safe, it too
often happens that in an unguarded moment he yields to temptation
and relapses into his old habits. A patient of the writer, after seven
years' abstinence from drink, again became its victim in
consequence of the incautious suggestion of a young medical man,
met at a summer hotel, to take brandy for some transient disorder,
and died after eight months of uncontrollable excesses. It is
necessary to guard the patient against the temptation to drink. To
secure this he may he sent as a voluntary patient for a length of time
to a suitable institution, or, still better, he may place himself under the
care of a conscientious, clear-headed country doctor in a sparsely-
settled region, preferably in the mountains or at the seaside. The
malaise, depression, insomnia, and other nervous symptoms when
of moderate degree are best treated by abundance of nutritious and
easily-assimilable food, taken often and in moderate amounts. To
this end gastro-intestinal disturbances may be practically
disregarded, except in so far as they regulate the selection of a
highly nutritious diet. As a matter of fact, in the early periods of
chronic alcoholism, while visceral lesions of a grave character are
yet absent, appetite and digestion alike improve in the majority of
cases upon the withdrawal of alcohol, provided a sufficiently
abundant and easily assimilable dietary is insisted upon. Grave
visceral lesions characterize a more advanced alcoholic cachexia
and necessarily complicate the treatment. Nevertheless, even here
the indication is the withdrawal of the poison. The nervous symptoms
require special medication. The whole group of tonics, from simple
bitters to quinia and strychnia, is here available. It is impossible to
lay down rules for the treatment of particular cases except in the
most general manner. In the absence of conditions calling for special
treatment, such as gastritis, hepatic or pulmonary congestion, fatty
heart, etc., good results follow the frequent administration of small
doses of quinia and strychnia; thus, the patient may take one grain of
quinia six or eight times a day, or a little gelatin-coated pill containing
1/200–1/100 of a grain of strychnia every hour during the waking day,

amounting in all to one-twentieth, one-tenth, or one-fifth of a grain in

the course of twenty-four hours. This treatment is often followed by
the relief of tremor, the quieting of nervous irritability, and the
production of good general results. The malaise, the general
depression, and especially the sinking feeling at the pit of the
stomach so often complained of by patients, are best relieved by
food. Fluid extract of coca is also useful in these conditions. The
value of cocaine in the management of the nervous symptoms of
chronic alcoholism, and in particular as a temporary substitute for
alcohol, is doubtful. The writer, having used it in a number of cases
by the mouth and hypodermically in doses of ¼–1 grain, has had
variable results. In some cases it temporarily relieved the craving
and concomitant symptoms; in others it failed wholly: in one instance
one-fourth of a grain was followed by great nervous depression. It is
desirable not to inform the patient of the nature of the remedy,
especially if its use be followed by good results, lest the cocaine
itself supplant alcohol as an habitual narcotic. Cold or tepid
sponging, the occasional hot bath at bedtime, and the Turkish bath
are useful adjuvants to the treatment. As a rule, opium is
contraindicated. Sleep often follows the administration of a cupful of
hot broth or milk at bedtime. Lupulin is here useful, and the writer
has come to regard an ethereal extract of lupulin in doses of from
one to three grains as a valuable and harmless hypnotic. If
necessary, hypnotic doses of chloral or paraldehyde may be used,
but care is required in their administration, and their early
discontinuance is advisable. If anæmia be profound, chalybeate
tonics do good, and among the preparations of iron pills of the dried
sulphate with carbonate of potassium (Blaud's pills) are especially
useful.

The obesity of drunkards, as a rule, diminishes on the withdrawal of

alcohol. Under circumstances of partial or complete abstinence from
drink measures to reduce the weight of such patients are wholly
inadmissible.

In conditions characterized by failure of mental power, in beginning

dementia or threatened insanity, the syrup of the hypophosphites,
the compound syrup of the phosphates, or cod-liver oil should be
administered. These remedies are likewise useful in various forms of
alcoholic paralysis, as are also faradism and galvanism employed
secundum artem. The various forms of alcoholic insanity require
special treatment, only to be had in institutions designed for the care
of patients suffering from mental diseases in general.

Whilst it is desirable in the treatment of all forms of chronic

alcoholism to secure the permanent discontinuance of the alcoholic
habit, the skill, judgment, and experience of the physician must
determine the degree of rapidity with which this, when practicable, is
to be done. The number of cases in which alcohol can be
discontinued at once and finally is limited; those in which it can be
wholly given up in the course of a few days constitute the largest
proportion of the cases; finally, in a small number of cases alcohol
can only be withdrawn cautiously and by degrees.53 Whilst it is in
most cases essential to remove the patient from his customary
surroundings and companionships, it is in the highest degree
important to provide for him mental occupation and amusement. To
this end a wholesome open-air life, with sufficient daily exercise to
induce fatigue, is highly desirable, as indeed is the companionship of
interested and judicious friends.
53 It must be borne in mind that in chronic alcoholism acute maladies of all kinds,
including traumatism, both accidental and surgical, act as exciting causes of delirium
tremens. The part played by the abrupt diminution or withdrawal of alcohol under such
 circumstances is often an important one. It is the opinion of the writer that a certain
amount of alcohol should be administered for a time at least in the accidental injuries
and acute sicknesses of alcoholic subjects, and that the reduction should be gradually
made.

The Treatment of Delirium Tremens.—The patient should be

confined in a large, well-aired apartment, without furniture except his
bed, and when practicable he should have a constant attendant. The
favorable influence of a skilful nurse in tranquillizing these patients is
very great. The custom of strapping them to the bed by the wrists
and ankles is to be deprecated. If the case be a mild one, and
especially during convalescence, open-air exercise in the sunshine
with an attendant is of benefit; care must, however, be taken to
guard against the danger of escape.

Under no circumstances should visitors be permitted to see the

patient. In young persons the treatment may be preceded by an
active saline or mercurial purge. In elderly persons, those suffering
from cachectic conditions, or in cases characterized by marked
debility and feeble circulation—conditions frequent in persons who
have had repeated attacks—it is not desirable to purge. Alcohol
should be either wholly withdrawn or more or less rapidly diminished.
It must be replaced by abundant food in the form of concentrated
broths or meat-extracts. In cases of vomiting these must be given
hot and in small doses frequently repeated. Bitter infusions may also
be given, or milk or equal parts of milk and Vichy water. If there be
thirst, the effervescent waters may be given freely. Patients often
drink with satisfaction and apparent benefit hop tea, which may be
made simply with water or with equal parts of water and porter.

The medicinal treatment will depend to a large extent upon the

peculiarities of the case. In mild cases a combination of the watery
extract of opium in small doses, not exceeding a quarter of a grain,
with quinia and digitalis, repeated every four or six hours, is often
useful. Although the view once entertained that the graver symptoms
were the result of prolonged sleeplessness is no longer tenable, the
induction of sleep, or at all events of mental and physical repose, is
among the more important therapeutical indications. For this purpose
hypnotic doses of opium are not only not desirable, but are even, in
the majority of instances, attended with danger. The sleep which
follows repeated and increasing doses of opium in delirium tremens
has too often terminated in coma deepening into death. As
calmatives, extract of cannabis indica, hyoscyamus, or the fluid
extract of piscidia are useful. As hypnotics, the bromides, chloral,
and paraldehyde yield, in the order here given, the best results. The
bromides are better in large single doses than in small doses often
repeated, better in combination than singly. Chloral, either by the
mouth or by the rectum, in doses of from twenty to forty grains, is
often followed by beneficial sleep. It is contraindicated where the
heart's action is much enfeebled. Paraldehyde, in doses of half a
drachm to one drachm, repeated at intervals of two or three hours
until sleep is induced, is still more efficient. This drug may be
administered without the fear of its exerting a depressing influence
upon the heart. The depression characteristic of grave delirium
tremens may be combated by repeated small doses of champagne
or by carbonate of ammonium in five- or ten-grain doses; the
vomiting, by withholding food and medication by the mouth, and
giving them for some hours wholly by the rectum or hypodermically.
Excessive restlessness is sometimes favorably influenced by cold
affusion, followed by brisk friction and warm blankets with continuous
artificial heat. The cold pack has proved useful.

Digitalis may be employed, ex indicatione symptomatica, but the

enormous doses of tincture of digitalis used by the late Jones of
Jersey and others are here mentioned only to be condemned.

To sum up, the chief indications for treatment are complete isolation,
the withdrawal of alcohol, abundant, readily assimilable, nutritious
food, and control of the reflex excitability of the nervous system.

III. Hereditary Alcoholism.—The treatment of the vicious propensities

of the descendants of alcoholic parents does not fall directly within
the province of the physician. It is among the most difficult problems
of education. The recognition of the cause of evil traits manifested in
childhood and youth may do something to avert dangers commonly
unsuspected. All things considered, the outlook is not hopeful. The
recognition, on the part of the physician, of the influence of
hereditary alcoholism in cases of arrested development, feeble
organization, or declared disease of the nervous system will perhaps
do less to aid his treatment in many cases than to reconcile him to its
want of full success. The cry of warning is to those who are eating
sour grapes that the teeth of their children will be set on edge.

IV. Dipsomania.—The general indications for the treatment of

dipsomania are two: first, the management of the paroxysm; second,
the control of the general condition itself.

First, then, during the paroxysm the patient must be saved, in so far
as is possible, from the danger of injuring himself or others and from
squandering his property. If the excesses are of such a degree as to
render it practicable, the same treatment must be carried out as in
cases of acute alcoholic mania and delirium tremens—namely,
confinement in a suitable apartment under the care of an
experienced nurse and the control of the doctor. Unfortunately, this
plan is not always practicable in the early days of the outbreak. Here
tonics, coca, and repeated small doses of quinia and strychnia are of
advantage. Courses of arsenic at the conclusion of, and in the
intervals between, the paroxysms are of use, on account of the
excellent influence they exert on the general nutrition. These may be
advantageously alternated with iron, cod-liver oil, and the compound
syrup of the phosphates or of the hypophosphites. Hydrotherapy
may also be used with advantage, and the influences of a well-
regulated hydropathic establishment are much more favorable than
those of institutions specially devoted to the treatment of alcoholic
subjects. In the latter the moral atmosphere is apt to be bad; the
patients support each other, and too often conspire to obtain in
secret that which is denied them openly, or, if the discipline be too
strict for this, they sympathize with each other in their restraint, react
unfavorably upon each other in the matter of shame and loss of self-
respect, and plot together to secure their liberty.
Few dipsomaniacs in the earlier periods are proper subjects for
treatment in hospitals for the insane. If cerebral excitement or
sleeplessness persist after the paroxysms, chloral, paraldehyde, or
the bromides in large doses may be used to secure sleep. Various
combinations of the bromides are often of use where the single salts
fail. It must not be forgotten that during the paroxysm there is great
danger lest the patient do himself or others harm. When there are
indications of an impending attack, and during the period of
depression following the attacks, benefit is derived from the daily use
of bitter infusions. As a matter of fact, however, the management of
these cases is among the most unsatisfactory of medical
undertakings. The difficulty is increased by the latent character of the
mental disorder in the intervals between the attacks. Even when
such patients voluntarily enter hospitals for the insane, they cannot
be retained there sufficiently long to derive any permanent benefit.
What we want is, in the words of Clouston, “an island where whiskey
is unknown; guardianship, combined with authority, firmness,
attractiveness, and high, bracing moral tone; work in the open air, a
simple natural life, a return to mother Earth and to Nature, a diet of
fruits, vegetables, bread, milk, eggs, and fish, no opportunity for one
case to corrupt another, and suitable punishments and deprivations
for offences against the rules of life laid down. All these continued for
several years in each case, and the legal power to send patients to
this Utopia for as long a period as medical authority determines, with
or without their consent.”

THE OPIUM HABIT AND KINDRED AFFECTIONS.