Chapter 1

A Historical Introduction
to Photocatalysis

Juan M. Coronado

As early as in 1911, 76 years after Berzelius coined the word catalysis, the term
photocatalysis appeared in several scientific communications. In Germany, Eibner
incorporated this concept in his studies on the effect of the illumination of ZnO on
the bleaching of Prussian blue (Eibner 1911). Contemporaneously, the term
photocatalysis achieved additional relevance when it was displayed in the title of a
few articles dealing with the degradation of oxalic acid under illumination in the
presence of uranyl (UO2+) salts (Bruner and Kozak 1911; Landau 1913). These
pioneering experiments, performed by recognized scientists in France and Ger-
many, explored the unusual photochemical properties of this cation of the actinide
element, and they laid the foundations of the actinometric measurements, which
are used even now for determining the flux of photons in photochemical reactions.
However, nowadays this process is not usually described as photocatalytic, despite
the fact that it implies the absorption of light by the uranyl ions in solution and
their interaction in an excited state with the organic species to yield CO2 and
water. After those seminal reports, the interest on these processes decayed for
almost a decade and the following reference in the literature was published in
1921. In this work, (Baly et al. 1921) studied the production of formaldehyde under
visible light, using colloidal uranium salts and ferric hydroxides as catalysts.
Shortly after, the group of Baur at the ETH of Zurich reported that the irradiation
of a ZnO suspension promoted the reduction of Ag+ salts to Ag0 (Baur and Perret
1924). A few years later, the influence of rutile in the light-induced aging of paints
and fabrics was recognized (Keidel 1929). Following this research line, (Doodeve
and Kitchener 1938) investigated for the first time the ability of TiO2 to act as
photosensitizer for bleaching dyes in the presence of oxygen in the late 1930s. This
work reported that UV absorption produces active oxygen species on the TiO2
surface, causing the discoloration of organic chemicals by photooxidation,

J. M. Coronado (&)
Institute IMDEA Energa, Avenida de Ramn de la Sagra, 3
28935 Mstoles, Madrid, Spain
e-mail: juanmanuel.coronado@imdea.org

J. M. Coronado et al. (eds.), Design of Advanced Photocatalytic Materials 1

for Energy and Environmental Applications, Green Energy and Technology,
DOI: 10.1007/978-1-4471-5061-9_1, Springer-Verlag London 2013
2 J. M. Coronado

Fig. 1.1 Annual evolution of

the number of articles of
Scientific Citation Index
(SCI) publications related to
photocatalysis from 1910 to
1981. The dashed line marks
the publication of the seminal
article of Fujishima and
Honda. However, it is
important to note that such
work is not included in these
data because it does not
contain the term
photocatalysis (data
obtained from ISI web of
knowledge)

although TiO2 itself remains unchanged after the process. Therefore, some of the
basic features of heterogeneous photocatalysis were already discovered during
these early investigations. However, in the absence of practical applications, these
processes were as much a curiosity and, frequently, an annoying drawback of
inorganic pigments. Consequently, the interest on these characteristics of semi-
conductors almost faded in the following decades, as it can be appreciated in
Fig. 1.1. Nevertheless, some topics related to the interaction of semiconductors
with adsorbed molecules, like the mechanism of photosensitization in the presence
of dyes molecules or the effect of gases on photoconductivity, were investigated in
the late 1950s by the group of Terenin at the University of St. Petersburg (Terenin
1955; Serpone 2012). However, the opportunities of using these photoactive
materials to induce chemical transformations continued to be overlooked at that
time. In the 1960s, this situation started to change slowly when a Russian group
headed by Filimonov (1964) began to explore the odds of using materials such as
ZnO or TiO2 for isopropanol photooxidation. In parallel, different Japanese groups
studied the heterogeneous photooxidation of organic solvents in the presence of
ZnO (Kato and Mashio 1964; Ikekawa et al. 1965). Simultaneously, in Germany,
Doerffler and collaborators observed the promotion of carbon monoxide oxidation
over illuminated ZnO (Doerffler 1964). The interest on the photocatalytic oxida-
tion processes continued in the early 1970s with the work by Teichners group on
the partial oxidation of paraffins and olefins over TiO2 (Formenti et al. 1970),
whereas Tanaka and Blyholde (1970) studied the photocatalytic decomposition of
nitrous oxide.
At that point, this technology was ready for a change of paradigm, and this step
forward was prompted, at least partly, by the economic situation at the beginning
of the 1970s decade. In 1973, crude prices, traditionally stable, skyrocketed
1 A Historical Introduction to Photocatalysis 3

suddenly due to the embargo of the organization of Arab Petroleum Exporting

Countries (OAPEC), and for the first time the future scarcity of oil became a
serious concern. This oil crisis led to an unprecedented impulse of the research in
alternative energy sources so as to overcome the dependence on petroleum. In
those economically convulse times, two Japanese researchers, Fujishima and
Honda (1972), reported in an article in Nature the electrochemical photolysis of
water using a rutile electrode exposed to near-UV light and connected to a plat-
inum counter electrode through an electrical load. This apparently modest work
opened up a new world of possibilities for the production of clean hydrogen using
abundant and inexpensive water and sunlight. Accordingly, this report is still
immensely popular as it can be inferred from the number of citations that it
accumulates, approaching 6,500 by the end of 2012. However, the influence of this
article was not immediate, and up to late 1970, water splitting basically lied on the
side of photoelectrochemistry. This started to change when Nozik (1977), at that
time working for Allied Chemical Corporation, evidenced that external potential
was not required to split the water molecule and the photoactivity could be boosted
if a noble metal (e.g., Pt) was incorporated. Subsequent investigations by Wagner
and Somorjai (1980) compared the photogeneration of H2 over platinized SrTiO3
single crystals with and without potential. In a similar study, Sakata and Kawai
(1981) reported the production of H2 and CH4 upon irradiation of Pt/TiO2 sus-
pensions in aqueous ethanol with high quantum efficiency: ca. 38 %.
The influence of Fujishimas work was also important to consolidate the pre-
ponderance of TiO2 among photoactive materials because its stability in aqueous
solution was established under a wide range of pH and external potentials.
Therefore, the relevance of this semiconductor progressively increased with works
such as that of Bickley et al. who tested the photooxidation of isopropanol on rutile
TiO2 (Bickley et al. 1973). In a similar way, it is worth to highlight the pioneering
studies by Bards group at the University of Texas, which showed that cyanide
(CN-) could be efficiently photooxidized to cyanate (CNO-) in alkaline condi-
tions and in the presence of TiO2 and oxygen (Frank and Bard 1977).
Therefore, it seems clear that photocatalysis, along its already centennial his-
tory, has acquired knowledge from very different disciplines. Evidently, photo-
chemistry, catalysis and, to a lesser extent, semiconductor physics have
historically shaped our understanding of this phenomena, which depends on the
solid interactions with radiation but also on surface reactivity. Interestingly,
photoelectrocatalysis, as a closely related process, has contributed enormously to
boost energetic applications, and both technologies have growth intertwined. Most
recently, nanotechnology has provided new exciting possibilities for the devel-
opment of more efficient and sophisticated photocatalytic materials, although it has
also brought new concerns related to the toxicity of nanostructured solids.
Although it was once considered a problem for promoting the discoloration of
paints and dyes, photocatalysis progressively has evolved to become a well-
established technology, which holds the promise of many environmentally friendly
solutions for the society demands.
4 J. M. Coronado

References

Baly ECC, Heilbron IM, Barker WF (1921) Photocatalysis. Part I. The synthesis of formaldehyde
and carbohydrates from carbon dioxide and water. J Chem Soc 119:10251035
Baur E, Perret A (1924) The action of light on dissolved silver salts in the presence of zinc oxide.
Helv Chim Acta 7:910915
Bickley RI, Munuera G, Stone FS (1973) Photoadsorption and photocatalysis on rutile surface. II.
Photocatalytic oxidation of isopropanol. J Catal 31:398407
Bruner L, Kozak J (1911) Information on the photocatalysis I the light reaction in uranium salt
plus oxalic acid mixtures. Z Elktrochem Angew P 17:354360
Doerffler W. Hauffe K. (1964) Heterogeneous photocatalysis I. Influence of oxidizing and
reducing gases on the electrical conductivity of dark and illuminated zinc oxide surfaces.
J Catal 3:156170
Doodeve CF, Kitchener JA (1938) The mechanism of photosensitization by solids trans. Faraday
Soc 34:902912
Eibner A (1911) Action of light on pigments I. Chem-Ztg 35:753755
Filimonov VN (1964) Photocatalytic oxidation of gaseous isopropanol on ZnO ? TiO2. Dokl
Akad Nauk SSSR 154(4):922925
Formenti M, Juillet F, Teichner SJ (1970) Controlled photooxidation of paraffins and olefins over
anatase at room temperature. C R Seances Acad, Sci Ser C 270C:138141
Frank SN, Bard AJ (1977) Heterogeneous photocatalytic oxidation of cyanide ion in aqueous
solutions at titanium dioxide powder. J Am Chem Soc 99:303304
Fujishima A, Honda K (1972) Electrochemical photolysis of water at a semiconductor electrode.
Nature 238:3738
Ikekawa A, Kamiya M, Fujita Y, Kwan T (1965) Competition of homogeneous and
heterogeneous chain terminations in heterogeneous photooxidation catalysis by ZnO. Bull
Chem Soc Jpn 38:3236
Kato S, Mashio F (1964) Titanium dioxide-photocatalyzed oxidation. I. Titanium dioxide
photocatalyzed liquid phase oxidation of tetralin, Kogyo Kagaku Zasshi 67:11361140
Keidel E (1929) The fading of aniline dyes in the presence of titanium white. Farben-Zeitung
34:12421243
Landau M (1913) Le phnomne de la photocatalyse. Compt Rend 156:18941896
Nozik AJ (1977) Photochemical diodes. Appl Phys Lett 30(11):567570
Sakata T, Kawai T (1981) Heterogeneous photocatalytic production of hydrogen and methane
from ethanol and water. Chem Phys Lett 80:341344
Serpone N, Emeline AV, Horikoshi S, Kuznetsov VN, Ryabchukb VK (2012) On the genesis of
heterogeneous photocatalysis: a brief historical perspective in the period 1910 to the mid-
1980s. Photochem Photobiol Sci 11:11211150
Tanaka KI, Blyholde G (1970) Photocatalytic and thermal catalytic decomposition of nitrous
oxide on zinc oxide. J Chem Soc D-Chem Comm 18:1130
Terenin AN (1955) The desorption of adsorbed gases from metals and semiconductors, and their
adsorption under the influence of light. Probl Kinet Katal 8:1733
Wagner FT, Somorjai GA (1980) Photocatalytic and photoelectrochemical hydrogen production
on strontium titanate single crystals. J Am Chem Soc 102:54945502