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Metal Oxide-Based Photocatalysis
This page intentionally left blank
Metal Oxides Series
Metal Oxide-Based
Photocatalysis
Fundamentals and Prospects
for Application
Adriana Zaleska-Medynska
Series Editor
Ghenadii Korotcenkov
Elsevier
Radarweg 29, PO Box 211, 1000 AE Amsterdam, Netherlands
The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
50 Hampshire Street, 5th Floor, Cambridge, MA 02139, United States
© 2018 Elsevier Inc. All rights reserved.
No part of this publication may be reproduced or transmitted in any form or by any means,
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seek permission, further information about the Publisher’s permissions policies and our
arrangements with organizations such as the Copyright Clearance Center and the Copyright
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This book and the individual contributions contained in it are protected under copyright by
the Publisher (other than as may be noted herein).
Notices
Knowledge and best practice in this field are constantly changing. As new research and
experience broaden our understanding, changes in research methods, professional practices,
or medical treatment may become necessary.
Practitioners and researchers must always rely on their own experience and knowledge in
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In using such information or methods they should be mindful of their own safety and the
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To the fullest extent of the law, neither the Publisher nor the authors, contributors, or
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of products liability, negligence or otherwise, or from any use or operation of any methods,
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Library of Congress Cataloging-in-Publication Data

A catalog record for this book is available from the Library of Congress
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library
ISBN: 978-0-12-811634-0
For information on all Elsevier publications

visit our website at https://www.elsevier.com/books-and-journals
Publisher: Matthew Deans

Acquisition Editor: Kayla Dos Santos
Editorial Project Manager: Andrae Akeh
Production Project Manager: Swapna Srinivasan
Cover Designer: Miles Hitchen
Typeset by SPi Global, India
Contents
List of contributors ix
1 Introduction 1
1.1 Introduction 1
2 Fundamentals of metal oxide-based photocatalysis 3

Anna Goła˛biewska, Kobylanski Marek P., Adriana Zaleska-Medynska
2.1 Principles of metal oxide-based photocatalysis 3
2.2 Requirements of metal oxides 23
2.3 Role of noble metals in photocatalysis 34
References 38
Further reading 49
3 Metal oxide photocatalysts 51

Ewelina Grabowska, Martyna Marchelek, Marta Paszkiewicz-Gawron,
3.1 Synthesis of metal oxides used in photocatalysis 51
3.2 Unitary metal oxides (advantages, disadvantages, achievements) 65
3.3 Nanostructured MeIOx/MeIIOx heterojunction photocatalysts 123
3.4 Metal/MeOx photocatalysts 140
3.5 Composite-based photocatalysts 150
3.6 Outlook 155
References 157
Further reading 209
4 Application of metal oxide-based photocatalysis 211

Bajorowicz Beata, Kobylanski Marek P., Malankowska Anna,
Mazierski Paweł, Nadolna Joanna, Pieczy nska Aleksandra,
4.1 Water treatment 211
4.1.1 Types of contamination 212
4.1.2 Photocatalyst immobilization 213
4.1.3 Photocatalytic reactors 214
4.1.4 Effect of reaction parameters on the photocatalytic process 216
4.1.5 Scale-up process and prospects 220
References 220
vi Contents
Further reading 222

4.2 Hydrogen production 223
4.2.1 Basic principle of photocatalytic hydrogen generation by water
splitting 223
4.2.2 Strategies for achieving photocatalytic water splitting 224
4.2.3 Brief overview of metal oxide semiconductors in photocatalytic
water splitting 225
4.2.4 Chemical additives for H2 and O2 production enhancement 226
4.2.5 Metal oxide co-catalysts for photocatalytic water splitting 227
4.2.6 Evaluation of photocatalytic water splitting 228
4.2.7 Photoreactor design 229
4.2.8 Conclusions and prospects 232
References 233
Further reading 237
4.3 Air depollution and volatile organic compound (VOC)
removal using different photocatalysts 237
4.3.1 The mechanism of pollutant photo-oxidation 239
4.3.2 Photodisinfection of pathogens 243
4.3.3 Factors that impact the photocatalytic oxidation process 244
4.3.4 Immobilization techniques 245
4.3.5 Photoreactor design for photocatalytic air purification 246
4.3.6 Conclusions and future prospects 248
References 248
4.4 Hydrocarbon generation (CO2 reduction) 252
4.4.1 Fundamental aspects for photocatalytic reduction of CO2 252
4.4.2 Photocatalyst design for photocatalytic CO2 reduction 256
4.4.3 Important factors for photocatalytic reduction of CO2 258
4.4.4 Photoreactors for CO2 reduction 259
References 262
4.5 Photochemical transformation of specific compounds 265
4.5.1 Types of photocatalysts 267
4.5.2 Role of external conditions 270
4.5.3 Synthesis of organic compounds 272
4.5.4 Reactors for phototransformation 274
4.5.5 Scaling-up process and prospects 275
References 276
4.6 Medical applications: Application in photodynamic therapy 279
4.6.1 Phocatalysts 280
4.6.2 Light penetration 283
4.6.3 Conclusions and perspectives 284
References 285
4.7 Applications in construction, building materials, and textiles 287
4.7.1 Introduction 287
Contents vii
4.7.2 Superhydrophilicity mechanism 288

4.7.3 Exterior construction materials 290
4.7.4 Interior construction materials 293
4.7.5 New applications 294
4.7.6 Perspectives, problems, and limitations 295
References 296
Further reading 297
4.8 Photoelectrocatalysis (PEC) for energy generation 297
4.8.1 Photoelectrocatalysts for solar energy conversion 297
4.8.2 PEC hydrogen generation 309
References 312
Further reading 319
4.9 Integration and coupling of heterogeneous photocatalysis
with other advanced oxidation processes 319
4.9.1 Photocatalytic ozonation 320
4.9.2 Photoelectrocatalysis 325
4.9.3 Heterogeneous photo-Fenton and photoelectro-Fenton methods 327
4.9.4 Sonophotocatalysis 332
References 335
Further reading 340
5 Outlook and prospects 341

Index 345
List of contributors
Pieczy
nska Aleksandra University of Gdansk, Gdansk, Poland
Malankowska Anna University of Gdansk, Gdansk, Poland
Bajorowicz Beata University of Gdansk, Gdansk, Poland
Anna Goła˛biewska University of Gdansk, Gdansk, Poland
Ewelina Grabowska University of Gdansk, Gdansk, Poland
Nadolna Joanna University of Gdansk, Gdansk, Poland
Martyna Marchelek University of Gdansk, Gdansk, Poland
Kobyla
nski Marek P. University of Gdansk, Gdansk, Poland
Marta Paszkiewicz-Gawron University of Gdansk, Gdansk, Poland
Mazierski Paweł University of Gdansk, Gdansk, Poland
Adriana Zaleska-Medynska University of Gdansk, Gdansk, Poland

Introduction
University of Gdansk, Gdansk, Poland
1
1.1 Introduction
Nano- or microparticles of metal oxides irradiated by an appropriate light spectrum
(in the ultraviolet and visible range) may serve as a source of active oxygen species
as well as a source of photogenerated electrons and holes. These unique properties
(so called photocatalytic properties) may be used in a wide range of environmental
friendly processes, such as:
(1) pollutant degradation or removal from the gas and aqueous phases (water, wastewater and
air treatment technologies);
(2) pollutant degradation at the surface of building materials (self-cleaning surfaces);
(3) conversion of solar energy into energy of chemical bonds (via water photosplitting or CO2
conversion into useful hydrocarbons);
(4) conversion of solar energy into electric energy (solar cells);
(5) photochemical transformation of specific chemical compounds.
Some undoubted advantages of the photocatalytic process are the ability to carry it out
in ambient conditions of temperature and pressure, the possibility of using solar light
to drive chemical reactions, and the possibility to reuse photocatalyst particles.
Hydroxyl radicals, as well as other active oxygen species produced at the surface
of irradiated metal oxide particles, could be a powerful and green oxidant employed
to degrade organic pollutants and to remove inorganic compounds and microorgan-
isms present in water, wastewater, or air. On the other hand, the mechanism of the
photocatalytic process is quite complicated, the efficiency of most of the processes
mentioned above is not too high at present, and moreover, the photoactivity of metal
oxide particles is affected by a wide spectrum of factors. Notwithstanding this, the
immense value of heterogeneous photocatalysis lies in its great potential to use solar
energy to conduct chemical reactions and to convert solar energy into energy of chem-
ical bonds. Efficient utilization of solar light for water splitting to generate hydrogen
(clean energy carrier) and for artificial photosynthesis (CO2 photoconversion) seems
to be a Holy Grail for the chemical community. Metal oxide photocatalysts could also
be employed to produce energy via photoelectrochemical processes.
This book presents the principles and fundamentals of metal oxide-based hetero-
geneous photocatalysis and highlights the current developments and future potential
of applications of unitary metal oxides, as well as their hybrids with noble metal
nanoparticles and other semiconductors. The book consists of three main chapters,
presenting the mechanisms of metal oxide-based photocatalysts excitation, the most
important requirements for metal oxides used in photocatalysis, preparation methods
Metal Oxide-Based Photocatalysis. https://doi.org/10.1016/B978-0-12-811634-0.00001-9

2 Metal Oxide-Based Photocatalysis
of metal oxides used in photocatalysis, advantages, disadvantages, and achievements

of the most important metal oxides (TiO2, WO3, ZnO, Fe2O3, Ta2O5, CuO) and the
most important applications (water treatment, hydrogen production, air treatment,
chemical synthesis, medical applications and applications in construction).
We hope that this book summarizes and organizes the knowledge in the field of
metal-oxide based photocatalysis and that it can also be used in the classroom for
undergraduate and graduate students focusing on heterogeneous photocatalysis, sus-
tainable chemistry, energy conversion and storage, nanotechnology, chemical engi-
neering, environmental protection, optoelectronics, sensors, and surface and
interface science.
Fundamentals of metal
oxide-based photocatalysis 2
Anna Goła˛biewska, Kobylan ski Marek P., Adriana Zaleska-Medynska
University of Gdansk, Gdansk, Poland
2.1 Principles of metal oxide-based photocatalysis

The discovery of metal oxide-based photocatalysis was published in 1972 by
Fujishima and Honda, who demonstrated that photoirradiation of a TiO2-covered elec-
trode immersed in an aqueous electrolyte led to the production of O2 and H2 from TiO2
and Pl electrodes, respectively (so-called Honda-Fujishima effect) [1]. Notwithstand-
ing this, some reports describing the ability of TiO2 particles to produce photocatalytic
oxidation of organic compounds had been presented prior to this discovery. Thus, the
ability of ZnO and TiO2 to generate photocatalytic degradation of organic compounds
in the gas phase was announced in 1961 [2] and 1964 [3], respectively, and the photo-
catalytic oxidation of tetralin (1,2,3,4-tetrahydronaphthalene) in aqueous TiO2 sus-
pension was reported in 1964 [4]. Since 1977, when Frank and Bard explored the
possibility of employing TiO2 to decompose cyanide in aqueous suspension [5], there
has been increasing interest in the environmental applications of such a process.
2.1.1 Mechanism of photocatalytic reactions

In contrast to metals, which possess a continuum of electronic states, semiconductors
have an empty region in which there are no accessible energy levels that promote the
recombination of an electron and a hole produced by photoactivation of a solid [6].
This empty region, which extends from the top of the filled valence band to the bottom
of the vacant conduction band, is called the bandgap. Thus, the electronic structure of
semiconductors is characterized by a filled valence band (VB) and an empty conduc-
tion band (CB). When a semiconductor is irradiated by a photon of energy hv that
equals or surpasses the bandgap energy (Eg), an excited electron (e) moves from
the VB to the CB, leaving a hole (h+) behind (Eq. 2.1) [7]. The excited-state CB elec-
trons and the VB holes can (1) recombine and be deactivated, (2) be trapped in meta-
stable surface states, or (3) react with surrounding species.
In the absence of a suitable scavenger or a surface defect state, photogenerated
charge carriers can recombine and be deactivated radiatively (release of light) or non-
radiatively (release of heat) (Eq. 2.2). If a relevant scavenger or a surface defect state is
available to trap the electron or hole, recombination is avoided and e/h+ pairs can
react with electron donors and electron acceptors adsorbed on the surface of the semi-
conductor or within the circumfluent electrical double layer of charged particles,
Metal Oxide-Based Photocatalysis. https://doi.org/10.1016/B978-0-12-811634-0.00002-0
as shown in Fig. 2.1. The VB holes are powerful oxidizers (+1.0 to +3.5 V vs NHE [nor-
mal hydrogen electrode], depending on the semiconductor and pH) and the CB elec-
trons are good reducers (+0.5 to 1.5 V vs NHE) [8]. For TiO2 (the most used metal
oxide in heterogeneous photocatalysis), the redox potential for photogenerated holes
is +2.53 V vs NHE (at pH 7), while the redox potential for CB electrons is 0.52 V [9].
In subsequent reactions, oxygen, as a primary electron acceptor, generates super-
oxide radicals (O2 ) (Eq. 2.3) that undergo further reactions to produce hydroxyl
l
( OH) radicals (Eqs. 2.5, 2.6), which are extremely powerful oxidants [10]. Mean-
while, positive holes oxidize OH or H2O at the semiconductor surface to produce
l l
OH radicals (Eqs. 2.4, 2.8, reprinted from [11]). Afterwards, the OH radicals oxidize
organic compounds (e.g., organic pollutants) resulting in their mineralization and
the formation of CO2, H2O, and eventually simple inorganic compounds containing
heteroatoms (Eq. 2.9, reprinted from [11]).
Semiconductor + hv ! hVB
+
+ e
CB (2.1)
+
hVB + e
CB ! energy (2.2)
e
CB + O2,ad ! O2

(2.3)
Fig. 2.1 Formation of active species at the surface of a semiconductor (photocatalysts) after
light absorption (hv Eg): (i) initiation of an oxidative pathway of electron donors (D) by VB
holes; (ii) initiation of a reductive pathway of electron acceptors (A) by CB electrons.
Based on A.L. Linsebigler, G. Lu, J.T. Yates Jr, Photocatalysis on TiO2 surfaces: principles,
mechanisms, and selected results, Chem. Rev. 95 (1995) 735–758; M.R. Hoffmann, S.T.
Martin, W. Choi, D.W. Bahnemann, Environmental applications of semiconductor
photocatalysis, Chem. Rev. 95 (1995) 69–96; M. Pelaez, N.T. Nolan, S.C. Pillai, M.K. Seery, P.
Falaras, A.G. Kontos, P.S. Dunlop, J.W. Hamilton, J.A. Byrne, K. O’Shea, A review on the
visible light active titanium dioxide photocatalysts for environmental applications, Appl. Catal.
B Environ. 125 (2012) 331–349.
Fundamentals of metal oxide-based photocatalysis 5
O2 + H + ! HO2 (2.4)
2HO2 ! H2 O2 + O2 (2.5)
H2 O2 + e ! OH + OH (2.6)
+
hVB + H2 O ! OH + H + (2.7)
+
hVB + OHads ! OH (2.8)

OH + pollutants !!! H2 O + CO2 (2.9)
If the oxidation potential of the VB holes is not sufficient to form OH radicals, O2 is

l
the dominant oxidant. This might be a major obstacle for the practical application of
VB holes, because O2 has a much lower redox potential than
OH ½E0 ðO2 , 2H + =H2 O2 Þ ¼ 0:91V; E0 (OH , H+/H2O) ¼ 2.31 V vs NHE) [12].
l
The ability of a semiconductor to undergo the transfer of photoinduced electrons to

adsorbed species on its surface is a function of the positions of the CB and VB edges
and the redox potential of the adsorbate. The potential level of the acceptor molecules
or species thermodynamically has to be placed below (i.e., more positive than) the
lower edge of the semiconductor CB. The potential level of the donor has to be located
higher than (i.e., more negative than) the upper edge of the semiconductor VB to be
able to provide an electron to the vacant hole. The correlation between the band-edge
positions of the TiO2 photocatalyst and the relevant redox couples at pH 7 is summa-
rized in Fig. 2.2, while the value of the bandgap and the band-edge positions for the
most common metal oxides are presented in Section 2.2 (Table 2.4.).
For hydrogen production (in a water-splitting process), the bottom level of the CB
should be more negative than the reduction potential of H+/H2 (0 V vs NHE), while the
top level of the VB should be more positive than the oxidation potential of O2/H2O
(1.23 V) for efficient hydrogen and oxygen production from water by photocatalysis,
as shown in Fig. 2.3. Even the band-edge positions of TiO2 are suitable for water pho-
todecomposition, where only TiO2 becomes inactive because of the presence of a
large overpotential for the production of H2 and O2 on the surface of TiO2 [6].
Linsebigler et al. indicated that maintained photodecomposition of water in the
presence of TiO2 is possible under the following experimental conditions [6]:
1. Use of a photoelectrochemical cell with a TiO2 anode and a metal cathode (e.g., Pt) and a
small, externally applied electrical potential (>0.25 V) [6]. In this system, the photoexcita-
tion of TiO2 pumps electrons from its VB into its CB. The electrons then move through the
external circuit to the Pt cathode where H2 is produced, while O2 is formed on the TiO2.
2. Use of TiO2 powder modified by metal nanoparticles (e.g., Pt) for H2 generation and by
metal oxide particles (e.g., RuO2) for O2 production. In this system, irradiation of TiO2
results in the injection of electrons into the Pt particles and holes into the RuO2 particles.
The trapped charges reduce water to hydrogen at the Pt surface and the trapped holes oxidize
water to oxygen at the RuO2 surface due to a significant reduction in the overpotential for H2
and O2 formation by the presence of Pt and RuO2, respectively.
Fig. 2.2 Potentials for various redox processes that occur on the surface of TiO2 at pH 7.
Reproduced with permission from J. Kou, C. Lu, J. Wang, Y. Chen, Z. Xu, R.S. Varma,
Selectivity enhancement in heterogeneous photocatalytic transformations, Chem. Rev. 117
(2017) 1445–1514.
Fig. 2.3 Mechanism of photocatalytic

water splitting for hydrogen
production over semiconductor
particles.
Based on M. Ni, M.K.H.
Leung, D.Y.C. Leung, K. Sumathy,
A review and recent developments in
photocatalytic water-splitting using
TiO2 for hydrogen production,
Renew. Sust. Energy Rev. 11 (2007)
401–425.
3. Introduction into the reaction environment of a sacrificial species, which removes one of the
formed products and results in the shift of the reaction equilibrium toward further water pho-
tosplitting. Thus, it could be predicted that if the sacrificial agent is oxidized by the product
from the reaction with holes (e.g., O2), maintained H2 production will be observed [6].
The efficiency of converting solar energy to hydrogen (i.e., photocatalytic water-
splitting) on a single semiconductor is still limited owing to the following reasons [66]:
1. Quick back reaction between photogenerated e/h+ pairs: CB electrons can react with VB
holes followed by energy release (via radiative or nonradiative decay);
2. Backward reaction: splitting of water molecules into hydrogen and oxygen increases energy,
so the backward reaction, i.e., the recombination of hydrogen and oxygen into water, pro-
ceeds easily;
3. Limited number of metal oxides excited by visible light: The bandgap of most stable semi-
conductors (e.g., TiO2) is greater than 3.2 eV, so only ultraviolet (UV) light can be utilized
for hydrogen production. The solar spectrum reaching ground level contains only about 4%
of UV light and about 50% of visible light. Thus, the inability to absorb light from the visible
region limits the efficiency of solar-driven photocatalysis to produce hydrogen [66].
Titanium dioxide has high photostability, is chemically inert, and has relatively high
oxidation efficiency under UV light (λ < 387 nm), the energy of which exceeds the
TiO2 bandgap (from 3.0 to 3.2 eV for the rutile and anatase forms, respectively). This
makes TiO2 a very popular and commonly used semiconductor in heterogeneous pho-
tocatalysis. However, the application of metal oxide-based photocatalysis on a large
scale requires photocatalysts with high reactivity under visible light (λ > 400 nm) to
be able to use renewable solar energy. The five main approaches to forcing photocatalytic
activity from wide-bandgap semiconductors (e.g., TiO2) under visible light irradiation
are (1) doping, (2) sensitization, (3) charge transfer complex formation, (4) coupling
with a narrow-bandgap semiconductor, and (5) addition of noble metal nanoparticles.
According to the Kisch classification, metal oxide-based photocatalysis has two
reaction modes: direct and indirect [67]. In direct photocatalysis, light excitation
(hv) results in the generation of an e/h+ pair localized at the semiconductor surface,
followed by the two interfacial electron transfer (IFET) reactions with donor and
acceptor species (Figs. 2.1 and 2.3). In indirect photocatalysis, electrons or holes that
appear at the surface of the semiconductor originate from an adsorbed molecule (e.g.,
semiconductor photosensitization).
2.1.1.1 Doped semiconductors

The activity of a doped semiconductor under visible light is due to a new energy level
produced in the bandgap of the semiconductor by the dispersion of dopant atoms (cat-
ions or anions) in the crystal structure of the semiconductor (Fig. 2.4). Transition
metals, rare earth metals, noble metals, and poor metals can be used for cation doping.
Doping with transition metals tunes the electronic structure and shifts the light
absorbed from UV to visible light, thus improving the photocatalytic activity of
wide-bandgap semiconductors. The observed redshift is caused by the charge transfer
between the d electrons and the CB or the VB of the semiconductor. The transition
metal creates a new electron state inside the electronic structure of the wide-bandgap
Fig. 2.4 Mechanism of visible

light-induced excitation through the
metal- or nonmetal-doped wide-
bandgap semiconductor.
semiconductor by capturing the excited electrons from the VB of the semiconductor

and preventing the recombination of charge carriers [63]. As metal ions are incorpo-
rated into the TiO2 lattice, impurity energy levels are formed in the bandgap of TiO2,
as indicated by Eqs. 2.10, 2.11 [66]:
Mn + + hv ! Mðn + 1Þ + + e
CB (2.10)
Mn + + hv ! Mðn1Þ + + hVB
+
(2.11)
where M and Mn+ represent metal and metal ion dopant, respectively. The energy level of
Mn+/M(n1)+ should be less negative than that of the CB edge of TiO2, while the energy
level of Mn+/M(n+1)+ should be less positive than that of the VB edge of TiO2 [66].
Depending on the redox energy state of the doping transition metal, the substitution of
metal ions into the TiO2 (or other metal oxide) introduces an intraband state close to the
CB or VB edge, inducing visible light absorption at subbandgap energies [68]. The addi-
tional benefit of doping with transition metal is the enhanced trapping of electrons, which
inhibits the recombination of electrons and holes during illumination [6]. However, the
type of transition metal, its content, and the microstructural characteristics of the
metal oxide are the main factors which affect the effectiveness of the photodegradation
of miscellaneous compounds induced by visible light irradiation [63,69,70].
The next popular approach for changing the optical response of the semiconductor to
visible light is to dope with anionic nonmetals, such as N, C, S, B, P, and I [71]. Com-
pared to doping with cations, the role of nonmetallic anions as recombination centers
might be minimized. For nonmetal-doped TiO2, the impurity states are near the VB
edge but do not act as charge carriers. Both theoretical [72] and experimental [73] stud-
ies revealed that for N-doped TiO2, the N 2p localized states were just above the top of
the O 2p VB.
However, the oxidation power and mobility of photogenerated holes in the elec-
tronic state of isolated N are lower than those in the VB of TiO2. Thus, in the case
of N-doped TiO2, superoxide radicals are responsible for organic compound decom-
position rather than OH radicals [74]. Doping by S, C, and P also induces mid-bandgap
levels leading to visible light absorption. Doping with F does not shift the TiO2
bandgap but it does enhance surface acidity and cause formation of reduced Ti3+ ions
owing to the charge compensation between F and Ti4+.
2.1.1.2 Semiconductor photosensitization

In semiconductor photosensitization, photoexcited electrons or holes appear in the CB
or the VB of the semiconductor, respectively, from the excited state of organic mol-
ecules adsorbed on the surface of the semiconductor. This type of photoinduced elec-
tron transfer is considered a weak-type interaction between a semiconductor band and
the surface molecule and is known as the Sakata-Hiramoto-Hashimoto (SHH) mech-
anism [75] (Fig. 2.5). According to the SHH model, photosensitization results from
photoinduced electron transfer and depends on the type of semiconductor [76]. In
n-type semiconductors, electrons are injected into the CB, with possible contribution
of the empty surface state (Fig. 2.5A). When the energy of the highest occupied molec-
ular orbital (HOMO) of the photosensitizer is sufficiently low, hole injection into the
VB of a p-type semiconductor is observed (Fig. 2.5B).
The indirect photosensitization process, which involves excitation of the adsorbed
dye followed by rapid electron injection from the excited state of the dye into the CB
of the semiconductor, is privileged for covalently bound photosensitizer due to the fact
Fig. 2.5 Energy diagrams showing indirect photosensitization of (A) n- and (B) p-type
semiconductors according to the SHH mechanism: (A) under photoexcitation of an adsorbed
dye, electrons are transferred from the excited dye to the CB of the semiconductor; (B) under
photoexcitation of the adsorbed dye, holes are injected from the excited dye to the VB of the
semiconductor.
Based on T. Sakata, K. Hashimoto, M. Hiramoto, New aspects of electron transfer on
semiconductor surface: dye-sensitization system, J. Phys. Chem. 94 (1990) 3040–3045; W.
Macyk, K. Szaciłowski, G. Stochel, M. Buchalska, J. Kuncewicz, P. Łabuz, Titanium(IV)
complexes as direct TiO2 photosensitizers, Coord. Chem. Rev. 254 (2010) 2687–2701.
that it allows only for unsteady interaction between chromophore and bands or surface
states of the semiconductor. Thus, the excited dye molecules transfer electrons into the
CB of the semiconductor (e.g., TiO2), while the dye itself is converted into its cationic
radical. The semiconductor acts only as a mediator for transferring electrons from the
photosensitizer to the substrate on the semiconductor surface, which acts as an elec-
tron acceptor, and the VB of the semiconductor stays uninfluenced. In this action, the
energy of the lowest unoccupied molecular orbital (LUMO) of the dye molecules is
supposed to be more negative than that of the CB of the semiconductor. The injected
electrons move quickly to the surface of the semiconductor where they are scavenged
by O2 to form O2 and the hydrogen peroxide radical OOH. These reactive species
l
l
can also be disproportionate to yield the hydroxyl radical OH (Fig. 2.6A). In addition
to the above-mentioned species, 1O2 can also be formed under some reaction condi-
tions. Oxygen has two singlet excited states above the triplet ground states. This makes
3
O2 an efficient quencher for almost all other excited states. 1O2 is produced by
quenching the excited state of the photosensitizer with 3O2, as summarized in
Eqs. 2.12, 2.13, where S refers to the photosensitizer.
3
S ∗ + 3 O2 ! 1 S + 1 O2 (2.12)
S∗ + 3 O2 ! S + + O2 (2.13)
The subsequent radical chain reaction leads to the degradation of the dye. The time for
electron injection between the semiconductor and the adsorbate depends on the nature
of the sensitizer, the semiconductor, and their interaction [11]. Some frequently used
dyes and their absorption wavelength maxima are listed in Table 2.1.
Fig. 2.6 Indirect photosensitization: (A) formation of oxygen active species at the surface
of the photosensitized semiconductor; (B) formation of hydrogen at the surface of the
photosensitized semiconductor (dye-mediated water splitting).
Based on S.G. Kumar, L.G. Devi, Review on modified TiO2 photocatalysis under
UV/visible light: selected results and related mechanisms on interfacial charge carrier
transfer dynamics, J. Phys. Chem. A 115 (2011) 13211–13241.
Table 2.1 Dyes used for photocatalysis
Water splitting Pollutant degradation Solar cells
λmax λmax λmax

Dye (nm) Class Dye (nm) Class Dye (nm) Class
Thionine 596 Thiazines Chrysoidine R 455 Azo Cumarine 343 480 Cumarines
(TH+)
Toluidine Blue 630 Thiazines Acid Red 29 510 Chromotrope Hemicyanine, HC-1 535 Hemicyanine
(Tb +) 2R
Methylene 665 Thiazines Acid Red 14 515 Azo Thienylflourene 538 Fluorene
Blue (MB)
New 650 Thiazines Reactive Red 22 538 Azo 4-N,N- 406 N,N-
methylene Dimethylamine-benzaldehyde Diametylamines
Blue
Azure A 635 Thiazines Acid Red 27 521 Azo Phenothiazine, Z4 470 Thiazines
Azure B 647 Thiazines Reactive Red 198 518 Azo Indoline, Ind 1 491 Indolynes
Azure C 620 Thiazines Acid Red 2 430 Azo N,N- 450 N,N-
Dimethylamine-cyanoacetic Diametylamines
acid
Phenosafranin 520 Phenazines Acid Red 18 507 Azo Porphyrin 400–650 Porphyrines
(PSF)
Safranin-O 520 Phenazines Acid Red 176 519 Chromotrope Zinc carboxyphtholocyanine 680 Zn-complex
(Saf-O/SO) 2R
Safranin-T 520 Phenazines Reactive Red 15 500 Azo N3 380 Ru-complex
(Saf-T/ST)
Neutral Red 534 Phenazines Basic Blue 41 600 Azo Black Dye 605 Ru-complex
(NR)
Fluorescein 490 Xanthenes Acid Yellow 17 400 Azo N719 540 Ru-complex
Continued
Table 2.1 Continued
Water splitting Pollutant degradation Solar cells
λmax λmax λmax

Dye (nm) Class Dye (nm) Class Dye (nm) Class
Erythrosin 530 Xanthenes Reactive Yellow 426 Azo C101 547 Ru-complex
17
Erythrosin B 525 Xanthenes Acid Yellow 23 455 Azo Rhododendron 540 Natural
(flowers)
Rhodamin 551 Xanthenes Reactive Yellow 410 Azo Violet 546 Natural
B (Rh.B) 14 (flowers)
Rose Bengal 550 Xanthenes Reactive Yellow 419 Azo Tangerine peel 446 Natural (fruit)
145
Pyronine 545 Xanthenes Acid Orange 10 480 Azo Shiso 440 Natural (leaves)
Y (PY)
Eosin 514 Xanthenes Acid Orange 7 485 Azo Bixa arellana L. 474 Natural (seeds)
Rhodamin 6G 524 Xanthenes Acid Orange 8 490 Azo
Acridine 492 Acridines Acid Orange 12 488 Azo
Orange (AO)
Proflavin (PF) 444 Acridines Reactive Orange 496 Azo
16
Acridine 442 Acridines Direct Yellow 12 395 Azo
Yellow (AY)
Fusion 545 Triphenyl Direct Blue 160 570 Azo
methane
deriv.
Crystal Violet 578 Triphenyl Direct Red 80 580 Azo
methane
deriv.
Malachite 625 Triphenyl Congo Red 524 Azo
Green methane
deriv.
Methyl Violet 580 Triphenyl Acid Brown 14 465 Azo
methane
deriv.
Reactive Black 5 597 Azo
Acid Black 1 618 Azo
Acid Blue 80 626 Anthraquinone
Acid Blue 25 600 Anthraquinone
Reactive Blue 4 596 Anthraquinone
Reactive Blue 19 592 Anthraquinone
Alizarin Red 342 Anthraquinone
Basic Violet 3 550 Triarylmethane
Acid Blue 7 625 Triarylmethane
Gentian Violet 536 Triarylmethane
Acid Yellow 73 490 Xanthenes
Rhodamine-B 550 Xanthenes
Sulforhodamine B 565 Xanthenes
Modified from M. Ni, M.K.H. Leung, D.Y.C. Leung, K. Sumathy, A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production, Renew. Sust. Energy
Rev. 11 (2007) 401–425; A.R. Khataee, M.B. Kasiri, Photocatalytic degradation of organic dyes in the presence of nanostructured titanium dioxide: Influence of the chemical structure of dyes, J.
Mol. Catal. A Chem. 328 (2010) 8–26; N.A. Ludin, A.M. Al-Alwani Mahmoud, A. Bakar Mohamad, A.A.H. Kadhum, K. Sopian, N.S. Abdul Karim, Review on the development of natural dye
photosensitizer for dye-sensitized solar cells, Renew. Sust. Energy Rev. 31 (2014) 386–396.
2.1.1.3 Charge transfer interaction

Another way to modify a wide-bandgap semiconductor (such as TiO2) for visible light
absorption is the formation of a charge transfer (CT) complex between the semicon-
ductor and the surface adsorbate, neither of which absorbs visible light [77–81]. The
mechanism of CT complex-mediated visible light excitation is different from that of
common dye photosensitization. In CT sensitization, the electron is photoexcited
directly from the ground-state adsorbate to the CB of the semiconductor, without
the involvement of the excited state of the adsorbate.
The strong interaction between the semiconductor CB and a surface molecule can
be represented by the Creutz-Brunschwig-Sutin model [82–84]. For strong electronic
coupling, the interaction between a ligand and the surface of the semiconductor results
in the formation of a surface coordination species (Fig. 2.7A and B). New energy
levels are formed with the appropriate arrangement of molecular orbitals. For an
n-type semiconductor (Fig. 2.7A), a bonding orbital is created via interaction of
the HOMO level of the surface ligand with the empty surface state. Typically, the
resulting surface state, with HOMO and LUMO characteristics, is situated at the sur-
face ligand (electron donor) and constitutes a part of the CB. In this case, excitation of
the surface complex leads to optical electron transfer from the surface molecule to the
CB. The opposite occurs when the p-type semiconductor interacts with the electron
acceptor (Fig. 2.7B).
The simple surface complexes of TiO2 have three basic structures: (1) monodentate
structure with the organic ligands engaging one coordination site of TiO2, (2)
Fig. 2.7 Energy diagrams showing direct photosensitization of (A) n- and (B) p-type
semiconductors according to the Creutz-Brunschwig-Sutin model (LMCT: ligand-to-metal
charge transfer; MLCT: metal-to-ligand charge transfer; Eg: bandgap energy; EF: Fermi level).
Based on T. Sakata, K. Hashimoto, M. Hiramoto, New aspects of electron transfer on
semiconductor surface: dye-sensitization system, J. Phys. Chem. 94 (1990) 3040–3045;
W. Macyk, K. Szaciłowski, G. Stochel, M. Buchalska, J. Kuncewicz, P. Łabuz,
Titanium(IV) complexes as direct TiO2 photosensitizers, Coord. Chem. Rev. 254 (2010)
2687–2701.
bidentate chelating structure with the ligand occupying two coordination sites, and (3)
bidentate bridging structure composed of a chelating ligand binding two neighboring
Ti centers. The bidentate surface complexes form only if the ligand owns at least two
donor groups or one group containing two donor atoms. The opportunity for bidentate
complex formation does not preclude complexation via the monodentate mode [76].
The following substances are able to form a CT complex with the surface of TiO2:
catechol [85], 8-hydroxyorthoquinoline [86], 1,1-binaphthalene-2,2-diol [87],
chlorophenol [88], 2,4,5-trichlorophenol [89], and calixarene [90].
2.1.1.4 Composite semiconductors

Visible light can be utilized by coupling a wide-bandgap semiconductor with a
narrow-bandgap semiconductor. In this system, visible light photons are absorbed by
the narrow-bandgap semiconductor (Eg < 3 eV) resulting in the formation of e/h+
pairs. If the CB level of the narrow-bandgap semiconductor is more negative than
that of the wide-bandgap semiconductor, electrons from the narrow-bandgap semi-
conductor are injected into the wide-bandgap semiconductor (Fig. 2.8).
Fig. 2.8 Mechanism of visible light-induced excitation through the heterojunction between
wide- and narrow-bandgap semiconductors.
Based on S.G. Kumar, L.G. Devi, Review on modified TiO2 photocatalysis under UV/visible
light: selected results and related mechanisms on interfacial charge carrier transfer
dynamics, J. Phys. Chem. A 115 (2011) 13211–13241; K. Rajeshwar, N.R. de Tacconi, C.R.
Chenthamarakshan, Semiconductor-based composite materials: preparation, properties,
and performance, Chem. Mater. 13 (2001) 2765–2782.
The energy gap between the corresponding band levels guarantees the transport of
charge carriers from one particle to its neighbor and favors the separation between the
e/h+ pairs. The photogenerated electrons transferred to the CB of the wide-bandgap
semiconductor are involved in the formation of O2 and subsequently H2O2
and HO2 . If the oxidation potential of the photogenerated holes is greater than
+2.27 V, then OH radicals are formed via HO or H2O oxidation. However, in most
l
cases, OH is not generated by visible light-responsive semiconductors because of an
inadequate VB position.
Visible light-responsive photocatalysts have been successfully obtained by
combining TiO2 with Ag2O [13,91], Cu2O [32], Fe2O3 [92], ZnO with Fe2O3 [36],
and Ag2O [93].
2.1.1.5 Semiconductor modified by noble metal nanoparticles

In a hybrid nanostructure consisting of plasmonic metal nanoparticles and a wide-
bandgap semiconductor, the incident visible light excites the localized surface
plasmon resonance (LSPR) in the metal nanocrystals. The transfer of plasmonic
energy from the plasmonic metal nanoparticles to the semiconductor results in the
appearance of e/h+ pairs in the semiconductor. The energy concentrated in the local-
ized plasmonic oscillations is transferred to the semiconductor via three main mech-
anisms: (1) direct electron transfer (DET), (2) local electromagnetic field
enhancement (LEMF) of the semiconductor charge separation process, and (3) reso-
nant energy transfer (RET) [94]. These mechanisms, and the role of noble metal
nanoparticles in heterogeneous photocatalysis, are discussed in Section 2.3.
In the DET mechanism, electrons are transferred from the plasmonic metal to
the CB of the semiconductor if the metal particle is connected with the semicon-
ductor surface. The alignment of the band-edge positions of the semiconductor and
the Fermi level of the plasmonic metal influences the DET mechanism. Electrons
from the metal can be injected into the semiconductor at energies below Eg if the
electronic energy levels match. DET occurs when the LSPR in the nanoparticles is
excited by visible light, followed by decoherence of LSPR, leaving a number of
hot electrons for injection into the semiconductor matrix (Fig. 2.9A). Hot electrons
are electrons whose distribution can be fundamentally described by the Fermi function,
but with an elevated effective temperature [95]. An efficient way to catch hot electrons
is to form a Schottky barrier with an appropriate semiconductor. The efficiency of the
transfer of hot electrons, with energy higher than the Schottky barrier energy, into the
semiconductor depends on their energy (Fig. 2.9B). Generation of plasmonic hot elec-
trons has been confirmed for TiO2 combined with Au, Ag, or Pt nanoparticles [96–98],
ZnO with added Au nanocrystals, Au nanoparticles seated on CeO2, Au on WO3, and
Al2O3 with added Au and Ag nanoparticles [99].
Similar to the other above-mentioned mechanisms, the injected electrons move
quickly to the surface of the semiconductor, where they are trapped by O2 to form
O2 and OOH, and if they are disproportionate, OH is obtained (Fig. 2.9A).
l l
Fig. 2.9 Schematic illustration of (A) mechanism of visible light-induced excitation of

plasmonic nanoparticles at the surface of a wide-bandgap semiconductor and (B) energy band
diagram of Schottky barrier formed at metal/n-type semiconductors interface.
Based on S. Mukherjee, F. Libisch, N. Large, O. Neumann, L.V. Brown, J. Cheng, J.B.
Lassiter, E.A. Carter, P. Nordlander, N.J. Halas, Hot electrons do the impossible: plasmon-
induced dissociation of H2 on Au, Nano Let. 13 (2013) 240–247; A. Bumajdad, M. Madkour,
Understanding the superior photocatalytic activity of noble metals modified titania under UV
and visible light irradiation, Phys. Chem. Chem. Phys. 16 (2014) 7146–7158.
2.1.2 Kinetics of photocatalysis [100]

The photodegradation rate of a chemical compound on the surface of a metal oxide-
based semiconductor follows the Langmuir-Hinshelwood (L-H) mechanism. In accor-
dance with the L-H model, given by Eq. (2.14), the rate of photocatalytic reaction (r) is
proportional to the fraction of surface coverage by organic substrate (θx), where: kr is
the reaction rate constant, C is the concentration of organic species and K is the Lang-
muir adsorption constant [101]:
dC kr KC
r¼ ¼ kr θ x ¼ (2.14)
dt 1 + KC
The appropriateness of Eq. (2.14) relies upon the following presumptions: (1) the reac-
tion system is in dynamic equilibrium; (2) the reaction occurs on the surface of photo-
catalysts; and (3) there are no limits for the competition between byproducts and
reactive oxygen species for the metal oxide active surface sites [101].
Recently, Mills et al. [102] reviewed ten proposed reaction mechanisms. The reac-
tion processes that support the reaction mechanisms, described below, are given in
Table 2.2. Table 2.3 presents some of the common assumptions and their associated
rate equations.
Table 2.2 Key reaction processes

No. Process Ratea
Core processes
Generation
G TiO2 + hν ! h+ + e k0ρ
Recombination
B1 h+ + e ! heat kr[h +][e]

B2 OH =hs+ + e ! H2 O=OH = > O2 s + heat kr1 OH =hs+ ½e
Trapping

T1 h + + H2 O=OH = > O2 s ! OH =hs+ kT1[h+]
Interfacial electron transfer
R1 h+ + P ! products kP[h+][P]

R2 OH =hs+ + P ! products kP OH =hs+ ½P
R3 e + O2 ! O2 kO2 ½e ½O2
Other processes
T2 OH l ! h+ + (H2O/OH/O2)s k_T1[OH l]
R4 h+ + P ! P+ kP1[h+][P]
R5 h+ + P+ ! products kP2[h+][P+]
B3 e + P+ ! P kb[e][P+]
T3 h+ + T ! T+ kT3[h+]
T4 e + T ! T kT4[e]

T5 hs+ + T∗ ! T∗ + kT5 hs+
Adsorption
L1 Pbulk + S Ð P [P] ¼ [S]OKL[P]sol/(1 + KL[P]sol)
L1 Pbulk + S ! P kads[P]sol[S]
L2 P! Pbulk + S Kdes[P]
a
Unless stated otherwise, all concentrations are surface concentrations and are in units of mol m2 and all rates are
in units of mol m2 s1. Bulk solution concentrations are identified by the subscript “sol,” e.g., [P]sol, in the
Langmuir equation. Thus, it is often assumed that KL[P]sol ≪ 1, so [P] ¼ [S]oKL[P]sol, i.e., [P] ∝ [P]sol. If P is
nonspecifically adsorbed, then [P] ∝ [P]sol for all values of [P]sol.
Reproduced with permission from A. Mills, C. O’Rourke, K. Moore, Powder semiconductor photocatalysis in
aqueous solution: an overview of kinetics-based reaction mechanisms, J. Photochem. Photobiol. A Chem. 310
(2015) 66–105.
2.1.3 Generation and separation of charge carriers

The recombination rate of photoexcited e/h+ pairs straightforwardly affects the reac-
tion rate of any photochemical process that appears on the surface of the metal oxide.
Thus, the recombination of photoexcited e/h+ pairs should be suppressed for the
charge transfer process on the semiconductor surface to be efficient. Recombination
can be suppressed by trapping the photogenerated electrons, the photogenerated holes,
or both, thus extending the lifetime of the separated electrons and holes to more than a
fraction of a nanosecond [110].
Table 2.3 Kinetics model and associated rate equations
Rate Processes Type Ref.
X1 X2 ρθ ½P X2 ¼ (kp/kT1) but at low ρ, ν ¼ 1 and G, B1, T1, Langmuir-Ollis [103]

r¼ X1 ¼ k0, and at high ρ, ν ¼ 0.5 and
1 + X2 ½P R2, T2 Langmuir (case
X1 ¼ kT1(k0/kr)1/2 III; ER
mechanism)
X1 X2 ½Psol X1 ¼ (kT1k0/kT3); X2 ¼ (kT4kp/kr1k0) G, B2, T1, Emeline [104]
r¼
1 + X2 ½Psol =ρ [S]0KL R2, T3, T4, (Langmuir
L1 mechanism)
X1 X2 ρ½Psol X1 ¼ (k0[S]0kp/kT1) and X2 ¼ KL, and G, T1, R1, Salvador (Direct [105]
r¼
1 + X2 ½Psol assuming kp[S]0/kT1 ≪ 1 L1 Transfer, DT
mechanism)
X1 ρθ ½Psol X1 ¼ αKL[S]0; θ ¼ constant, (G, B1, T3, Ollis disrupted [106]
r ¼ αρθ ½P ¼
(where: 0.5 θ 1; X2 ¼ α/kdes; R1) + L1, adsorption model
1 + X2 ρθ + X3 ½Psol
X3 ¼ KL0 L1’, L2’ (nonequilibrated
! adsorption)
X1 ¼ 2kpkO2[O2]/kr and X2 ¼ k0/X1 G, B1, R1, Quadratic Gerischer [107]
X2 ρ 1=2
r ¼ ½PX1 1+ 1 c R3 (case: α)
½P
!
X2 ρ 1=2 X1 ¼ kpkO2[O2]/2kr1 and X2 ¼ 2k0/X1 G, B2, T1, Salvador (indirect [105]
r ¼ ½PX1 1+ 1 c R2, R3 transfer, IT
½P
mechanism)

X2 ½P 2 + ð4X1 ½PÞ= 1 + ð1 + 8X1 ½PÞ1=2 X1 ¼ δγ=βθ ¼ kP1 kb =ðkO2 ½O2 kP2 Þ G, B2, T1, Marin (quadratic [108]
r¼ X2 ¼ δβ=α ¼ ðkP1 kO2 ½O2 =kr1 ; R3, R4, R5, with back reaction)
2 1 + ð1 + 8X1 ½PÞ1=2 X3 ¼ k0 B3
0 0 0 111=2 1
B B B 4 1 + ð1 + 8X1 ½PÞ1=2 X3 ρ CC C
@1 + @1 + @ 2 AA Ac
X2 ½P 2 + ð4X1 ½PÞ= 1 + ð1 + 8X1 ½PÞ1=2
Continued
Another random document with
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a girl in a pale blue dress stooping to pick grasses. She was hatless
and golden-haired, and in one hand she bore a bunch of something
purple, some kind of long grass whose name he did not know. He
watched her at first exactly as he might have watched some perfect
theatrical spectacle, with just that kind of detached admiration and
rich impersonal enchantment. The pose of her as she stooped, the
flaunt of the grasses in her hand, the movement of her head as she
tossed back her laughing hair, the winding yellow path she trampled
across the meadows: all these things he watched and strangely
admired.
He lay watching for a long while, still without guessing who she
was, till the sun went in behind a cloud and he felt drowsy. He closed
his eyes and leaned back cushioned amongst the turf.
He woke with a sensation of intense chilliness; the sun had gone

in and even its approximate position in the sky could not be
determined because of the heaviness of the clouds. He looked at his
watch; it was ten minutes past one; he must have slept for over an
hour.
The sky was almost the most sinister thing he ever saw. In the
east a faint deathly pallor hung over the horizon, but the piling clouds
from the west were pushing it over the edge of the world. That faint
pallor dissolved across the sky into the greyness deepening into a
western horizon of pitch black. Here and there this was shot through
with streaks of dull and sombre flame as if each of the hills in that
dark land was a sulky volcano. It was cold, and yet the wind that
blew in from the gloom was strangely oppressive; the grasses bent
low as if weighed down by its passing. Deep in the cleft by
Parminters the river gleamed like a writhing venomous snake, the
sky giving it the dull shimmer of pewter. To descend across those
dark meadows to the coils of the stream seemed somehow an
adventure of curious and inscrutable horror. Speed stood up and
looked far into the valley. The whole scene seemed to him unnatural;
the darkness was weird and baffling; the clouds were the grim
harbingers of a thunderstorm. And to him there seemed momentarily
a strangeness in the aspect of everything; something deep and
fearsome, imminent, perhaps, with tragedy. He felt within him a
sombre presaging excitement.
It began to rain, quietly at first, then faster, faster and at last
overwhelmingly. He had brought no mackintosh. He stuffed the
essays into his coat pocket, swung his bicycle off the turf where he
had laid it, and began to run down the hill with it. His aim was to get
to the village and shelter somewhere till the storm was over. Halfway
down he paused to put up his coat-collar, and there, looking across
the meadows, he saw again that girl in the pale-blue dress. He was
nearer to her now and recognised her immediately. She was dressed
in a loose-fitting and rather dilapidated frock which the downpour of
rain had already made to cling to the soft curves of her body; round
her throat, tightly twined, was a striped scarf which Speed, quick to
like or to dislike what he saw, decided was absolutely and garishly
ugly. And yet immediately he felt a swift tightening of his affection for
her, for Millstead was like that, full of stark uglinesses that were
beautiful by their intimacy.... She saw him and stopped. Details of
her at that moment encumbered his memory ever afterwards. She
was about twenty yards from him and he could see a most
tremendous wrist-watch that she wore—an ordinary pocket watch
clamped on to a strap. And from the outside pocket of her dress
there protruded the chromatic cover of a threepenny novelette. (Had
she read it? Was she going to read it? Did she like it? he wondered
swiftly.) She still carried that bunch of grasses, now rather soiled and
bedraggled, tightly in her hand. He imagined, in the curiously vivid
way that was so easy to him, the damp feel of her palm; the heat and
perspiration of it: somehow this again, a symbol of secret and bodily
intimacy, renewed in him that sudden kindling affection for her.
He called out to her: "Miss Ervine!"
She answered, a little shyly: "Oh, how are you, Mr. Speed?"
"Rather wet just at present," he replied, striding over the tufts of
thick grass towards her. "And you appear to be even wetter than I
am. I'm afraid we're in for a severe thunderstorm."
"Oh well, I don't mind thunderstorms."
"You ought to mind getting wet." He paused, uncertain what to say
next. Then instinct made him suddenly begin to talk to her as he
might have done to a small child. "My dear young lady, you don't
suppose I'm going to leave you here to get drenched to the skin, do
you?"
She shrugged her shoulders and said: "I don't know what you're
going to do."
"Have you had anything to eat?"
"I don't want anything."
"Well, I suggest that we get into the village as quick as we can
and stay there till the rain stops. I was also going to suggest that we
spent the time in having lunch, but as you don't want anything, we
needn't."
"But I don't want to wait in the village, Mr. Speed. I was just going
to start for home when it came on to rain."
Speed said: "Very well, if you want to get home you must let me
take you. You're not going to walk home through a thunderstorm.
We'll have a cab or something."
"And do you really think you'll get a cab in Parminters?"
He answered: "I always have a good try to get anything I want to."
For all her protests she came with him down the meadow and out
into the sodden lane. As they passed the gate the first flash of
lightning lit up the sky, followed five seconds after by a crash of
thunder.
"There!" he exclaimed triumphantly, as if the thunder and lightning
somehow strengthened his position with her: "You wouldn't like to
walk to Millstead through that, would you?"
She shrugged her shoulders and looked at him as if she hated his
interference yet found it irresistible.
VI
It was altogether by good luck that he did get a cab in the village;
a Millstead cab had brought some people into Parminters and was
just setting back empty on the return journey when Speed met it in
the narrow lane. Once again, this time as he opened the cab-door
and handed her inside, he gave her that look of triumph, though he
was well aware of the luck that he had had. Inside on the black
leather cushions he placed in a conspicuously central position his
hat and his bundle of essays, and, himself occupying one corner,
invited her to take the other. All the time the driver was bustling
round lifting the bicycle on to the roof and tying it securely down,
Speed sat in his corner, damp to the skin, watching her and
remembering that Miss Harrington had told him that she hated men.
All the way during that three-mile ride back to Millstead, with the
swishing of the rain and the occasional thunder and the steady jog-
trot of the horse's hoofs mingling together in a memorable medley of
sound, Speed sat snugly in his corner, watching and wondering.
Not much conversation passed between them. When they were
nearing Millstead, Speed said: "The other day as I passed near your
drawing-room window I heard somebody playing the Chopin waltzes.
Was it you?"
"It might have been."
He continued after a pause: "I see there's a Chopin recital
advertised in the town for next Monday week. Zobieski, the Polish
pianist, is coming up. Would you care to come with me to it?"
It was very daring of him to say that, and he knew it. She coloured
to the roots of her wet-gold hair, and replied, after a silence:
"Monday, though, isn't it?—I'm afraid I couldn't manage it. I always
see Clare on Mondays."
He answered instantly: "Bring Clare as well then."
"I—I don't think Clare would be interested," she replied, a little
confused. She added, as if trying to make up for having rejected his
offer rather rudely: "Clare and I don't get many chances of seeing
each other. Only Mondays and Wednesday afternoons."
"But I see you with her almost every day."
"Yes, but only for a few minutes. Mondays are the only evenings
that we have wholly to ourselves."
He thought, but did not dare to say: And is it absolutely necessary
that you must have those evenings wholly to yourselves?
He said thoughtfully: "I see."
He said nothing further until the cab drew up outside the main
gate of Millstead School. He was going to tell the driver to proceed
inside as far as the porch of the Head's house, but she said she
would prefer to get out there and walk across the lawns. He smiled
and helped her out. As he looked inside the cab again to see if he
had left any papers behind he saw that the gaudily-coloured
novelette had fallen out of her pocket and on to the floor. He picked it
up and handed it to her. "You dropped this," he said merely. She
stared at him for several seconds and then took it almost sulkily.
"I suppose I can read what I like, anyway," she exclaimed, in a
sudden hot torrent of indignation.
He smiled, completely astonished, yet managed to say, blandly:
"I'm sure I never dreamt of suggesting otherwise."
He could see then from her eyes, half-filling with tears of
humiliation, that she realised that she had needlessly made a fool of
herself.
"Please—please—don't come with me any further," she said,
awkwardly. "And thanks—thanks—very much—for—for bringing me
back."
He smiled again and raised his hat as she darted away across the
wet lawns. Then, after paying the driver, he walked straightway into
the school and down into the prefects' bathroom, where he turned on
the scalding hot water with jubilant anticipation.
VII
The immediate result of the incident was an invitation to dine at

the Head's a few days later. "It was very—um, yes—thoughtful and
considerate of you, Mr. Speed," said the Head, mumblingly. "My
daughter—a heedless child—just like her to omit the—um—
precaution of taking some—um, yes—protection against any
possible change in the weather."
"I was rather in the same boat myself, sir," said Speed, laughing.
"The thunderstorm was quite unexpected."
"Um yes, quite so. Quite so." The Head paused and added, with
apparent inconsequence: "My daughter is quite a child, Mr. Speed—
loves to gather flowers—um—botany, you know, and—um—so
forth."
Speed said: "Yes, I have noticed it."
Dinner at the Head's house was less formal than on the previous
occasion. It was a Monday evening and Clare Harrington was there.
Afterwards in the drawing-room Speed played a few Chopin studies
and Mazurkas. He did not attempt to get into separate conversation
with Miss Ervine; he chatted amiably with the Head while the two
girls gossiped by themselves. And at ten o'clock, pleading work to do
before bed, he arose to go, leaving the girls to make their own
arrangements. Miss Ervine said good-bye to him with a shyness in
which he thought he detected a touch of wistfulness.
When he got up to his own room he thought about her for a long
while. He tried to settle down to an hour or so of marking books, but
found it impossible. In the end he went downstairs and let himself
outside into the school grounds by his own private key. It was a
glorious night of starshine, and all the roofs were pale with the
brightness of it. Wafts of perfume from the flowers and shrubbery of
the Head's garden accosted him gently as he turned the corner by
the chapel and into the winding tree-hidden path that circumvented
the entire grounds of Millstead. It was on such a night that his heart's
core was always touched; for it seemed to him that then the strange
spirit of the place was most alive, and that it came everywhere to
meet him with open arms, drenching all his life in wild and
unspeakable loveliness. Oh, how happy he was, and how hard it was
to make others realise his happiness! In the Common-Room his
happiness had become proverbial, and even amongst the boys,
always quicker to notice unhappy than happy looks, his beaming
smile and firm, kindling enthusiasm had earned him the nickname of
"Smiler."
He sat down for a moment on the lowest tier of the pavilion seats,
those seats where generations of Millsteadians had hurriedly
prepared themselves for the fray of school and house matches. Now
the spot was splendidly silent, with the cricket-pitch looming away
mistily in front, and far behind, over the tips of the high trees, the
winking lights of the still noisy dormitories. He watched a bat flitting
haphazardly about the pillars of the pavilion stand. He could see,
very faintly in the paleness, the score of that afternoon's match
displayed on the indicator. Old Millstead parish bells, far away in the
town, commenced the chiming of eleven.
He felt then, as he had never felt before he came to Millstead, that
the world was full, brimming full, of wonderful majestic beauty, and
that now, as the scented air swirled round him in slow magnificent
eddies, it was searching for something, searching with passionate
and infinite desire for something that eluded it always. He could not
understand or analyse all that he felt, but sometimes lately a deep
shaft of ultimate feeling would seem to grip him round the body and
send the tears swimming into his eyes, as if for one glorious moment
he had seen and heard something of another world. It came
suddenly to him now, as he sat on the pavilion seats with the silver
starshine above him and the air full of the smells of earth and
flowers; it seemed to him that something mighty must be abroad in
the world, that all this tremulous loveliness could not live without a
meaning, that he was on the verge of some strange and magic
revelation.
Clear as bells on the silent air came the sound of girls' voices. He
heard a rich, tolling "Good night, Clare!" Then silence again, silence
in which he seemed to know more things than he had ever known
before.
CHAPTER THREE
One afternoon he called at Harrington's, in the High Street, to buy

a book. It was a tiny low-roofed shop, the only one of its kind in
Millstead, and with the sale of books it combined that of newspapers,
stationery, pictures and fancy goods. It was always dark and
shadowy, yet, unlike the Head's study at the school, this gloom
possessed a cheerful soothing quality that made the shop a pleasant
haven of refuge when the pavements outside were dazzling and sun-
scorched. It was on such an afternoon that Speed visited the shop
for the first time. Usually he had no occasion to, for, though he dealt
with Harrington's, an errand-boy visited the school every morning to
take orders and saved him the trouble of a walk into the village. This
afternoon, however, he recollected a text-book that he wanted and
had forgotten to order; besides, the heat of the mid-afternoon
tempted him to seek shelter in one or other of the tranquil diamond-
windowed shops whose sun-blinds sprawled unevenly along the
street. It was the hottest day of the term, so far. A huge thermometer
outside Harrington's gave the shade temperature as a little over
seventy-nine; all the roadway was bubbling with little gouts of soft
tar. The innumerable dogs of Millstead, quarrelsome by nature, had
called an armistice on account of the heat, and lay languidly across
shady sections of the pavement. Speed, tanned by a week of
successive hot days, with a Panama pushed down over his forehead
to shield his eyes from dazzle, pushed open the small door and
entered the cool cavern of the shop.
His eyes, unaccustomed to the gloom, were blind for a moment,
but he heard movement of some kind behind the counter. "I want an
atlas of the British Isles," he said, feeling his way across the shop. "A
school atlas, I mean. Cheap, rather, you know—about a shilling or
one-and-sixpence."
He heard Clare's voice reply: "Yes, Mr. Speed, I know what you
want. Hot weather, isn't it?"
"Very."
She went on, searching meanwhile along some shelves: "Nice of
you not to bother about seeing me home the other night, Mr. Speed."
He said, with a touch of embarrassment: "Well, you see, you told
me. About—about Miss Ervine getting jealous, you know."
"It was nice of you to take my information without doubting it."
He said, rather to his own surprise: "As a matter of fact, I'm not
sure that I don't doubt it. Miss Ervine seems to me a perfectly
delightful and natural girl, far too unsophisticated to be jealous of
anybody. The more I see of her the more I like her."
After a pause she answered quietly: "Well, I'm not surprised at
that."
"I suppose," he went on, "with her it's rather the opposite. I mean,
the more she sees of me the less she likes me. Isn't that it?"
"I shouldn't think she likes you any less than she did at first....
Here's the atlas. It's one and three—I'd better put it on your account,
eh?"
"Yes, yes, of course.... So you think—"
She interrupted him quickly with: "Mr. Speed, you'd better not ask
me what I think. You're far more subtle in understanding people than
I am, and it won't take you long to discover what Helen thinks of you
if you set about with the intention.... Those sketch-blocks you
ordered haven't come in yet.... Well, good afternoon!"
Another customer had entered the shop, so that all he could do
was to return a rather dazed "Good afternoon" and emerge into the
blazing High Street. He walked back to the school in a state of not
unpleasant puzzlement.
II
The term progressed, and towards the end of May occurred the
death of Sir Huntly Polk, Bart., Chairman of the Governors of
Millstead School. This would not have in any way affected Speed
(who had never even met Sir Huntly) had not a Memorial Service
been arranged at which he was to play Chopin's Funeral March on
the chapel organ. It was a decent modern instrument, operated
usually by Raggs, the visiting organist, who combined a past
reputation of great splendour with a present passion for the vox
humana stop; but Speed sometimes took the place of Raggs when
Raggs wanted time off. And at the time fixed for the Sir Huntly Polk
Memorial Service Raggs was adjudicating with great solemnity at a
Northern musical festival.
Speed was not a particularly good organist, and it was only
reluctantly that he undertook Raggs' duty for him. For one thing, he
was always slightly nervous of doing things in public. And for another
thing, he would have to practice a great deal in order to prepare
himself for the occasion, and he had neither the time nor the
inclination for hours of practice. However, when the Head said: "I
know I can—um, yes—rely upon you, Mr. Speed," Speed knew that
there was no way out of it. Besides, he was feeling his way in the
school with marvellous ease and accuracy, and each new duty
undertaken by special request increased and improved his prestige.
After a few days' trial he found it was rather pleasant to climb the
ladder to the organ-loft amid the rich cool dusk of the chapel, switch
on the buzzing motor that operated the electric power, and play, not
only Chopin's Funeral March but anything else he liked. Often he
would merely improvise, beginning with a simple theme announced
on single notes, and broadening and loudening into climax. Always
as he played he could see the shafts of sunlight falling amidst the
dusty pews, the many-coloured glitter of the stained-glass in the oriel
window, and in an opaque haze in the distance the white cavern of
the chapel entrance beyond which all was light and sunshine. The
whole effect, serene and tranquillising, hardly stirred him to any
distinctly religious emotion, but it set up in him acutely that emotional
sensitiveness to things secret and unseen, that insurgent
consciousness, clear as the sky, yet impossible to translate into
words, of deep wells of meaning beneath all the froth and commotion
of his five passionate senses.
There was a mirror just above the level of his eyes as he sat at
the keyboard, a mirror by means of which he could keep a casual
eye on the pulpit and choir-stalls and the one or two front pews. And
one golden afternoon as he was playing the adagio movement out of
Beethoven's "Sonata Pathétique," a stray side-glance into the mirror
showed him that he had an audience—of one. She was sitting at the
end of the front pew of all, nearest the lectern; she was listening,
very simply and unspectacularly. Speed's first impulse was to stop;
his second to switch off from the "Sonata Pathétique" into something
more blatantly dramatic. He had, with the first kindling warmth of the
sensation of seeing her, a passionate longing to touch somehow her
emotions, or, if he could not do that, to stir her sentimentality, at any
rate; he would have played the most saccharine picture-palace trash,
with vox humana and tremolo stops combined, if he had thought that
by doing so he could fill her eyes. Third thoughts, however, better
than either the second or first, told him that he had better finish the
adagio movement of the Sonata before betraying the fact that he
knew she was present. He did so accordingly, playing rather well;
then, when the last echoes had died away, he swung his legs over
the bench and addressed her. He said, in a conversational tone that
sounded rather incongruous in its surroundings: "Good afternoon,
Miss Ervine!"
She looked up, evidently startled, and answered, with a half-smile:
"Oh, good afternoon, Mr. Speed."
He went on: "I hope I haven't bored you. Is there anything in
particular you'd like me to play to you?"
She walked out of the pew and along the tiled arena between the
choir-stalls to a point where she stood gazing directly up at him. The
organ was on the south side of the choir, perched rather
precipitously in an overhead chamber that looked down on to the
rest of the chapel rather as a bay-window looks on to a street. To
Speed, as he saw her, the situation seemed somewhat like the
balcony scene with the positions of Romeo and Juliet reversed. And
never, he thought, had she looked so beautiful as she did then, with
her head poised at an upward angle as if in mute and delicate
appeal, and her arms limply at her side, motionless and
inconspicuous, as though all the meaning and significance of her
were flung upwards into the single soaring glance of her eyes. A
shaft of sunlight, filtered through the crimson of an apostle's robe,
struck her hair and kindled it at once into flame; her eyes, blue and
laughing, gazed heavenwards with a look of matchless tranquillity.
She might have been a saint, come to life out of the sun-drenched
stained-glass.
She cried out, like a happy child: "Oh, I have enjoyed it, Mr.
Speed! All of it. I do wish I could come up there and watch you play!"
With startled eagerness he answered: "Come up then—I should
be delighted! Go round into the vestry and I'll help you up the
ladder."
Instinct warned him that she was only a child, interested in the
merely mechanical tricks of how things were done; that she wanted
to see the working of the stops and pedals more than to hear the
music; that this impulse of hers did not betoken any particular
friendliness for him or admiration for his playing. Yet some secondary
instinct, some quick passionate enthusiasm, swept away the
calculating logic of that, and made him a prey to the wildest and
raptest of anticipations.
In the vestry she blushed violently as he met her; she seemed
more a child than ever before. And she scampered up the steep
ladder into the loft with an agility that bewildered him.
He never dreamt that she could so put away all fear and
embarrassment of his presence; as she clambered up on to the end
of the bench beside him (for there was no seating-room anywhere
else) he wondered if this were merely a mood of hers, or if some real
and deep change had come over her since their last meeting. She
was so delicately lovely; to see her there, with her eyes upon him, so
few inches from his, gave him a curious electrical pricking of the
skin. Sometimes, he noticed, her eyes watched his hands steadily;
sometimes, with a look half-bold, half-timid, they travelled for an
instant to his face. He even wondered, with an egotism that made
him smile inwardly, if she were thinking him good-looking.
"Now," he said, beginning to pull out the necessary stops, "what
shall we have?—'The Moonlight Sonata,' eh?"
"Yes," she assented, eagerly. "I've heard Clare talk about it."
He played it to her; then he played her a medley of Bach, Dvorak,
Mozart, Mendelssohn and Lemare. He was surprised and pleased to
discover that, on the whole, she preferred the good music to the not
so good, although, of course, her musical taste was completely
unsophisticated. Mainly, too, it was the music that kept her attention,
though she had a considerable childish interest in his manual
dexterity and in the mechanical arrangement of the stops and
couplings. She said once, in a pause between two pieces: "Aren't
they strange hands?" He replied, laughing away his embarrassment:
"I don't know. Are they?"
After he had played, rather badly but with great verve, the Ruy
Blas Overture of Mendelssohn, she exclaimed: "Oh, I wish I could
play like that!"
He said: "But you do play the piano, don't you? And I prefer the
piano to the organ: it's less mechanical."
She clapped her hands together in a captivatingly childish gesture
of excitement and said: "Oh yes, the piano's lovely, isn't it? But I
can't play well—oh, I wish I could!"
"You could if you practised hard enough," he answered, with
prosaic encouragement. "I can hear you sometimes, you know, when
I'm in my room at nights and the window's open. I think you could
become quite a good player."
She leaned her elbow on the keys and started in momentary fright
at the resulting jangle of sound. "I—I get so nervous," she said. "I
don't know why. I could never play except to myself—and Clare."
She added, slowly, and as if the revelation had only barely come to
her: "Do you know—it's strange, isn't it—I think—perhaps—I think I
might be able to play in front of you—now—without being nervous!"
He laughed boisterously and swung himself off the bench. "Very
well, then, that's fine news! You shall try. You shall play some of the
Chopin waltzes to me. Not very suitable for an organ, but that
doesn't matter. Sit further on this bench and play on the lower
keyboard. Never mind about the pedals. And I'll manage the stops
for you."
She wriggled excitedly into the position he had indicated and,
laughing softly, began one of the best-known of the waltzes. The
experiment was not entirely successful, for even an accomplished
pianist does not play well on an organ for the first time, nor do the
Chopin waltzes lend themselves aptly to such an instrument. But one
thing, and to Speed the main thing of all, was quite obvious: she
was, as she had said she would be, entirely free from nervousness
of him. After ploughing rather disastrously through a dozen or so
bars she stopped, turned to him with flushed cheeks and happy
eyes, and exclaimed: "There! That's enough! It's not easy to play, is
it?"
He said, smiling down at her: "No, it's rather hard, especially at
first.... But you weren't nervous then, were you?"
"Not a bit," she answered, proudly. She added, with a note of
warning: "Don't be surprised if I am when you come in to our house
to dinner. I'm always nervous when father's there."
Almost he added: "So am I." But the way in which she had
mentioned future invitations to dinner at the Head's house gave him
the instant feeling that henceforward the atmosphere on such
occasions would he subtly different from ever before. The Head's
drawing-room, with the baby grand piano and the curio-cabinets and
the faded cabbage-like design of the carpet, would never look quite
the same again; the Head's drawing-room would look, perhaps, less
like a cross between a lady's boudoir and the board-room of a City
company; even the Head's study might take on a kindlier, less
sinister hue.
He said, still with his eyes smiling upon her: "Who teaches you the
piano?"
"A Miss Peacham used to. I don't have a teacher now."
"I don't know," he said, beginning to flush with the consciousness
of his great daring, "if you would care to let me help you at all. I
should be delighted to do so, you know, at any time. Since—" he
laughed a little—"since you're no longer a scrap nervous of me, you
might find me useful in giving you a few odd hints."
He waited, anxious and perturbed, for her reply. After a sufficient
pause she answered slowly, as if thinking it out: "That would be—
rather—fine—I think."
Most inopportunely then the bell began to ring for afternoon-
school, and, most inopportunely also, he was due to take five beta in
drawing. They clambered down the ladder, chatting vivaciously the
while, and at the vestry door, when they separated she said eagerly:
"Oh, I've had such a good time, Mr. Speed. Haven't you?"
"Rather!" he answered, with boyish emphasis and enthusiasm.
That afternoon hour, spent bewilderingly with five beta in the art-
room that was full of plaster casts and free-hand models and framed
reproductions of famous pictures, went for Speed like the passage of
a moment. His heart and brain were tingling with excitement,
teeming with suppressed consciousness. The green of the lawns as
he looked out of the window seemed greener than ever before; the
particles of dust that shone in the shafts of sunlight seemed to him
each one mightily distinct; the glint of a boy's golden hair in the
sunshine was, to his eyes, like a patch of flame that momentarily put
all else in a haze. It seemed to him, passionately and tremendously,
that for the first time in his life he was alive; more than that even: it
seemed to him that for the first time since the beginning of all things
life had come shatteringly into the world.
III
"I should think, Mr. Speed, you have found out by now whether
Helen likes you or not."
Those words of Clare Harrington echoed in his ears as he walked
amidst the dappled sunlight on the Millstead road. They echoed first
of all in the quiet tones in which Clare had uttered them; next, they
took on a subtle, meaningful note of their own; finally, they
submerged all else in a crescendo of passionate triumph. Speed was
almost stupefied by their gradually self-revealing significance. He
strode on faster, dug his heels more decisively into the dust of the
roadside; he laughed aloud; his walking-stick pirouetted in a joyful
circle. To any passer-by he must have seemed a little mad. And all
because of a few words that Clare Harrington, riding along the lane
on her bicycle, had stopped to say to him.
June, lovely and serene, had spread itself out over Millstead like a
veil of purest magic; every day the sun climbed high and shone
fiercely; every night the world slept under the starshine; all the
passage of nights and days was one moving pageant of
wonderment. And Speed was happy, gloriously, overwhelmingly
happy. Never in all his life before had he been so happy; never had
he tasted, even to an infinitesimal extent, the kind of happiness that
bathed and drenched him now. Rapturously lovely were those long
June days, days that turned Millstead into a flaming paradise of
sights and sounds. In the mornings, he rose early, took a cold plunge
in the swimming-bath, and breakfasted with the school amidst the
cool morning freshness that, by its very quality of chill, seemed to
suggest bewitchingly the warmth that was to come. Chapel followed
breakfast, and after that, until noon, his time was spent in the Art and
Music Rooms and the various form-rooms in which he contrived to
satisfy parental avidity for that species of geography known as
commercial. From noon until midday dinner he either marked books
in his room or went shopping into the town. During that happy hour
the cricket was beginning, and the dining-hall at one o'clock was gay
with cream flannels and variously chromatic blazers. Speed loved
the midday meal with the school; he liked to chat with his neighbours
at table, to listen to the catalogue of triumphs, anxieties, and
anticipations that never failed to unfold itself to the sympathetic
hearer. Afterwards he was free to spend the afternoon as he liked.
He might cycle dreamily along the sleepy lanes and find himself at
tea-time in some wrinkled little sun-scorched inn, with nothing to do
but dream his own glorious dreams and play with the innkeeper's
languid dog and read local newspapers a fortnight old. Or he might
stay the whole afternoon at Millstead, lazily watching the cricket from
a deck-chair on the pavilion verandah and sipping the tuck-shop's
iced lemonade. Less often he would play cricket himself, never
scoring more than ten or a dozen runs, but fielding with a dogged
energy which occasionally only just missed deserving the epithet
brilliant. And sometimes, in the excess of his enthusiasm, he would
take selected parties of the boys to Pangbourne Cathedral, some
eighteen miles distant, and show them the immense nave and the
Lady Chapel with the decapitated statues and the marvellous
stained-glass of the Octagon.
Then dinner, conversational and sometimes boisterous, in the
Masters' Common-Room, and afterwards, unless it were his evening
for taking preparation, an hour at least of silence before the corridors
and dormitories became noisy. During this hour he would often sit by
the open window in his room and hear the rooks cawing in the high
trees and the clankety-clank of the roller on the cricket-pitch and all
the mingled sounds and commotions that seemed to him to make
the silence of the summer evenings more magical than ever. Often,
too, he would hear the sound of the Head's piano, a faint half-
pathetic tinkle from below.
Half-past eight let loose the glorious pandemonium; he could hear
from his room the chiming of the school-bell, and then, softly at first,
but soon rising to a tempestuous flood, the tide of invasion sweeping
down the steps of the Big Hall and pouring into the houses. Always it
thrilled him by its mere strength and volume of sound; thrilled him
with pride and passion to think that he belonged to this heart that
throbbed with such onrushing zest and vitality. Soon the first
adventurous lappings of the tide reached the corridor outside his
room; he loved the noise and commotion of it; he loved the shouting
and singing and yelling and the boisterous laughter; he loved the
faint murmur of conflicting gramophones and the smells of coffee
and cocoa that rose up from the downstairs studies; he loved the
sound of old Hartopp's voice as he stood at the foot of the stairs at
ten o'clock and shouted, in a key that sent up a melodious echoing
through all the passages and landings: "Time, gentlemen, time!"—
And when the lights in the dormitories had all been put out, and
Millstead at last was silent under the stars, he loved above all things
the strange magic of his own senses, that revealed him a Millstead
that nobody else had ever seen, a Millstead rapt and ethereal, one
with the haze of night and the summer starshine.
He told himself, in the moments when he reacted from the
abandonment of his soul to dreaming, that he was sentimental, that
he loved too readily, that beauty stirred him more than it ought, that
life was too vividly emotional, too mighty a conqueror of his senses.
But then, in the calm midst of reasoning, that same wild, tremulous
consciousness of wonder and romance would envelop him afresh
like a strong flood; it was a fierce, passionate ache in his bones, only
to be forgotten for unreal, unliving instants. And one moment, when
he sat by the window hearing the far-off murmur of Chopin on the
Head's piano, he knew most simply and perfectly why it was that all
this was so. It was because he was very deeply and passionately in
love. In his dreams, his wild and bewitching dreams, she was a fairy-
child, ethereal and half unreal, the rapt half-embodied spirit of
Millstead itself, luring him by her sweet and fragrant vitality. He saw
in the sunlight always the golden glint of her hair; in music no more
than subtle and exquisite reminders of her; in all the world of sights
and sounds and feelings a deep transfiguring passion that was his
own for her.
And in the flesh he met her often in the school grounds, where
she might say: "Oh, Mr. Speed, I'm so glad I've met you! I want you
to come in and hear me play something." They would stroll together
over the lawns into the Head's house and settle themselves in the
stuffy-smelling drawing-room. Doctor and Mrs. Ervine were
frequently out in the afternoons, and Potter, it was believed, dozed in
the butler's pantry. Speed would play the piano to the girl and then
she to him, and when they were both tired of playing they talked
awhile. Everything of her seemed to him most perfect and delicious.
Once he asked her tactfully about reading novelettes, and she said:
"I read them sometimes because there's nothing in father's library
that I care for. It's nearly all sermons and Latin grammars."
Immediately it appeared to him that all was satisfactory and
entrancingly explained; a vague unrestfulness in him was made
suddenly tranquil; her habit of reading novelettes made her more
dear and lovable than ever. He said: "I wonder if you'd like me to
lend you some books?—Interesting books, I promise you."—She
answered, with her child-like enthusiasm: "Oh, I'd love that, Mr.
Speed!"
He lent her Hans Andersen's fairy tales.
Once in chapel, as he declaimed the final verse of the eighty-
eighth Psalm, he looked for a fraction of a second at the Head's pew
and saw that she was watching him. "Lover and friend hast Thou put
far from me, and mine acquaintance into darkness."—He saw a
blush kindle her cheeks like flame.
One week-day morning he met the Head in the middle of the
quadrangle. The Head beamed on him cordially and said: "I
understand, Mr. Speed, that you—um—give my daughter—
occasional—um, yes—assistance with her music. Very kind of you,
I'm sure—um, yes—extremely kind of you, Mr. Speed."
He added, dreamily: "My daughter—still—um, yes—still a child in
many ways—makes few friends—um, yes—very few. Seems to have
taken quite an—um, yes—quite a fancy to you, Mr. Speed."
And Speed answered, with an embarrassment that was
ridiculously schoolboyish: "Indeed, sir?—Indeed?"
IV
Speech Day at Millstead.

Speed sat shyly on his chair on the platform, wrapping his gown
round him nervously, and gazing, every now and then, at the
fashionably-dressed throng that crowded the Big Hall to its utmost
capacity. It was a day of ordeals, but his own chief ordeal was safely
past; the school-choir had grappled quite creditably with Stanford's
Te Deum at the chapel service that morning. He was feeling very
happy, even amidst his nervousness. His eyes wandered to the end
of the front row of the auditorium, where Helen Ervine and Clare
Harrington sat together. They were gossiping and laughing.
The Chairman, Sir Henry Briggs, rose to introduce the principal
guest, Lord Portway. Lord Portway, so said Sir Henry Briggs, needed
no introduction. Lord Portway....
Speed listened dreamfully.
Then Lord Portway. Lord Portway confessed himself to be a poor
speaker, but hoped that it would not always be those with a glib
tongue that got on in the world. (Laughter and cheers.) When he
(Lord Portway) was at school he was ashamed to say that he never
received a single prize. (More laughter.) He hoped that all the boys
of Millstead, whether they had prizes or not, would remember that it
wasn't always the prize-winners at school who did best in the battle
of life. (Hear, hear.) He would just like to give them all a word or two
of advice. Be thorough. (Cheers.) Brilliance wasn't everything. If he

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Metal oxide-based photocatalysis :

fundamentals and prospects for

Metal Oxide-Based Nanofibers and Their Applications 1st

Metal Oxide Powder Technologies: Fundamentals,

Carbon-Based Metal Free Catalysts: Preparation,

Renewable Polymers and Polymer-Metal Oxide Composites:

Feedstock Technology for Reactive Metal Injection

Theory and practice of metal oxide catalyst design for

Biopolymer-Based Metal Nanoparticle Chemistry for

(eBook PDF) Evidence-Based Practice for Nurses:

Library of Congress Cataloging-in-Publication Data

For information on all Elsevier publications

Publisher: Matthew Deans

2 Fundamentals of metal oxide-based photocatalysis 3

3 Metal oxide photocatalysts 51

4 Application of metal oxide-based photocatalysis 211

Further reading 222

4.7.2 Superhydrophilicity mechanism 288

5 Outlook and prospects 341

Malankowska Anna University of Gdansk, Gdansk, Poland

Bajorowicz Beata University of Gdansk, Gdansk, Poland

Anna Goła˛biewska University of Gdansk, Gdansk, Poland

Ewelina Grabowska University of Gdansk, Gdansk, Poland

Nadolna Joanna University of Gdansk, Gdansk, Poland

Martyna Marchelek University of Gdansk, Gdansk, Poland

Marta Paszkiewicz-Gawron University of Gdansk, Gdansk, Poland

Mazierski Paweł University of Gdansk, Gdansk, Poland

Adriana Zaleska-Medynska University of Gdansk, Gdansk, Poland

Metal Oxide-Based Photocatalysis. https://doi.org/10.1016/B978-0-12-811634-0.00001-9

of metal oxides used in photocatalysis, advantages, disadvantages, and achievements

2.1 Principles of metal oxide-based photocatalysis

2.1.1 Mechanism of photocatalytic reactions

If the oxidation potential of the VB holes is not sufficient to form OH radicals, O2 is

The ability of a semiconductor to undergo the transfer of photoinduced electrons to

Fig. 2.3 Mechanism of photocatalytic

2.1.1.1 Doped semiconductors

Fig. 2.4 Mechanism of visible

semiconductor by capturing the excited electrons from the VB of the semiconductor

2.1.1.2 Semiconductor photosensitization

λmax λmax λmax

λmax λmax λmax

2.1.1.3 Charge transfer interaction

2.1.1.4 Composite semiconductors

2.1.1.5 Semiconductor modified by noble metal nanoparticles

Fig. 2.9 Schematic illustration of (A) mechanism of visible light-induced excitation of

2.1.2 Kinetics of photocatalysis [100]

Table 2.2 Key reaction processes

2.1.3 Generation and separation of charge carriers

X1 X2 ρθ ½P X2 ¼ (kp/kT1) but at low ρ, ν ¼ 1 and G, B1, T1, Langmuir-Ollis [103]

He woke with a sensation of intense chilliness; the sun had gone

The immediate result of the incident was an invitation to dine at

One afternoon he called at Harrington's, in the High Street, to buy

Speech Day at Millstead.

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X1 X2 ρθ ½P X2 ¼ (kp/kT1) but at low ρ, ν ¼ 1 and G, B1, T1, Langmuir-Ollis [103]