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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,
electronic or mechanical, including photocopying, recording, or any information storage
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seek permission, further information about the Publisher’s permissions policies and our
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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
evaluating and using any information, methods, compounds, or experiments described herein.
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,
products, instructions, or ideas contained in the material herein.

Library of Congress Cataloging-in-Publication Data

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A catalogue record for this book is available from the British Library
ISBN: 978-0-12-811634-0

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Publisher: Matthew Deans

Acquisition Editor: Kayla Dos Santos
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Production Project Manager: Swapna Srinivasan
Cover Designer: Miles Hitchen
Typeset by SPi Global, India
Contents

List of contributors ix

1 Introduction 1
Adriana Zaleska-Medynska
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,
Adriana Zaleska-Medynska
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,
Adriana Zaleska-Medynska
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
4.4.5 Conclusions and prospects 261
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
4.8.3 Conclusions and prospects 312
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
4.9.5 Conclusions and prospects 334
References 335
Further reading 340

5 Outlook and prospects 341

Adriana Zaleska-Medynska

Index 345
This page intentionally left blank
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

This page intentionally left blank
Introduction
Adriana Zaleska-Medynska
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

© 2018 Elsevier Inc. All rights reserved.
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
© 2018 Elsevier Inc. All rights reserved.
4 Metal Oxide-Based Photocatalysis

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.
6 Metal Oxide-Based Photocatalysis

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.
Fundamentals of metal oxide-based photocatalysis 7

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
8 Metal Oxide-Based Photocatalysis

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 ! Mðn
1Þ + + hVB
+
(2.11)

where M and Mn+ represent metal and metal ion dopant, respectively. The energy level of
Mn+/M(n
1)+ 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.
Fundamentals of metal oxide-based photocatalysis 9

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.
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Title: The Wyvern mystery

Author: Joseph Sheridan Le Fanu

Illustrator: Brinsley Le Fanu

Release date: July 19, 2022 [eBook #68569]

Language: English

Original publication: United Kingdom: Ward and Downey, 1889

Credits: an anonymous Project Gutenberg volunteer

*** START OF THE PROJECT GUTENBERG EBOOK THE

WYVERN MYSTERY ***
“She stood up—how pretty she was!—looking on her work.”
 THE
WYVERN MYSTERY
A Novel.

BY
J. S. LE FANU,
AUTHOR OF “UNCLE SILAS,” “GUY DEVERELL,” ETC.

WITH ILLUSTRATIONS BY B. S. LE FANU.

London:
WARD AND DOWNEY,
12, YORK STREET, COVENT GARDEN.
1889.
 CONTENTS.
I. ALICE MAYBELL
II. THE VALE OF CARWELL
III. THE GRANGE
IV. THE OLD SQUIRE AND ALICE MAYBELL
V. THE TERRACE GARDEN
VI. THE OLD SQUIRE UNLIKE HIMSELF
VII. THE SQUIRE’S ELDEST SON COMES HOME
VIII. NEVER DID RUN SMOOTH
IX. IN WHICH THE SQUIRE LOSES HIS GOLD-HEADED CANE
X. THE DRIVE OVER CRESSLEY COMMON BY MOONLIGHT
XI. HOME
XII. THE OMEN OF CARWELL GRANGE
XIII. AN INSPECTION OF CARWELL GRANGE
XIV. A LETTER
XV. HARRY ARRIVES
XVI. A PARTY OF THREE
XVII. MILDRED TARNLEY’S WARNING STORY
XVIII. THE BROTHERS’ WALK
XIX. COMING IN
XX. HARRY APPEARS AT THE GRANGE
XXI. HARRY’S BEER AND CONVERSATION
XXII. THE TROUT
XXIII. THE VISITOR
XXIV. THE SUMMONS
XXV. LILLY DOGGER IS SENT TO BED
XXVI. THE LADY HAS HER TEA
XXVII. THROUGH THE HOUSE
XXVIII. THE BELL RINGS
XXIX. TOM IS ORDERED UP
XXX. THE OLD SOLDIER GROWS MORE FRIENDLY, AND
FRIGHTENS MRS. TARNLEY
XXXI. NEWS FROM CRESSLEY COMMON
XXXII. AN UNLOOKED-FOR RETURN
XXXIII. CHARLES FAIRFIELD ALONE
XXXIV. AWAKE
XXXV. RESTLESS
XXXVI. THROUGH THE WALL
XXXVII. A MESSENGER
XXXVIII. UNREASONABLE BERTHA
XXXIX. AN ABDUCTION
XL. PURSUIT
XLI. DAY—TWILIGHT—DARKNESS
XLII. HATHERTON
XLIII. THE WELCOME
XLIV. THE WYKEFORD DOCTOR
XLV. SPEECH RETURNS
XLVI. HARRY DRINKS A GLASS AND SPILLS A GLASS
XLVII. HOME TO WYVERN
XLVIII. A TWILIGHT VISIT
XLIX. THE HEIR OF THE FAIRFIELDS
L. BERTHA VELDERKAUST
LI. SERGEANT-MAJOR ARCHDALE
LII. A TALK WITH THE SQUIRE
LIII. HARRY FAIRFIELD GROWS UNEASY
LIV. A DRIVE TO TWYFORD
LV. HOW FARES THE CHILD?
LVI. THE OLD SQUIRE LEAVES WYVERN
LVII. MARJORY TREVELLIAN
LVIII. THE ENCHANTED GARDEN
LIX. AN OLD FRIEND
LX. TOM ORANGE
LXI. THE HOUR AND THE MAN
LXII. THE MARCH TO NOULTON FARM
LXIII. A SILENT FAREWELL
LXIV. THE MARCH BY NIGHT
CONCLUSION
 THE WYVERN MYSTERY.

CHAPTER I.
ALICE MAYBELL.

In the small breakfast parlour of Oulton, a pretty girl, Miss Alice

Maybell, with her furs and wrappers about her, and a journey of forty
miles before her—not by rail—to Wyvern, had stood up to hug and
kiss her old aunt, and bid her good-bye.
“Now, do sit down again; you need not be in such a hurry—you’re
not to go for ten minutes or more,” said the old lady; “do, there’s a
darling.”
“If I’m not home before the sun goes down, aunt, Mr. Fairfield will
be so angry,” said the girl, laying a hand on each shoulder of kind old
Lady Wyndale, and looking fondly, but also sadly, into her face.
“Which Mr. Fairfield, dear—the old or the young one?”
“Old Mr. Fairfield, the Squire, as we call him at Wyvern. He’ll really
be angry, and I’m a little bit afraid of him, and I would not vex him for
the world—he has always been so kind.”
As she answered, the young lady blushed a beautiful crimson, and
the old lady, not observing it, said—
“Indeed, I don’t know why I said young—young Mr. Fairfield is old
enough, I think, to be your father; but I want to know how you liked
Lord Tremaine. I told you how much he liked you. I’m a great
believer in first impressions. He was so charmed with you, when he
saw you in Wyvern Church. Of course he ought to have been
thinking of something better; but no matter—the fact was so, and
now he is, I really think, in love—very much—and who knows? He’s
such a charming person, and there is everything to make it—I don’t
know what word to use—but you know Tremaine is quite a beautiful
place, and he does not owe a guinea.”
“You dear old auntie,” said the girl, kissing her again on the cheek,
“wicked old darling—always making great matches for me. If you had
remained in India, you’d have married me, I’m sure, to a native
prince.”
“Native fiddlestick; of course I could if I had liked, but you never
should have married a Mahomedan with my consent. Never mind
though; you’re sure to do well; marriages are made in heaven, and I
really believe there is no use in plotting and planning. There was
your darling mamma, when we were both girls together, I said I
should never consent to marry a soldier or live out of England, and I
did marry a soldier, and lived twelve years of my life in India; and
she, poor darling, said again and again, she did not care who her
husband might be, provided he was not a clergyman, nor a person
living all the year round in the country—that no power could induce
her to consent to, and yet she did consent, and to both one and the
other, and married a clergyman, and a poor one, and lived and died
in the country. So, after all, there’s not much use in planning
beforehand.”
“Very true, auntie; none in the world, I believe.”
The girl was looking partly over her shoulder, out of the window,
upward towards the clouds, and she sighed heavily; and recollecting
herself, looked again in her aunt’s face and smiled.
“I wish you could have stayed a little longer here,” said her aunt.
“I wish I could,” she answered slowly, “I was thinking of talking
over a great many things with you—that is, of telling you all my long
stories; but while those people were staying here I could not, and
now there is not time.”
“What long stories, my dear?”
“Stupid stories, I should have said,” answered Alice.
“Well come, is there anything to tell?” demanded the old lady,
looking in her large, dark eyes.
“Nothing worth telling—nothing that is—” and she paused for the
continuation of her sentence.
“That is what?” asked her aunt.
 “I was going to talk to you, darling,” answered the girl, “but I could
not in so short a time—so short a time as remains now,” and she
looked at her watch—a gift of old Squire Fairfield’s. “I should not
know how to make myself understood, I have so many hundred
things, and all jumbled up in my head, and should not know how to
begin.”
“Well, I’ll begin for you. Come—have any visitors looked in at
Wyvern lately?” said her aunt.
“Not one,” she answered.
“No new faces?”
“No, indeed.”
“Are there any new neighbours?” persisted the old lady.
“Not one. No, aunt, it isn’t that.”
“And where are these elderly young gentlemen, the two Mr.
Fairfields?” asked the old lady.
The girl laughed, and shook her head.
“Wandering at present. Captain Fairfield is in London.”
“And his charming younger brother—where is he?” asked Lady
Wyndale.
“At some fair, I suppose, or horse-race; or, goodness knows
where,” answered the girl.
“I was going to ask you whether there was an affair of the heart,”
said her aunt. “But there does not seem much material; and what
was the subject? Though I can’t hear it all, you may tell me what it
was to be about.”
“About fifty things, or nothings. There’s no one on earth, auntie,
darling, but you I can talk anything over with; and I’ll write, or, if you
let me, come again for a day or two, very soon—may I?”
“Of course, no,” said her aunt gaily. “But we are not to be quite
alone, all the time, mind. There are people who would not forgive me
if I were to do anything so selfish, but I promise you ample time to
talk—you and I to ourselves; and now that I think, I should like to
hear by the post, if you will write and say anything you like. You may
be quite sure nobody shall hear a word about it.”
By this time they had got to the hall-door.
“I’m sure of that, darling,” and she kissed the kind old lady.
 “And are you quite sure you would not like a servant to travel with
you; he could sit beside the driver?”
“No, dear auntie, my trusty old Dulcibella sits inside to take care of
me.”
“Well, dear, are you quite sure? I should not miss him the least.”
“Quite, dear aunt, I assure you.”
“And you know you told me you were quite happy at Wyvern,” said
Lady Wyndale, returning her farewell caress, and speaking low, for a
servant stood at the chaise-door.
“Did I? Well, I shouldn’t have said that, for—I’m not happy,”
whispered Alice Maybell, and the tears sprang to her eyes as she
kissed her old kinswoman; and then, with her arms still about her
neck, there was a brief look from her large, brimming eyes, while her
lip trembled; and suddenly she turned, and before Lady Wyndale
had recovered from that little shock, her pretty guest was seated in
the chaise, the door shut, and she drove away.
“What can it be, poor little thing?” thought Lady Wyndale, as her
eyes anxiously followed the carriage in its flight down the avenue.
“They have shot her pet-pigeon, or the dog has killed her guinea-
pig, or old Fairfield won’t allow her to sit up till twelve o’clock at night,
reading her novel. Some childish misery, I dare say, poor little soul!”
But for all that she was not satisfied, and her poor, pale, troubled
look haunted her.
 CHAPTER II.
THE VALE OF CARWELL.

In about an hour and a half this chaise reached the Pied Horse, on
Elverstone Moor. Having changed horses at this inn, they resumed
their journey, and Miss Alice Maybell, who had been sad and
abstracted, now lowered the window beside her, and looked out
upon the broad, shaggy heath, rising in low hillocks, and breaking
here and there into pools—a wild, and on the whole a monotonous
and rather dismal expanse.
“How fresh and pleasant the air is here, and how beautiful the
purple of the heath!” exclaimed the young lady with animation.
“There now—that’s right—beautiful it is, my darling; that’s how I
like to see my child—pleasant-like and ’appy, and not mopin’ and
dull, like a sick bird. Be that way always; do, dear.”
“You’re a kind old thing,” said the young lady, placing her slender
hand fondly on her old nurse’s arm, “good old Dulcibella: you’re
always to come with me wherever I go.”
“That’s just what Dulcibella’d like,” answered the old woman, who
was fat, and liked her comforts, and loved Miss Alice more than
many mothers love their own children, and had answered the same
reminders, in the same terms, a good many thousand times in her
life.
Again the young lady was looking out of the window—not like one
enjoying a landscape as it comes, but with something of anxiety in
her countenance, with her head through the open window, and
gazing forward as if in search of some expected object.
“Do you remember some old trees standing together at the end of
this moor, and a ruined windmill, on a hillock?” she asked suddenly.
“Well,” answered Dulcibella, who was not of an observant turn, “I
suppose I do, Miss Alice; perhaps there is.”
“I remember it very well, but not where it is; and when last we
passed, it was dark,” murmured the young lady to herself, rather
than to Dulcibella, whom upon such points she did not much mind.
“Suppose we ask the driver?”
She tapped at the window behind the box, and signed to the man,
who looked over his shoulder. When he had pulled up she opened
the front window and said—
“There’s a village a little way on—isn’t there?”
“Shuldon—yes’m, two mile and a bit,” he answered.
“Well, before we come to it, on the left there is a grove of tall trees
and an old windmill,” continued the pretty young lady, looking pale.
“Gryce’s mill we call it, but it don’t go this many a day.”
“Yes, I dare say; and there is a road that turns off to the left, just
under that old mill?”
“That’ll be the road to Church Carwell.”
“You must drive about three miles along that road.”
“That’ll be out o’ the way, ma’am—three, and three back—six
miles—I don’t know about the hosses.”
“You must try, I’ll pay you—listen,” and she lowered her voice.
“There’s one house—an old house—on the way, in the Vale of
Carwell; it is called Carwell Grange—do you know it?”
“Yes’m; but there’s no one livin’ there.”
“No matter—there is; there is an old woman whom I want to see;
that’s where I want to go, and you must manage it, I shan’t delay you
many minutes, and you’re to tell no one, either on the way or when
you get home, and I’ll give you two pounds for yourself.”
“All right,” he answered, looking hard in the pale face and large
dark eyes that gazed on him eagerly from the window. “Thank’ye,
Miss, all right, we’ll wet their mouths at the Grange, or you wouldn’t
mind waiting till they get a mouthful of oats, I dessay?”
“No, certainly; anything that is necessary, only I have a good way
still to go before evening, and you won’t delay more than you can
help?”
“Get along, then,” said the man, briskly to his horses, and forthwith
they were again in motion.
The young lady pulled up the window, and leaned back for some
minutes in her place.
“And where are we going to, dear Miss Alice?” inquired Dulcibella,
who dimly apprehended that they were about to deviate from the
straight way home, and feared the old Squire, as other Wyvern folk
did.
“A very little way, nothing of any consequence; and Dulcibella, if
you really love me as you say, one word about it, to living being at
Wyvern or anywhere else, you’ll never say—you promise?”
“You know me well, Miss Alice—I don’t talk to no one; but I’m
sorry-like to hear there’s anything like a secret. I dread secrets.”
“You need not fear this—it is nothing, no secret, if people were not
unreasonable, and it shan’t be a secret long, perhaps, only be true to
me.”
“True to you! Well, who should I be true to if not to you, darling?
and never a word about it will pass old Dulcibella’s lips, talk who will;
and are we pretty near it?”
“Very near, I think; it’s only to see an old woman, and get some
information from her—nothing, only I don’t wish it to be talked about,
and I know you won’t.”
“Not a word, dear. I never talk to any one, not I, for all the world.”
In a few minutes more they crossed a little bridge spanning a
brawling stream, and the chaise turned the corner of a by-road to the
left, under the shadow of a group of tall and sombre elms,
overtopped by the roofless tower of the old windmill. Utterly lonely
was the road, but at first with only a solitariness that partook of the
wildness and melancholy of the moor which they had been
traversing. Soon, however, the uplands at either side drew nearer,
grew steeper, and the scattered bushes gathered into groups, and
rose into trees, thickening as the road proceeded. Steeper grew the
banks, higher and gloomier. Precipitous rocks showed their fronts,
overtopped by trees and copse. The hollow which they had entered
by the old windmill had deepened into a valley and was now
contracted to a dark glen, overgrown by forest, and relieved from
utter silence only by the moan and tinkle of the brook that wound its
way through stones and brambles, in its unseen depths. Along the
side of this melancholy glen about half way down, ran the narrow
road, near the point where they now were, it makes an ascent, and
as they were slowly mounting this an open carriage—a shabby,
hired, nondescript vehicle—appeared in the deep shadow, at some
distance, descending towards them. The road is so narrow that two
carriages could not pass one another without risk. Here and there
the inconvenience is provided against by a recess in the bank, and
into one of these the distant carriage drew aside. A tall female figure,
with feet extended on the opposite cushion, sat or rather reclined in
the back seat. There was no one else in the carriage. She was
wrapped in gray tweed, and the driver had now turned his face
towards her, and was plainly receiving some orders.
Miss Maybell, as the carriage entered this melancholy pass, had
grown more and more anxious; and pale and silent, was looking
forward through the window, as they advanced. At sight of this
vehicle, drawn up before them, a sudden fear chilled the young lady
with, perhaps, a remote prescience.
 CHAPTER III.
THE GRANGE.

The excited nerves of children people the darkness of the nursery

with phantoms. The moral and mental darkness of suspense
provokes, after its sort, a similar phantasmagoria. Alice Maybell’s
heart grew still, and her cheeks paled as she looked with most
unreasonable alarm upon the carriage, which had come to a
standstill.
There was, however, the sense of a great stake, of great
helplessness, of great but undefined possible mischiefs, such as to
the “look-out” of a rich galleon in the old piratical days, would have
made a strange sail, on the high seas, always an anxious object on
the horizon.
And now Miss Alice Maybell was not reassured by observing the
enemy’s driver get down, and taking the horses by the head, back
the carriage far enough across the road, to obstruct their passage,
and this had clearly been done by the direction of the lady in the
carriage.
They had now reached the point of obstruction, the driver pulled
up; Miss Maybell had lowered the chaise window and was peeping.
She saw a tall woman, wrapped up and reclining, as I have said. Her
face she could not see, for it was thickly veiled, but she held her
hand, from which she had pulled her glove, to her ear, and it was not
a young hand nor very refined,—lean and masculine, on the
contrary, and its veins and sinews rather strongly marked. The
woman was listening, evidently, with attention, and her face, veiled
as it was, was turned away so as to bring her ear towards the
speakers in the expected colloquy.
Miss Alice Maybell saw the driver exchange a look with hers that
seemed to betoken old acquaintance.
“I say, give us room to pass, will ye?” said Miss Maybell’s man.
“Where will you be going to?” inquired the other, and followed the
question with a jerk of his thumb over his shoulder, toward the lady in
the tweed wrappers, putting out his tongue and winking at the same
time.
“To Church Carwell,” answered the man.
“To Church Carwell, ma’am,” repeated the driver over his shoulder
to the reclining figure.
“What to do there?” said she, in a sharp under-tone, and with a
decided foreign accent.
“What to do there?” repeated the man.
“Change hosses, and go on.”
“On where?” repeated the lady to her driver.
“On where?” repeated he.
“Doughton,” fibbed Miss Maybell’s man, and the same repetition
ensued.
“Not going to the Grange?” prompted the lady, in the same under-
tone and foreign accent, and the question was transmitted as before.
“What Grange?” demanded the driver.
“Carwell Grange.”
“No.”
Miss Alice Maybell was very much frightened as she heard this
home-question put, and, relieved by the audacity of her friend on the
box, who continued—
“Now then, you move out of that.”
The tall woman in the wrappers nodded, and her driver
accordingly pulled the horses aside, with another grin and a wink to
his friend, and Miss Maybell drove by to her own great relief.
The reclining figure did not care to turn her face enough to catch a
passing sight of the people whom she had thus arbitrarily detained.
She went her way toward Gryce’s mill, and Miss Maybell pursuing
hers toward Carwell Grange, was quickly out of sight.
A few minutes more and the glen expanded gently, so as to leave
a long oval pasture of two or three acres visible beneath, with the
little stream winding its way through the soft sward among scattered
trees. Two or three cows were peacefully grazing there, and at the
same point a converging hollow made its way into the glen at their
right, and through this also spread the forest, under whose shadow
they had already been driving for more than two miles.
 Into this, from the main road, diverged a ruder track, with a rather
steep ascent. This by-road leads up to the Grange, rather a stiff pull.
The driver had to dismount and lead his horses, and once or twice
expressed doubts as to whether they could pull their burden up the
hill.

The Grange.

Alice Maybell, however, offered not to get out. She was nervous,
and like a frightened child who gets its bed-clothes about its head,
the instinct of concealment prevailed, and she trembled lest some
other inquirer should cross her way less easily satisfied than the first.
They soon reached a level platform, under the deep shadow of
huge old trees, nearly meeting overhead. The hoarse cawing of a
rookery came mellowed by short distance on the air. For all else, the
place was silence itself.
 The man came to the door of the carriage to tell his “fare” that they
had reached the Grange.
“Stay where you are, Dulcibella, I shan’t be away many minutes,”
said the young lady, looking pale, as if she was going to execution.
“I will, Miss Alice; but you must get a bit to eat, dear, you’re
hungry, I know by your looks; get a bit of bread and butter.”
“Yes, yes, Dulcie,” said the young lady, not having heard a syllable
of this little speech, as looking curiously at the old place, under
whose walls they had arrived, she descended from the chaise.
Under the leafy darkness stood two time-stained piers of stone,
with a wicket open in the gate. Through this she peeped into a paved
yard, all grass-grown, and surrounded by a high wall, with a fine
mantle of ivy, through which showed dimly the neglected doors and
windows of out-offices and stables. At the right rose, three stories
high, with melancholy gables and tall chimneys, the old stone house.
So this was Carwell Grange. Nettles grew in the corners of the
yard, and tufts of grass in the chinks of the stone steps, and the worn
masonry was tinted with moss and lichens, and all around rose the
solemn melancholy screen of darksome foliage, high over the
surrounding walls, and outtopping the gray roof of the house.
She hesitated at the door, and then raised the latch; but a bolt
secured it. Another hesitation, and she ventured to knock with a
stone, that was probably placed there for the purpose.
A lean old woman, whose countenance did not indicate a pleasant
temper, put out her head from a window, and asked:
“Well, an’ what brings you here?”
“I expected—to see a friend here,” she answered timidly; “and—
and you are Mrs. Tarnley—I think?”
“I’m the person,” answered the woman.
“And I was told to show you this—and that you would admit me.”
And she handed her, through the iron bars of the window, a little
oval picture in a shagreen case, hardly bigger than a pennypiece.
The old lady turned it to the light and looked hard at it, saying, “Ay
—ay—my old eyes—they won’t see as they used to—but it is so—
the old missus—yes—it’s all right, Miss,” and she viewed the young
lady with some curiosity, but her tones were much more respectful
as she handed her back the miniature.