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Springer Theses
Recognizing Outstanding Ph.D. Research

Tao-Tao Zhuang

Design, Synthesis
and Applications of
One-Dimensional
Chalcogenide Hetero-
Nanostructures
Novel Metal Sulfide
Hetero-Nanorods for Enhancing
Solar Energy Conversion
Springer Theses

Recognizing Outstanding Ph.D. Research

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Tao-Tao Zhuang

Design, Synthesis
and Applications
of One-Dimensional
Chalcogenide
Hetero-Nanostructures
Novel Metal Sulfide Hetero-Nanorods
for Enhancing Solar Energy Conversion
Doctoral Thesis accepted by
University of Science and Technology of China,
Hefei, China

123
Author Supervisor
Dr. Tao-Tao Zhuang Prof. Shu-Hong Yu
Department of Chemistry Department of Chemistry
University of Science and Technology University of Science and Technology
of China of China
Hefei, Anhui Hefei, Anhui
China China

ISSN 2190-5053 ISSN 2190-5061 (electronic)

Springer Theses
ISBN 978-981-13-0187-2 ISBN 978-981-13-0188-9 (eBook)
https://doi.org/10.1007/978-981-13-0188-9
Library of Congress Control Number: 2018938648

© Springer Nature Singapore Pte Ltd. 2018

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Supervisor’s Foreword

The heteronanostructures with multiple integrated functional components enable to

combine the advantages of different components and often even obtain synergetic
properties exceeding the functionality of individual component.
In particular, chalcogenide-based heterostructures are attracting significant
attention, owing to the unique physical and chemical properties decided by their
energy band gaps. Design rational synthesis approaches offer high degree of control
over composition, size, and morphology of novel heteronanostructures, and thus
achieving high conversion efficiency and long-term performance stability for
applications correlated with structural architectures is highly desired.
In this thesis, the synthesis, bandgap engineering, and applications of 1D
heteronanostrcutures are summarized and many related literatures are also high-
lighted in the introduction section. However, we still meet serious issues and
encounter severe challenges in the construction of unique 1D heteronanostrcutres
for targeted applications.
I. A seed-mediated colloidal solution-phase growth method was developed for
preparing binary chalcogenide heteronanostructures (Cu2S–PbS and Ag2S–ZnS).
II. A novel strategy was developed for fabricating ternary semiconductor–
semiconductor–metal heteronanorods. Basing on prepared ZnS nanorods, we
constructed unique 1D ternary heteronanorods -[S1-(S2/M)]-S1-[S1-(S2/M)]-S1-,
with segmented node sheaths S2 decorated by M (S1: ZnS; S2: CdS; M: Au, Pd, Pt)
through the chemical transformation strategy. The charge-separation efficacy in this
unique ternary nanosystem has been demonstrated by performance improvement of
optical-to-electrical conversion.
III. A post-synthetic processing technology was developed for producing
heteronanostructures for better performance. We demonstrated the synthesis of
unique binary -[ZnS-CdS]-ZnS-[ZnS-CdS]-ZnS- heteronanorods by integrating one
ZnS nanorod with segmented CdS tetrahedron sheaths and further constructed
ternary multi-tetrahedron sheath -[ZnS-(CdS/Au)]-ZnS-[ZnS-(CdS/Au)]-ZnS-
heteronanorods with Au nanoparticles only being grown on the vertexes and edges
of CdS tetrahedron sheaths.

v
vi Supervisor’s Foreword

IV. A synthetic technique was designed and developed for synthesizing ternary
chalcogenide heteronanorods with full-spectrum absorption. We integrated ZnS,
CdS, and Cu2-xS semiconductor sulfides one by one in a single nanocrystal, syn-
thesizing a unique ternary multi-node sheath ZnS-CdS-Cu2-xS heteronanorod so as
to realize full-spectrum absorption of solar energy.
This thesis elaborates a new and systematic approach that targets the synthesis of
1D complex heteronanostructures. These novel materials are used to optimize the
photo-electric/chemical conversion. These findings would open a new door to
rationally designing hybrid systems for solar energy conversion applications.

Hefei, China Prof. Shu-Hong Yu

February 2018
Parts of this thesis have been published in the following journal articles:

T. T. Zhuang, Y. Liu, Y. Li, M. Sun, Z. J. Sun, P. W. Du, J. Jiang and, S. H. Yu*,

1D Colloidal Hetero-Nanomaterials with Programmed Semiconductor Morphology
and Metal Location for Enhancing Solar Energy Conversion, Small 2017, 13,
1602629.
T. T. Zhuang#, Y. Liu#, Y. Li#, Y. Zhao, J Jiang*, and S. H. Yu*, Integration of
Semiconducting Sulfides for Full-Spectrum Solar Energy Absorption and Efficient
Charge Separation, Angew. Chem. Int. Ed. 2016, 55, 6396–6400. VIP paper. Front
Cover.
T. T. Zhuang, Y. Liu, M. Sun, S. L. Jiang, M. W. Zhang, X. C. Wang, Q. Zhang,
J. Jiang*, S. H. Yu*, A Unique Ternary Semiconductor-(Semiconductor/Metal)
Nano-Architecture for Efficient Photocatalytic Hydrogen Evolution, Angew. Chem.
Int. Ed. 2015, 54, 11495–11500. Hot paper. Inside Cover.
T. T. Zhuang, P. Yu, F. J. Fan, L. Wu, X. J. Liu, and S. H. Yu*, Controlled
synthesis of kinked ultrathin ZnS nanorods/nanowires triggered by chloride ions: A
Case Study, Small 2014, 10, 1394–1402.
T. T. Zhuang, F. J. Fan, M. Gong, S. H. Yu*, Cu1.94S nanocrystal seed mediated
solution-phase growth of unique Cu2S-PbS heteronanostructures, Chem. Commun.
2012, 48, 9762–9764.

vii
Acknowledgements

I would like to express my gratitude to all those who supported me during the
preparation of this thesis.
My deepest gratitude goes first and foremost to Prof. Shu-Hong Yu, my
supervisor, for his endless encouragement and guidance. I received his guidance
through the 6-year Ph.D. study and even for all stages of this thesis. He teaches me
how to do the research work, how to collaborate with others, and how to become a
respectable man. I do appreciate his patience, encouragement, and professional
instructions during my thesis writing. Without his consistent encouragement and
illuminating instruction, I would still grope in the darkness, amid thunder and
lightning. He works hard and spends every minute on scientific adventure, which
inspires us to do our best in the research. It is his influence and encouragement that
makes me decide to become a scholar and a teacher.
I also owe a special debt of gratitude to all the teachers and students in Yu
laboratory, from whose devoted enlightening lectures and helpful discussions I have
benefited a lot and academically prepared for the thesis. It would not have been
possible to have such a wonderful Ph.D. life without you.
Last but not least, my gratitude also extends to my parents, wife, brother, and
other relatives who have been assisting, supporting, and caring for me all of my life.
Your selfless love gives me courage to pursue my dream.

ix
Contents

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... 1
1.1 Semiconducting Hetero-Nanostructures . . . . . . . . . . . ......... 1
1.2 Synthetic Methodology of Chalcogenide
Hetero-Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . ......... 2
1.2.1 Colloidal Chalcogenide Hetero-Nanostructure
Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ......... 2
1.3 Band Engineering and Functions of 1D Chalcogenide
Hetero-Nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Seeded Growth Core/Shell Nanorods . . . . . . . . . . . . . . . . 8
1.3.2 Chalcogenide-Metal Heteronanorod . . . . . . . . . . . . . . . . . 12
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
2 Seeded Mediated Growth for Binary Chalcogenide
Heteronanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 23
2.1 Cu1:94 S Nanocrystal Seed Mediated Solution-Phase Growth
of Unique Cu2 S-PbS Heteronanostructures . . . . . . . . . . . . . . . ... 23
2.2 Controlled Synthesis of Kinked Ultrathin ZnS
Nanorods/Nanowires Triggered by Chloride Ions:
A Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 31
2.2.1 Synthesis and Characterization of Kinked and Straight
Ultrathin ZnS Nanorods . . . . . . . . . . . . . . . . . . . . . . . ... 33
2.2.2 The Effect of Chloride Ions on the Synthesis
of Kinked ZnS Nanostructures . . . . . . . . . . . . . . . . . . ... 36
2.2.3 The Effect of Reaction Temperature . . . . . . . . . . . . . . ... 38
2.2.4 Synthesis of Kinked ZnS Nanowires with Higher
Aspect Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2.5 Formation Mechanism of Kinked ZnS Nanorods . . . . . . . . 42
2.2.6 Optical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.2.7 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47

xi
xii Contents

3 A Unique Ternary Semiconductor-(Semiconductor/Metal)

Nano-Architecture for Efficient Photocatalytic Hydrogen
Evolution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 53
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 53
3.2 Synthesis Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 54
3.3 Structure Characterizations of Multi-node Sheath
Heteronanords . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 55
3.4 Theoretical Simulations of the Material Bandgap
Alignments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 61
3.5 Optical Properties and Photocatalytic Hydrogen Evolution
Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 64
3.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 69
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ...... 74
4 One-Dimensional Colloidal Hetero-Nanomaterials with
Programmed Semiconductor Morphology and Metal
Location for Enhancing Solar Energy Conversion . . . . . . . . . . .... 77
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 77
4.2 Synthesis Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .... 78
4.3 Structure Characterizations of Tetrahedron-Sheath
Heteronanorods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.4 Theoretical Simulations of the Material Bandgap Alignments . . . . 83
4.5 Photo-Electric/Chemical Conversion Application . . . . . . . . . . . . . 85
4.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5 Integration of Sulfides Enables Enhanced Full-Spectrum Solar
Energy Absorption and Efficient Charge Separation . . . . . . . . . . . . 95
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
5.2 Synthesis Design . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
5.3 Structure Characterizations of Ternary Heteronanorods . . . . . . . . . 96
5.4 Bandgap Alignment Simulations . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.5 Solar Energy Conversion Application . . . . . . . . . . . . . . . . . . . . . 105
5.6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
Chapter 1
Introduction

1.1 Semiconducting Hetero-Nanostructures

Semiconducting nanomaterials with the size between 1 and 100 nm are particular
attractive in the material science field due to the quantum confinement effects dic-
tating their unique optical and electronic properties [1–15]. Band gap energy (Eg ),
dependent by a composition, is the factor for characterizing bulk semiconductors.
The definition of Eg is the minimum energy, requiring to excite an electron from
the ground state valence band into the vacant conduction band. An electron enables
to be excited by the absorption of a photon with the energy greater than Eg , leav-
ing an orbital hole in the valance band. The negative electron and positive hole are
mobilized with an electric field to generate the current. The lowest energy state is
an electrostatically bonding electron-hole pair, named as the exciton. The exciton
has a finite size within the crystal, defined by the Bohr exciton diameter, organizing
the transition between the regime of bulk-like properties and the quantum confine-
ment effect. The high surface area of semiconducting nanomaterials enhances the
surface effect in applications. The quantum confinement effect and the surface effect
of semiconducting nanomaterials attracts researchers to investigate materials’ broad
applications in solar energy conversion, optoelectronic devices, molecular and cel-
lular imaging, and ultrasensitive detection [16–18].
In the past decades, a big development has been achieved in the synthesis of
colloidal semiconducting nanocrystals (CSNs) and in understanding of the factor
of composition, morphology, and size of the CSNs for their physical properties.
However, it is often difficult to simultaneously achieve sufficient efficiency, stability,
and low cost in luminescent and energy conversion devices with a single material
component. The hetero-nanostructures (HNs) with multiple integrated functional
components could combine the advantages of different components and often even
obtain synergetic properties exceeding the functionality of individual components
[19]. HNs’ physical properties are dependent on the potential energy profile, con-
trolled by the chemical composition of each component. HNs can be categorized

© Springer Nature Singapore Pte Ltd. 2018 1

T.-T. Zhuang, Design, Synthesis and Applications of One-Dimensional
Chalcogenide Hetero-Nanostructures, Springer Theses,
https://doi.org/10.1007/978-981-13-0188-9_1
2 1 Introduction

Fig. 1.1 Band gap alignments of heterostructures. a Type-I; b Type-II

into two major types referring to the relative position of the band gaps of different
components. Type-I structure is defined the band gap of one component is embed-
ded within the other component. When excitation, both excited electron and hole
carriers occupy the lowest electronic states, to the applications of photoemission
devices. In type-II structure, the band gaps of the two components are staggered with
respect to each other. The staggered band structure enables to a spatial separation
of the excited two kinds of carriers to different regions of the two compositions by
excitation, investigated in the energy conversion fields (Fig. 1.1).

1.2 Synthetic Methodology of Chalcogenide

Hetero-Nanostructures

As one important part of semiconductor materials, chalcogenide-based structures are

attracting significant attention, owing to the unique physical and chemical properties
decided by their energy band gaps. For instance, copper sulfide is a good candidate
for the solar energy barriers owing to its well photovoltaic effect; the transition metal
sulfides are favorable redox catalysts instead of platinum in the fuel cell field; the
lead sulfide with narrow band gap can be used as the infrared sensor. Quantum
confinement effects lead to size-dependent electronic structure of metal sulfides,
affecting the exciton wave function to change the density of electronic states and the
energy level separation (Fig. 1.2) [19, 20].

1.2.1 Colloidal Chalcogenide Hetero-Nanostructure Design

1.2.1.1 Synthetic Strategies

There are two strategies for colloidal HNCs synthesis: the single-stage and multi-
stage seeded growth. For the single-stage approach, the HNC can be prepared via
sequentially adding the precursors of the different components in the same reaction
system. However, this strategy is difficult to provide enough control for the targeted
1.2 Synthetic Methodology of Chalcogenide Hetero-Nanostructures 3

Fig. 1.2 a The colours of colloidal CdSe nanocrystal solutions under UV excitation. b Schematic
illustration of the quantum confinement effect on the band structure using a semiconductor material;
The suspensions of CdSe NCs shown in the bottom panel. Reproduced with permission from Ref.
[19]

synthesis of high-quality colloidal HNCs though it is appealing for the simplicity.

Uncontrolled interfacial alloying is easy to occur in the single-stage synthesis due to
that the concentration of monomers of the first component should still be substantial
when the second one is introduced. In contrast, for the multi-stage approach, it
is highly versatile, thus providing many advantages compared to the single-stage
strategy:
(a) Introducing performed nuclei to the reaction system is effective to separate
nucleation and growth, leading to the better control over the growth stage, both
under homo- and hetero-epitaxy.
(b) Different conditions can be used to grow each component of the hetero-
nanocrystal. Thus, synthesis of complex multi-component hetero-nanocrystals
with targeted control is possible.
(c) Post-synthetic of the seeds, such as purification, size-selection, and ligand
exchange, enables to improve the quality of the seeds for judicious surface
manipulation.
(d) Controlled hetero-interfacial alloying becomes possible via changing the growth
temperature or tuning the ratio between the precursors [21].
(e) The method is highly flexible due to the various synthesis techniques.
We will briefly discuss these techniques as below.
Introduction of seeds. This is the most general used technique to synthesize HNCs,
especially suited for slow growth. The new precursor for growing HNC is added to
the seed NCs solution with a suitable surfactant and reacted at a proper temperature
(so-called “heating up” method [22, 23]). Such heteroepitaxial growth may also be
photo- rather than thermally-induced. Photo boosted growth has been reported to
induce selective deposition of Au NCs on the sulfur-rich end facets of CdS NRs
[24]. The precursor addition should keep relatively constant growth rates to avoid
homogeneous nucleation, and can be performed by some methods: (1) dropwise
4 1 Introduction

addition of all precursors, (2) alternate injection of each precursor separately, or (3)
dropwise and alternate addition. The effectiveness of each method depends primarily
on the precursor reactivity.
Seed injection. For this strategy, one precursor and seed NCs are injected together
in a reaction solution, containing another precursor and surfactants. Using a high
concentration of precursors and proper surfactants can induce the anisotropic growth.
This technique enables to prepare anisotropic HNCs with well defined length and
diameter for various compositions, including dot core/shell nanorods, tetrapods, and
octapods.
Cation exchange. A large excess of the cation precursors of the new phase is
added to a solution of the initial NCs at mild temperatures (0–100 °C), resulting in
the exchange reaction in which the new cation diffuses into the seed NC and replaces
the parent cation, while keeping the anionic sublattice unaffected [25, 26]. The size
and shape of the parent NC is preserved [27]. This exchange process provides a very
attractive route to produce shape-controlled HNCs which are not attainable via the
conventional seeded growth methods.
Sacrificial domain replacement. This route is to obtain a HNC via the replacement
of a sacrificial component of a parent HNC using the desired component [28, 29].
This approach allows to fabricate the colloidal HNCs which are unfeasible through
direct heteroepitaxial growth methods because the shape and position of the sacrificial
domain are preserved. Basically, the above-mentioned ion exchange method can also
be regarded as one sort of the sacrificial replacement strategy.

1.2.1.2 Guidelines for the Synthesis

The present synthesis protocol for the colloidal HNC is still a largely empirical
endeavour, leading to some original conditions. The initial parameters are further
optimized relying on the outcome of these exploratory experiments. The develop-
ment requires a strangle approach of the complex nature of colloidal NCs via sys-
tematically exploring the multidimensional synthetic parameter space. This section
we will discuss how the fundamental principles presented above are able to used as
guidelines for a rational design of novel synthesis schemes.
Seed choice. In general, the choice is unlimited since all colloidal NCs can be used
as seeds, regardless of shape or composition. However, as we know the characteristics
of the seeds strongly affect the final shape of the HNCs and impose constraints on the
nature of the overgrowing segment. We here focus on one particular system—CdSe
based system—to reveal the decisive role of the seeds in the colloidal synthesis of
HNCs. CdSe QDs and based HNCs have been work horses of colloidal synthesis
since the inception of this field, and keep going to lead to new insights. Since many
sophisticated HNCs have been prepared based on CdSe seeds, these HNCs are ideal
to demonstrate the possibilities of the colloidal synthesis of HNCs. For instance, the
morphology and connectivity of the colloidal HNC can be tuned using NCs with
controlled shapes as seeds (Fig. 1.3) [30–32].
1.2 Synthetic Methodology of Chalcogenide Hetero-Nanostructures 5

Fig. 1.3 Schematic illustration shows the HNS morphologies that can be tuned by seeded growth
using CdSe nanocrystals with different shapes as seeds: a quasi-spherical NCs, b nanorods

HNC’s architecture choice. The morphology and composition of the overgrowing

domain are chosen based on the desired HNC’s properties and the new domain’s role.
The nature (metal and semiconductor, etc.) and properties (band position, electron
and hole effective masses, magnetic susceptibility, and optical transitions, etc.) of
the overgrowing material are considered as the essential parameters. Moreover, the
surfactant layer should be taken into account when designing the HNC’s architecture
due to its utilization of impart properties to the HNC. The composition’s choice is
not unrestricted. The overgrowing material should be chemically and structurally
compatible with the seed surface.
Reaction parameter choice. Precursors, surfactants, and temperature are gener-
ally considerable as reaction parameters. A unique synthesis technique should be
adopted relying on the intended morphology and composition of the HNCs. The
heterogeneous nucleation rates and heteroepitaxial growth dynamics are controlled
using some reaction parameters, including concentration and characteristics of seeds,
concentration and nature of precursors and surfactants, and the growth temperature.
These parameters are strongly interdependent, determining the HNC’s composition
and architecture by the optimum balance between them. We here briefly discuss
the examples of CdSe based HNCs for different shape categories to highlight the
considered essential aspects when tuning the reaction parameters [33].
(a) Concentric core/shell QDs. Concentric core/shell QDs have been focused as
the majority of the investigations on colloidal HNCs, resulting in the development of
synthetic methodology that achieves a high degree of control over the heteroepitaxial
shell growth and thus yielding highly luminescent and stable QDs. Slow heteroepi-
taxial growth on the facets of highly crystalline nearly seeds is the basis of obtaining
high-quality shells. The lattice mismatch between seed and shell should be small,
especially if thick shells (>3 layers) are desired. Alternatively, the lattice mismatch
can also be gradually adapted using gradient shells and a multishell approach (e.g.,
CdSe/CdS/(Cd-Zn)S/ZnS core/multishell QDs [34]).
6 1 Introduction

The growth temperature must be sufficiently low to prevent alloying, inter-particle

ripening, and homogeneous nucleation, but also high enough to enable the precursors
to react, and heterointerfacial annealing and relaxation. The binding between sur-
factant and the seed’s surface should be not too strong or too selective at the growth
temperature. Moreover, low monomer fluxes should be used to avoid homogeneous
nucleation and promote heteroepitaxial growth to prevail. The monomer flux is tuned
via the precursor reactivity and addition rate. Thus, high reactivity precursors should
be introduced at slower rates and at lower temperatures. The utilization of low reac-
tive precursors improves the flexibility of the synthesis protocols, since there are a
number of different precursors currently available. Another advantage of low reactive
precursors is the reactivity can be modulated by tuning surfactants.
An alternative method to avoid monomer accumulation during the growth for
thick shell is to increase the growth rate via increasing the reaction temperature.
However, this strategy still has undesired effects, since higher temperatures increase
not only the reactivity of the growing NCs, but also the mobility of surface atoms,
the solubility of NC, and the formation rate of monomer. Thus, it is easy to enhance
inter-NC ripening, interfacial alloying, and homogeneous nucleation.
(b) Heterodimers. Once the wettability between overgrowing material and the seed
is not good, the heterogeneous growth may occur only on a defined facet, so that the
lattice mismatch is minimized. A mechanism is used to grow Au NCs on CdSe seeds
(large lattice mismatch ~50%) [35], and thus yielding CdSe/Au heterodimers. The
heterogeneous nucleation of CdSe NCs on seeds has also been investigated, such
as CdSe@Fe2 O3 heterodimers [36] and CdSe@NaYF4 :Yb,Er heteronanostructures
[37]. Alternatively, the second material can first grow as an amorphous shell, cir-
cumventing the difficulty of lattice mismatch. The crystallization of the shell can
be induced by subsequent annealing, accompanied by the de-wetting and retraction,
resulting in the formation of a heterodimer [38].
(c) Core/shell nanorods. The shell growth on a nanorod seed is performed under
similar conditions to those used to synthesize concentric shells over a spherical-
like NC seed. Core/shell nanorods based on chalcogenide semiconductor materials
occurs primarily in the length direction owing to the higher reactivity of the polar
facets [39, 40].
(d) Heteronanorods, heterotetrapods, and nanodumbbells. Spherical-like CdSe
NCs are used as seeds for the heteroepitaxial growth of a serious of anisotropic
HNCs, such as CdSe/CdS dot-core/rod-shell nanorods and heterotetrapods. The dif-
ference with concentric core/shell QD growth is the control of growth conditions
that favor anisotropic growth, including high monomer concentration, high reaction
temperature, and surfactants that selectively bind to the non-polar facets of chalco-
genide WZ semiconductors. The shape of the HNC is dictated via the seed’s crystal
structure and shape under such conditions (e.g., WZ produces rods, while ZB yields
tetrapods or octapods, for tetrahedral or cuboctahedral seeds, respectively). In addi-
tion, CdS rod shells can grow on WZ CdSe seeds at low temperature (120–130 °C)
using highly active precursors (Cd(CH3 )2 and (TMS)2 S) and TOPO, TOP and HDA
as surfactants. It also needs an excess of the S precursor to grow anisotropic structure
in this case [41].
1.2 Synthetic Methodology of Chalcogenide Hetero-Nanostructures 7

The utilization of CdSe nanorods as seeds enables the formation of nanomatch-

sticks, nanodumbbells, heteronanorods, or heterotrapods, relying on the growth con-
ditions. High precursor concentration is good for producing heterorods and heterote-
trapods when under conditions that promote anisotropic growth [42–44]. Owing
to the reactivity difference between anion-terminated and cation-terminated polar
facets, linear heteroepitaxial growth may take place on one tip of the nanorod while
branching occurs at the other. In contrast, low monomer concentration and low tem-
perature that favor isotropic growth lead to produce nearly spherical NCs at both
tips of the rods, obtaining dumbbells. In addition, some special conditions such as
low temperature and fast injection of low concentration precursor will induce the
materials selectively grow on only on tip of the nanorod, yielding nanomatchsticks
[45]. Heteroepitaxial growth on CdSe tetrapod seeds may take place either by linear
extension of each arm or by branching at the tips of the arms, relying on the precursor
concentration.
Dimension of overgrowing segment control. The dimensions of the HNCs can
be tuned by the total amount of precursors added in reaction referring to the seed
concentration, the growth temperature, and the reaction time. Thus, it is essential
to understand the knowledge of the size, the shape, and the concentration in the
reaction of the NCs when used as seeds. The absorption spectroscopy is well known
used to determine the concentrations of seeds. It is common to use the band edge
absorption coefficient for this purpose. However, it also may lead to potentially large
errors in the concentration analysis because the band edge absorption coefficient
is strongly dependent on size and shape, and thus inherently sensitive to the size
dispersion of the NC ensemble. In contrast, the absorption coefficient at energies
far away from the band edge scales linearly with the NC volume, both for spherical
NCs and for nanorods, leading to a more reliable parameter, irrespective of size
and shape dispersion. Moreover, the bulk optical constants can directly determine
the absorption cross section at high energies [46]. Thus, to minimize the error of
the concentration of seeds, we recommend the utilization of the molar absorption
coefficient at higher energies than that of the band gap.

1.3 Band Engineering and Functions of 1D Chalcogenide

Hetero-Nanostructures

Tuning the physical properties by controlling the dimensions of nano semiconductors

attracts the interesting in the field of low dimensional material, including 0D QDs,
1D nanowires, and 2D quantum wells. 1D materials are good to achieve some novel
properties due to their dimension, size, and composition. The most investigation
of 1D chalcogenide heteronanostructures focus on binary heteronanorods based on
sulfides, categorized into two bins by the composition: semiconductor-semiconductor
and semiconductor-metal.
8 1 Introduction

1.3.1 Seeded Growth Core/Shell Nanorods

Seeded nanorods, one type of heteronanorods, are gained considerable attention in

recent years [20]. Such NCs, in which a core of one chalcogenide semiconductor is
embedded in another nanorod shaped shell, become as an important branch in the
heteronanostructure group. These materials enable unique properties induced by the
integration of domains with different dimensions in the same structure.

1.3.1.1 Optical Response, Excitonic Behavior, and Band Structure

Even though the chemical compositions are quite different in the heteronanorods,
sizes and dimensionalities vary greatly in these components, resulting in similar
properties despite different band structures. Particularly, when one component is
much more than the other, the overall absorption of the hybrid structure is domi-
nated by the larger component. This phenomenon is obvious in the type-I (and also
quasi type-II) structure, in which the core absorption is red-shifted in respect to the
shell absorption and the absorption characteristic of each component can be eas-
ily distinguished. Figure 1.4a shows the absorption and emission spectra of seeded
CdSe/CdSe nanorods (the diameter of CdSe core and CdS nanorod are 3.2 and 5 nm,
respectively; the length of CdS nanorods is 50 nm), and corresponding absorption and
emission spectra of CdSe core (inset). The absorption features above 500 nm result
from ground state transition in the CdSe core; while sharp exciton features below
500 nm are attributed to CdS shell, which is consistent with the bulk CdS (bandgap
of 2.482 eV). Just as quantum dots, the emission spectra of seeded nanorods are
right from the band edge state, which correspond to the lowest excited state in CdSe
nanocrystals. Shell passivation, to some extent, red shifts the emission owing to
the weakened confinement on excitons. Concomitantly, core passivation by the shell
greatly reduced dangling bonds on CdSe cores, as a result the quantum yield increases
substantially. Furthermore, ZnSe/ZnS system, derived from CdSe/CdS nanorods via
cation exchange reactions, shows a similar absorption characteristic (Fig. 1.4b) [47].
We can observe absorption features belonging to ZnSe core at a wavelength above
335 nm, and the enhanced absorption below 335 nm is attributed to photo excita-
tion of ZnS nanorods. The optical properties accord well with zinc-blende ZnS with
bandgap of 3.58 eV.
In the type-II structure, the absorption of large-volume component is can be either
stronger (CdTe/CdSe, Fig. 1.4c) or weaker (ZnSe/CdS [48], Fig. 1.4d) than the small-
volume one. In the latter case, absorption from the smaller one is just overlapped
with the larger one, thus undistinguishable in the spectrum. Absorption features
of the hybrids red shifted compared to single component due to the type-II band
structure. We can also observe electronic transitions from the type-II structure—a
weak absorption tail at the red side of single component (shallows in Fig. 1.4c–d).
The direct consequence of dimension difference is that, the extinction coefficient
in the large-volume component is significantly higher than the small one, even in
1.3 Band Engineering and Functions of 1D Chalcogenide Hetero-Nanostructures 9

Fig. 1.4 Absorption and PL spectra of samples: a CdSe/CdS dot in rod, b ZnSe/ZnS dot in rod, c
CdTe/CdSe dot in rod, and d ZnSe/CdS dot in rod. Reprinted with permission from Refs. [47, 58]

the multi-photon absorption process. Xing et al. found that cross sections for two-
and three-photon absorption are four orders of magnitude larger than CdSe QDs and
depends strongly on its volume [49, 50]. These results indicate the seeded nanorods
have applications in nonlinear optics. However, several difficulties lay in the road to
fully utilize the type-II structure for charge separation or type-I structure for light
emission, which requires not only efficient radiation absorption, but also efficient
charge transfer from shell to core and reduced carrier trapping by the interface/surface
defects. Taking CdSe/CdS as an example, chare carriers can transfer efficiently from
shell to core, greatly increasing the quantum yield of CdSe band-edge emission.
This suggests very little interface/surface traps in the CdSe/CdS system [51]. In
the type-II structure, chare separation elongates the radiative lifetime and increases
the ratio of nonradiative process. Consequently, the photoluminescence quantum
yield is commonly low. Despite that, PLQY of seeded ZnSe/CdS type-II nanorods
reaches up to 45% when excited at 532 nm (close to the bandgap). While PLQY
decreases to 26% when excitation wavelength is changed to 475 nm. It suggests that
the density of surface traps is higher than that of interface. Conversely, CdTe/CdSe
10 1 Introduction

system exhibits low PLQY in spite of the excitation energy, which is attributed to
the surface irregularity and traps.

1.3.1.2 Charge Carrier and Exciton Localization

The distribution of energetic carriers—which influences properties related with

excited states, such as PLQY, PL lifetime, and polarization—is of great signifi-
cance. Generally, their distribution is determined by the band offset in the system,
but quantum confinement effect and strain can also affect band offset and finally the
spatial distribution of charge carriers [52].
When the band offset is small, influences of the latter is much more obvious. In
the bulk, CdSe/CdS behaves type-I structure, the conduction band offset is 0.3 eV
and the valence band offset is 0.44 eV [53]. Therefore, electrons and holes are both
concentrated in the CdSe core. Luo and Wang conducted the charge patching ab initio
calculations and showed that strain, quantum confinement effect, piezoelectric effect,
and dipole moment interacts with each other, which may reduce the band offset and
even turn over the band structure into type-II [54]. Muller et al. concluded that
there exists obvious size effect in the CdSe/CdS seeded nanorods though optical
characterizations. They showed that the relationships between experimental radiative
lifetime, Stokes shift, and the aspect ratio of nanorods can be fitted with effective
mass approximation model (conduction band offset is assumed to be zero) [55, 56].
Transient photoluminescence and absorption results [57] showed that bleach signals
appear at both band-edge state and 460 nm, when excited at band-edge energy.
Bleaches at 460 nm is related to photoexcitation of nanorod shell. All these findings
can be attributed to the near-zero conduction-band offset. She et al. found that PLQY
in the seeded CdSe/CdS nanorod and its radiative lifetime obtained from the PL decay
test depends strongly on the shell volume, but independent of the core radius.
Although above results indicate that the conduction-band offset in the seeded
nanorods is zero, several additional experiments suggested a bulk-like type-I struc-
ture. Probably, the most direct characterization method is scanning tunneling spec-
troscopy measurements, which is able to detect the electronic structure at specific site
of nanorods. Figure 1.5a displays the experimental (black) and theoretically calcu-
lated curves of dI/dV versus applied potential for CdSe/CdS nanorods. These results
indicate the bandgap of nanorods is 2.8–2.9 eV (Fig. 1.5a, curve 1 and 2). The core sits
at 1/3 length of the nanorod, with bandgap of 2.3 eV (Fig. 1.5a, curve 3). Comparing
the tunneling current at different positions, we can find that the biases corresponding
to tunneling currents of valence band and conduction band, respectively, is lower
than the other two. As the tunneling current at specific position is determined by its
density of states, we can deduce that both electrons and holes are confined in the core.
Current imaging tunneling spectroscopy measurements found that the ground-state
wavefunctions localizes intensively (Fig. 1.5c). The experimental results coincide
well with the type-I structure (Fig. 1.5d).
Measurements on seeded type-II ZnSe/CdS nanorods (Fig. 1.5b) suggest that the
bandgap of CdS is 2.7–2.9 eV, as observed from curve 1 and 2. The bandgap at 1/4
1.3 Band Engineering and Functions of 1D Chalcogenide Hetero-Nanostructures 11

Fig. 1.5 dI/dV versus V tunnelling spectra at different locations along the a CdSe/CdS and b
ZnSe/ZnS seeded rods and the corresponding theoretical curves (red). The energy gap shown as
dashed lines. Insets show the 3D topographic STM images. c Cross-sections of a current image
(CdSe/CdS, 1.2 V, green curve) and of the calculated electron ground-state probability density
(blur curve), constructing the localization of the electron ground state in the core. d–e Schematic
illustration show the band structures and wave functions for these two HNCs. Reprinted with
permission from Ref. [58]

length of the nanorod is 2 eV, which is cause by ZnSe core (curve 3), consistent
with the type-II structure with conduction band offset of −1.02 eV and valence band
offset of 0.78 eV.

1.3.1.3 Application in Devices

Unique properties revealed in the heterostructured nanorods promise them attractive

applications in the optoelectronic devices. Seeded nanorods with type-I structure
(typically CdSe/CdS) have shown tunable emission, polarization, and high quantum
yields, thereby are suitable for various devices. Rifat et al. [59] fabricated light-
emitting devices with short CdSe/CdS nanorods (4.5 nm × 10 nm). Oriented nanorods
in polyvinylcarbazole (PVK) matrix through mechanical rubbing enable the device
polarized emission with electroluminescence polarization ratio of 1.6 and intensity of
0.65 Cd/A (overall external PLQY of 0.49%). Polarization ratio can be enhanced to
3.5 by modulating rubbing parameters. Rizzo et al. assembled CdSe/CdS nanorods on
the water/air interface through evaporation-induced self-assembly and further trans-
fer the film onto devices with PDMS for polarized LED. The polarization ratio can
be as high as devices fabricated by mechanical rubbing, but showed low photolumi-
nescence intensity. Nonetheless, this method opens new approaches for multi-layer
printing of polarized devices with high luminescence intensity [60].
Single CdSe/CdS nanorod is a potential single-photon sources (single-photon
emitter) for quantum information devices. Contrary to single-component nanorods,
density of states of CdSe core are more discrete, therefore can be used as room-
temperature single-photon sources. Semiconductor nanorods can also be used as
gain media for amplified spontaneous emission (ASE) and polarized lasing [61] due
12 1 Introduction

to their slow Auger recombination rates. Zavelani-Rossi et al. fabricated efficient

laser using “coffee strain” cycles of CdSe/CdS nanorods [62, 63]. They observed
low-threshold ASE and two-photon ASE [64, 65]. Intriguingly, in the short core-
shell nanorods, ASE comes from CdSe core; while in the long nanorods, ASE is
also observable from the shell, with emission wavelength blueshifted 70–130 nm
compared to PL peak. This strongly depends on the excitation energy and can be used
for optical switch. Moreover, the emission properties can be controlled by external
electric field, which will bend the band structure, shift the emission wavelength, or
switch the on/off state [66]. Besides, electric field can facilitate charge separation
and elongate exciton lifetime to several microseconds. These features can be utilized
for optical switch and optical memory devices, and further for optical modulation in
displays [67, 68].
Another interesting application of heteronanorods is color conversion to control
color temperature in energy-saving light-emitting devices. Shells in the nanorods can
absorb high-energy photons while cores emit more redshifted photons, achiving color
conversion from blue to red. Embedding nanorods into polymer matrix or microcaviy,
forming multilayer devices, can suppress the emission color and even the conversion
efficiency [69]. Recently, photon crystals containing these heterostructures becomes
fascinating and are promising for control over the emission color, polarization, width,
and direction [70, 71].

1.3.2 Chalcogenide-Metal Heteronanorod

Thanks to the rapid development in the syntheses of semiconductor and metal

nanocrystals, complex heterostructures based on them can be achieved now [72].
For colloidal semiconductor nanocrystals, quantum confinement effect contributes
to their unique optical/electronic properties; for colloidal metal nanocrystals, plas-
monic effect also acquires deep research. All of these findings pave the way for our
research in semiconductor-metal hybrid structures.

1.3.2.1 Optical Property

The combination of semiconductor and metal brings about synergistic effect rather
than a simple superposition of each component, as we can observe from the absorption
spectrum. In the matchstick-like and core-shell heterostructures, the coherent and
incoherent interactions between semiconductor and metal may induce broadening
and shift of the first exciton feature [73, 74] and red-shifted plasmon resonance
feature [75]. Changes of optical properties in the hybrid structure probably result
from formation of new electronic states at the interface of metal and semiconductor.
Shaviv et al. proved experimentally and theoretically that, electrodynamic effect
can explain the main absorption features in CdS-Au heterostructure [76]. As shown
in Fig. 1.6a, relationship between absorption cross section and wavelength in the CdS
1.3 Band Engineering and Functions of 1D Chalcogenide Hetero-Nanostructures 13

Fig. 1.6 a Plots of extinction cross section (µm2 ) versus wavelength for 16.5 × 5.8 nm bare CdS
nanorods (dashed black curve), 6 nm gold bare nanoparticles (rod dotted curve), a mixture of these
two domains (yellow plus blue area, narrow black curve), CdS-Au HNP (thick black line), and the
difference between HNP versus the mixture of its components (green area). b The corresponding
DDA simulations. Reprinted with permission from Ref. [76]

nanorods, Au nanoparticels, and their hybrids indicates that, the plasmon peak red
shift from 527 to 538 nm (ca. 50 meV). Considering dielectric functions in individual
component, discrete dipole approximation (DDA) simulations on heteronanostruc-
tures with the same dimension coincide with experimental results (Fig. 1.6b). The
fact that the real part of refractive index in semiconductors is larger than that of
solvent is presumed to be the reason for this shift. The refractive effect on plasmon
resonance peak is also applied for metal nanoparticles [77, 78]. The exciton and
plasmon peaks in CdS-Au are separated, however overlapped in CdSe-Au.
Metals on semiconductor will give rise to some new physical phenomena other
than absorption changes. Metals in the hybrids can be treated as a near-field source
[79, 80]. The resonant field can penetrate into semiconductors and fast decay on metal
surface, forming a strong gradient field. Near-field effect can be utilized to enhance
the oscillation strength of forbidden dipole transitions, thereby is able to control the
optical selection rules. Jain et al. proposed the atomistic simulations of oscillation
strength for each transition in matchstick-like CdSe-Au and CdS-Au nanorods. A
gradient resonant electric field propagates along the axis of nanorods, enabling the
quadrupole-induced transitions and multipolar transitions, which is prohibited in the
far-field selection rules [81].
The evolution of surface plasmon resonance (SPR) in metal-semiconductor core-
shell nanostructure suggests that changing the type and thickness of semiconductor
shell can modulate SPR effect. AuAg, Ag2 S-Au, and CdS-Au core-shell nanorods
show both transverse and longitudinal SPR signals. When Ag shell is grown on Au
nanorods, a blue-shift absorption feature is observed relative to SPR peaks in Au
nanorods, while a redshifted one is observed for CdS shell, which increase with
thicker shell. All these results are related with refractive index changes of the neigh-
boring shell [82].
14 1 Introduction

It’s also of significance to research the fluorescence enhancement [83, 84] and
quenching [85] of semiconductor-metal hererostructures. There are two explanations
for PL enhancement: first, enhanced excitation, which results from increased excita-
tion under SPR electric field; secondly, enhanced emission, which is influenced by
the coherent interactions between SPR near-field and transition dipole moment, thus
leading to increased radiative recombination rate [86]. The enhancement is strongly
correlated with the distance and interface between metal and semiconductor, and the
spectral overlaps between SPR and PL peak [87, 88]. Metal directly interfaced with
semiconductor usually leads to PL quenching because electrons on the excited states
of semiconductors will transfer to metals, increasing the nonradiative recombina-
tion rate and meanwhile shorten the PL lifetime. This effect is generally observed
in many heterojunctions, such as CdS-Au, CdSe-Au, and CdTe-Au nanoparticles.
Another interesting thing is that, the PL of semiconductor quantum dots and plas-
mon of metals may couple, especially when the PL is not completely quenched. This
process is delicately demonstrated in CdSe QDs coupled with metal nanowires [89].

1.3.2.2 Photo-Induced Charge Separation

Conjunction of semiconductor and metal in the form of a heterostructure can facili-

tate fast transfer and separation of photo-generated charge. Band alignment between
semiconductor and metal lower or elevate the Fermi level of metal into the bandgap
of semiconductor, promoting electron transfer from excited state of semiconductor
to Fermi level of metal. Holes may be localized at the surface trap states of semi-
conductors, forming type-II or quasi type-II core-shell structure. The efficiency and
rate of this process is dependent on the type, structure, and morphology of two com-
ponents. Charges transferred to metals (such as Au and Ag) can accumulate due
to single-electron charging effect, which leverage the Fermi level (ca. 0.1 eV per
electrons under vacuum condition) [90]. With the presence of irradiation and hole
scavengers, metals can continuously accept electrons until the equilibrium of Fermi
level and conduction band.
Charge transfer dynamics have great impact on applications of photovoltaic mate-
rials and photocatalysts. Many heterostructured systems have been extensively inves-
tigated via time-resolved spectroscopy. The discrepancies in their dynamics possibly
originate from material differences, interfacial properties, crystalline structures, and
surface traps of semiconductor and metal. Mongin et al. demonstrated the ultra-
fast separation process of photogenerated charges in single-metal tipped CdS-Au
nanorods. The electron transfer rate is estimated to be sub-100 fs [91]. Contributions
to the charge transfer can be calculated by detecting domains of semiconductor and
metal separately (the pump-probe method is shown in Fig. 1.7). Besides heat effect
from metals, the amplitude difference of pumps for metal SPR (Fig. 1.7a) and semi-
conductor absorption (Fig. 1.7b) can be attributed to charge transfer. Combining
this result with the absorption thresholds of CdS nanorods and CdS-Au nanorods
(480 nm), we can have the time scale of charge separation.
1.3 Band Engineering and Functions of 1D Chalcogenide Hetero-Nanostructures 15

Fig. 1.7 Ultrafast response to detect the Au nanoparticle spectra region, measuring CdS-Au
nanomatchsticks solution for a pump wavelength a /pump = 540 nm and b /pump = 400 nm.
Reprinted with permission from Ref. [26].

Transient absorption spectroscopy measurements of CdS-Pt [92, 93] and

ZnSe/CdS-Pt [94] suggest that their charge separation rate is slower, about 3–4 and
14 ps, respectively. The difference lies in the band alignment. For type-II ZnSe/CdS-
Pt, it may be the coulomb interaction between electrons and holes that leads to
longer charge-transfer time. Holes confined in the ZnSe core will also increase the
electron density nearby and reduce the overlap of electron wavefunction with that of
Pt domains. However, other technologies are still required to confirm the time scales
of charge transfer.
Besides, the charge separation process is affected by the environment. Sacrificing
agents, which act as hole scavengers, will affect the charge transfer dynamics. Berr
et al. demonstrated this influence via the surface-decorated CdS-Pt nanorods. With the
presence of hole scavenger, the averaging time for electrons transferring to Pt domains
is delayed up to 8000 ps, while the time is reduced to 400 ps for the same system
with the absence of scavenger [95]. Theoretic models suggest that, without hole
scavenger, electrons and holes are combined together due to coulomb interaction,
therefore electrons are localized near holes, which are trapped on the surface. As Pt
domains are mainly photo-deposited on surface defective sites., the electron wave
functions are largely overlapped with metal domains, resulting in fast charge transfer.
While in the presence of hole scavengers, weak-confined electrons will propagate
along the axis of nanorods, reducing the overlap of electron wave functions with metal
domains. Understanding and controlling the charge transfer dynamics by tuning the
structure and composition of heteronanostructures is vital to solar energy harvesting
and conversion.

1.3.2.3 Photocatalysis

One of the most attractive applications for heterostructures is photocatalysis. Syner-

getic effects discussed above, such as electronic structures, band alignment, charge
16 1 Introduction

Fig. 1.8 a Schematic illustration shows the photocatalytic reaction using HNPs. b Quantum effi-
ciency for hydrogen evolution using CdS-Pt rods (yellow), CdSe/CdS-Pt rods. Reprinted with
permission from Ref. [98]

separation, and light absorption, endow heteronanostructures the potential to be

highly efficient photocatalysis (Fig. 1.8a). Solution-phase photocatalytic reactions
are considered to be a heterogeneous catalytic process, in which dispersed nanocrys-
tals, such as metal oxides, sulfides, and nitrides, works as photocatalysts and some-
times the co-catalysts, such as noble metals (for instance, Pt, Rh, Au), transition
metals, and oxides (NiO, RuO2 ), are deposited on the photocatalysts. Conversion of
solar energy into chemical energy is the key for heteronanostructures in applications
involving photodegradation of organic pollutants [96], photoelectrochemical cells
[97], and photocatalytic water splitting [98, 99].
Proper integration of semiconductors with metals can modulate the band struc-
ture of photocatalytic systems to satisfy the required potential for specific redox
reaction. Furthermore, types and sizes of each components can also influence the
charge separation and accumulation on active site. As described above, type-II band
1.3 Band Engineering and Functions of 1D Chalcogenide Hetero-Nanostructures 17

structure is suitable for high-efficiency charge separation. Au and Pt nanoparticles

in heterostructures can show different charging process under irradiation.
Additionally, crystal structure can affect charge separation as well. Very few
crystalline defects and surface passivation that mitigate surface traps can avoid unde-
manded recombination sites. Meanwhile, high crystallinity is benefit to charge mobil-
ity in nanoparticles. Nanocrystal sizes will also affect the recombination probability
of electrons and holes. For small nanoparticles, the migration distance of to charge
carriers active sites reduces, lowering the recombination probability. For type-II het-
erostructured nanoparticles, the size effect turns to be contrary. Amirav et al. found
that longer CdSe/CdS-Pt nanorods have higher photocatalytic performance, because
the longer the nanorods, the better charge separation along the nanorods, thus lower
back recombination [100]. Figure 1.8b shows the influence of nanorod length on
quantum efficiency of photocatalytic water splitting. Nanorods with length of 60 nm
have higher QY than that of short nanorods.
Other aspects in this hybrid photocatalytic system are mostly investigated via
photocatalytic hydrogen evolution reaction. Beside the size of semiconductor, metal
domains as the co-catalysts will also affect the overall photocatalytic performance.
Subramanian et al. reported the influence of metal size on the charging behavior of
excited states. The negative shift of Fermi level in small metal nanoparticles allows
them higher reduction ability for surface redox reactions [101]. Nonetheless, inves-
tigations on other slightly different hybrid systems claimed that, when the metal size
is between 3–12 nm, their influences on the photocatalytic performance is negligible
[102]. More researches need to be conducted on other systems.
Until now, it remains great challenges to create alternative fuels and energies by
harvesting solar energy. The overall water splitting to hydrogen and oxydgen on a
single nanoparticle has yet to be achieved. To realize that, we need to connect two half-
cell reaction on discrete active sites, or simultaneously using sacrificing reductive
and oxidative agents for two half-reactions, respectively, for instance, ethanol and
sulfide ions as hole scavengers, Ag+ and Fe3+ as electron acceptors. Using different
sacrificing agents (SO3 2− , TEA, EDTA4− , and MeOH) for CdS-Pt nanorods, it’s
easy to find that the type of sacrificing agents are important to the photocatalytic
performance. The design and synthesis of robust heteronanostructured photocatalysts
is an urgent and heavy task.

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Another random document with
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left, because he always made me try it. So he may have tried to
ring.”
Dr. Major (turning the head and examining the throat): “It looks
as if he had clutched at his throat rather tightly this time, I must say.
Here is the mark of his thumb on this side and of his four fingers on
the other. Rather deep for the little strength he had. Odd that he
should have imagined that some one else was trying to choke him,
when he was always pressing at his own neck! Throat tuberculosis is
very painful at times. That would explain the desire to clutch at his
throat.”
Miss Liggett: “He was always believing that an evil spirit was
trying to choke him, doctor.”
Dr. Major: “Yes, I know—association of ideas. Dr. Scain and I
agree as to that. He had a bad case of chronic tuberculosis of the
throat, with accompanying malnutrition, due to the effect of the throat
on the stomach; and his notion about evil spirits pursuing him and
trying to choke him was simply due to an innate tendency on the part
of the subconscious mind to join things together—any notion, say,
with any pain. If he had had a diseased leg, he would have imagined
that evil spirits were attempting to saw it off, or something like that. In
the same way the condition of his throat affected his stomach, and
he imagined that the spirits were doing something to his food. Make
out a certificate showing acute tuberculosis of the esophagus as the
cause, with delusions of persecution as his mental condition. While I
am here we may as well look in on Mr. Baff.”
 III
CHAINS

A S Garrison left his last business conference in K——, where the

tall buildings, and the amazing crowds always seemed such a
commentary on the power and force and wealth of America and the
world, and was on his way to the railway station to take a train for G
——, his home city, his thoughts turned with peculiar emphasis and
hope, if not actual pleasure—and yet it was a pleasure, of a sad,
distressed kind—to Idelle. Where was she now? What was she
doing at this particular moment? It was after four of a gray November
afternoon, just the time, as he well knew, winter or summer, when
she so much preferred to be glowing at an afternoon reception, a
“thé dansant,” or a hotel grill where there was dancing, and always,
as he well knew, in company with those vivid young “sports” or
pleasure lovers of the town who were always following her. Idelle, to
do her no injustice, had about her that something, even after three
years of marriage, that drew them, some of the worst or best—
mainly the worst, he thought at times—of those who made his home
city, the great far-flung G——, interesting and in the forefront socially
and in every other way.
What a girl! What a history! And how strange that he should have
been attracted to her at all, he with his forty-eight years, his superior
(oh, very much!) social position, his conservative friends and equally
conservative manners. Idelle was so different, so hoyden, almost
coarse, in her ways at times, actually gross and vulgar (derived from
her French tanner father, no doubt, not her sweet, retiring Polish
mother), and yet how attractive, too, in so many ways, with that rich
russet-brown-gold hair of hers, her brown-black eyes, almost pupil-
less, the iris and pupil being of the same color, and that trig, vigorous
figure, always tailored in the smartest way! She was a paragon—to
him at least—or had been to begin with.
 How tingling and dusty these streets of K—— were, so vital
always! How sharply the taxis of this mid-Western city turned
corners!
But what a period he had endured since he had married her, three
years before! What tortures, what despairs! If only he could make
over Idelle to suit him! But what a wonderful thing that destroying
something called beauty was, especially to one, like himself, who
found life tiresome in so many ways—something to possess, a
showpiece against the certain inroads of time, something wherewith
to arouse envy in other persons.
At last they were reaching the station!
She did not deserve that he should love her. It was the most
unfortunate thing for him that he did, but how could he help it now?
How overcome it? How punish her for her misdeeds to him without
punishing himself more? Love was such an inscrutable thing; so
often one lavished it where it was not even wanted. God, he could
testify to that! He was a fine example, really. She cared about as
much for him as she did for the lamp-post on the corner, or an old
discarded pair of shoes. And yet— He was never tired of looking at
her, for one thing, of thinking of her ways, her moods, her secrets.
She had not done and was not doing as she should—it was
impossible, he was beginning to suspect, for her so to do—and still
—
He must stop and send her a telegram before the train left!
What a pleasure it was, indeed, anywhere and at all times, to have
her hanging on his arm, to walk into a restaurant or drawing-room
and to know that of all those present none had a more attractive wife
than he, not one. For all Idelle’s commonplace birth and lack of
position to begin with, she was the smartest, the best dressed, the
most alluring, by far—at least, he thought so—of all the set in which
he had placed her. Those eyes! That hair! That graceful figure,
always so smartly arrayed! To be sure, she was a little young for him.
Their figures side by side were somewhat incongruous—he with his
dignity and years and almost military bearing, as so many told him,
she with that air of extreme youthfulness and lure which always
brought so many of the younger set to her side wherever they
happened to be. Only there was the other galling thought: That she
did not wholly belong to him and never had. She was too interested
in other men, and always had been. Her youth, that wretched past of
hers, had been little more than a lurid streak of bad, even evil—yes,
evil—conduct. She had, to tell the truth, been a vile girl, sensuous,
selfish, inconsiderate, unrepentant, and was still, and yet he had
married her in spite of all that, knowing it, really. Only at first he had
not known quite all.
“Yes, all three of these! And wait till I get my sleeper ticket!”
No wonder people had talked, though. He had heard it—that she
had married him for his money, position, that he was too old, that it
was a scandal, etc. Well, maybe it was. But he had been fond of her
—terribly so—and she of him, or seemingly, at first. Yes, she must
have been—her manner, her enthusiasm, if temporary, for him!
Those happy, happy first days they spent together! Her quiet
assumption of the rôle of hostess in Sicard Avenue at first, her
manner of receiving and living up to her duties! It was wonderful, so
promising. Yes, there was no doubt of it; she must have cared for
him a little at first. Her brain, too, required a man of his years to
understand—some phases of her moods and ideas, and as for him
—well, he was as crazy about her then as now—more so, if anything
—or was he? Wasn’t she just as wonderful to him now as she had
been then? Truly. Yes, love or infatuation of this kind was a terrible
thing, so impossible to overcome.
“Car three, section seven!”
Would he ever forget the night he had first seen her being carried
into the Insull General on that canvas ambulance stretcher, her
temple bruised, one arm broken and internal injuries for which she
had to be operated on at once—a torn diaphragm, for one thing—
and of how she had instantly fascinated him? Her hair was loose and
had fallen over one shoulder, her hands limp. Those hands! That
picture! He had been visiting his old friend Dr. Dorsey and had
wondered who she was, how she came to be in such a dreadful
accident and thought her so beautiful. Think of how her beauty might
have been marred, only it wasn’t, thank goodness!
His telegram should be delivered in one hour, at most—that would
reach her in time!
Then and there he had decided that he must know her if she did
not die, that perhaps she might like him as he did her, on the instant;
had actually suffered tortures for fear she would not! Think of that!
Love at first sight for him—and for one who had since caused him so
much suffering—and in her condition, torn and bruised and near to
death! It was wonderful, wasn’t it?
How stuffy these trains were when one first entered them—coal
smoky!
And that operation! What a solemn thing it was, really, with only
himself, the doctor and three nurses in the empty operating room
that night. Dorsey was so tall, so solemn, but always so courageous.
He had asked if he might not be present, although he did not know
her, and because there were no relatives about to bar him from the
room, no one to look after her or to tell who she was, the accident
having occurred after midnight in the suburbs, he had been allowed
by Dorsey to come in.
“Yes, put them down here!”
He had pulled on a white slip over his business suit, and clean
white cotton gloves on his hands, and had then been allowed to
come into the observation gallery while Dorsey, assisted by the
hospital staff, had operated. He saw her cut open—the blood—heard
her groan heavily under ether! And all the time wondering who she
was. Her history. And pitying her, too! Fearing she might not come to!
How the memory of her pretty shrewd face, hidden under bandages
and a gas cone, had haunted him!
The train on this other track, its windows all polished, its dining-car
tables set and its lamps already glowing!
That was another of those fool dreams of his—of love and
happiness, that had tortured him so of late. From the first, almost
without quite knowing it, he had been bewitched, stricken with this
fever, and could not possibly think of her dying. And afterward, with
her broken arm set and her torn diaphragm mended, he had followed
her into the private room which he had ordered and had charged to
himself (Dorsey must have thought it queer!) and then had waited so
restlessly at his club until the next morning, when, standing beside
her bed, he had said: “You don’t know me, but my name is Garrison
—Upham Brainerd Garrison. Perhaps you know of our family here in
G——, the Willard Garrisons. I saw you brought in last night. I want
to be of service to you if I may, to notify your friends, and be of any
other use that I can. May I?”
How well he remembered saying that, formulating it all
beforehand, and then being so delighted when she accepted his
services with a peculiar, quizzical smile—that odd, evasive glance of
hers!
Men struck car wheels this way, no doubt, in order to see that they
were not broken, liable to fly to pieces when the train was running
fast and so destroy the lives of all!
And then she had given him her address—her mother’s, rather, to
whom he went at once, bringing her back with him. And so glad he
was to know that there was only her mother, no husband or— And
the flowers he had sent. And the fruit. And the gifts generally,
everything he thought she might like! And then that queer friendship
with Idelle afterwards, his quickly realized dream of bliss when she
had let him call on her daily, not telling him anything of herself, of
course, evading him rather, and letting him think what he would, but
tolerating him! Yes, she had played her game fair enough, no doubt,
only he was so eager to believe that everything was going to be
perfect with them—smooth, easy, lasting, bliss always. What a fool
of love he really was!
What a disgusting fat woman coming in with all her bags! Would
this train never start?
At that time—how sharply it had all burned itself into his memory!
—he had found her living as a young widow with her baby daughter
at her mother’s, only she wasn’t a widow really. It was all make-
believe. Already she had proved a riant scoffer at the conventions, a
wastrel, only then he did not know that. Where he thought he was
making an impression on a fairly unsophisticated girl, or at least one
not roughly used by the world, in reality he was merely a new
sensation to her, an incident, a convenience, something to lift her out
of a mood or a dilemma in which she found herself. Although he did
not know it then, one of two quarreling men had just attempted to kill
her via that automobile accident and she had been wishing peace,
escape from her own thoughts and the attentions of her two ardent
wooers, for the time being, at the time he met her. But apart from
these, even, there were others, or had been before them, a long line
apparently of almost disgusting—but no, he could not say quite that
—creatures with whom she had been—well, why say it? And he had
fancied for the moment that he was the big event in her life—or
might be! He!
But even so, what difference did all that make either, if only she
would love him now? What would he care who or what she was, or
what she had done before, if only she really cared for him as much
as he cared for her—or half as much—or even a minute portion! But
Idelle could never care for any one really, or at least not for him, or
him alone, anyway. She was too restless, too fond of variety in life.
Had she not, since the first six or seven months in which she had
known and married him, little more than tolerated him? She did not
really need to care for anybody; they all cared for her, sought her.
At last they were going!
Too many men of station and means—younger than himself, as
rich or richer, far more clever and fascinating in every way than he
would ever be (or she would think so because she really liked a
gayer, smarter type than he had ever been or ever could be now)—
vied with him for her interest, and had with each other before ever he
came on the scene. She was, in her queer way, a child of fortune, a
genius of passion and desire, really. Life would use her well for some
time yet, whatever she did to him or any other person, or whatever
he sought to do to her in revenge, if he ever did, because she was
interesting and desirable. Why attempt to deny that? She was far too
attractive yet, too clever, too errant, too indifferent, too spiritually
free, to be neglected by any one yet, let alone by such seeking, avid,
pleasure lovers as always followed her. And because she wouldn’t
allow him to interfere (that was the basis on which she had agreed to
marry him, her personal freedom) she had always been able to go
and do and be what she chose, nearly, just as she was going and
doing now.
These wide yards and that ruck of shabby yellow-and-black
houses, begrimed and dirty externally, and internally no doubt, with
souls in them nearly as drab, perhaps. How much better it was to be
rich like himself and Idelle; only she valued her station so lightly!
Always, wherever he went these days, and his affairs prevented
him from being with her very much, she was in his mind—what she
was doing, where she was going, with whom she might be now—ah,
the sickening thought, with whom she might be now, and where—
with that young waster Keene, possibly, with his millions, his
shooting preserve and his yacht; or Browne, equally young and still
in evidence, though deserted by her to marry him, Garrison; or
Coulstone, with whom Idelle had had that highly offensive affair in
Pittsburgh five years before, when she was only eighteen. Eighteen!
The wonder year! He, too, was here in G—— now after all these
years, this same Coulstone, and after Idelle had left him once! Yes,
he was hanging about her again, wanting her to come back and
marry him, although each of them had remarried!
That flock of crows flying across that distant field!
Of course, Idelle laughed at it, or pretended to. She pretended to
be faithful to him, to tell him all this was unavoidable gossip, the
aftermath of a disturbing past, before ever she saw him. But could he
believe her? Was she not really planning so to do—leave him and
return to Coulstone, this time legally? How could he tell? But think of
the vagaries of human nature and character, the conniving and
persuasive power of a man of wealth like Coulstone. He had left his
great business in Pittsburgh to come here to G—— in order to be
near her and annoy him (Garrison) really—not her, perhaps—with
his pleas and crazy fascination and adoration when she was now
safely and apparently happily married! Think of the strangeness, the
shame, the peculiarity of Idelle’s earlier life! And she still insisted that
this sort of thing was worth while! All his own station and wealth and
adoration were not enough—because he could not be eight or ten
people at once, no doubt. But why should he worry? Why not let her
go? To the devil with her, anyhow! She merely pretended to love him
in her idle, wanton spirit, because she could—well, because she
could play at youth and love!
Barkersburg—a place of 30,000, and the train not stopping! The
sun, breaking through for just one peep at this gray day, under those
trees!
The trouble with his life, as Garrison now saw it, was that
throughout it for the last twenty years, and before that even, in spite
of his youth and money, he had been craving the favor of just such a
young, gay, vigorous, attractive creature as Idelle or Jessica—she of
his earlier years—and not realizing it, until he met Idelle, his desire.
And this, of course, had placed him at a disadvantage in dealing with
women like them. Years before—all of fourteen now, think of it!—
there had been that affair between himself and Jessica, daughter of
the rich and fashionable Balloghs, of Lexington, which had ended so
disastrously for him. He had been out there on Colonel Ledgebrook’s
estate attending to some property which belonged to his father when
she had crossed his path at the colonel’s house, that great estate in
Bourbon County. Then, for the first time really, he had realized the
delight of having a truly beautiful girl interested in him, and him
alone, of being really attracted to him—for a little while. It was
wonderful.
The smothered clang of that crossing bell!
But also what a failure! How painful to hark back to that, and yet
how could he avoid it? Although it had seemed to end so favorably—
he having been able to win and marry her—still in reality it had
ended most disastrously, she having eventually left him as she did.
Jessica, too, was like Idelle in so many ways, as young, as gay,
nearly as forceful, not as pretty, and not with Idelle’s brains. You had
to admit that in connection with Idelle. She had more brains, force,
self-reliance, intuition, than most women he knew anything about,
young or old.
 But to return to Jessica. At first she seemed to think he was
wonderful, a man of the world, clever, witty, a lover of light, frivolous,
foolish things, such as dancing, drinking, talking idle nonsense,
which he was not at all. Yes, that was where he had always failed,
apparently, and always would. He had no flair, and clever women
craved that.
That flock of pigeons on that barn roof!
At bottom really he had always been slow, romantic, philosophic,
meditative, while trying in the main to appear something else,
whereas these other men, those who were so successful with
women at least, were hard and gay and quick and thoughtless, or so
he thought. They said and did things more by instinct than he ever
could, were successful—well, just because they were what they
were. You couldn’t do those things by just trying to. And gay, pretty,
fascinating women, such as Idelle or Jessica, the really worthwhile
ones, seemed to realize this instinctively and to like that kind and no
other. When they found a sober and reflective man like himself, or
one even inclined to be, they drew away from him. Yes, they did; not
consciously always, but just instinctively. They wanted only men who
tingled and sparkled and glittered like themselves. To think that love
must always go by blind instinct instead of merit—genuine, adoring
passion!
This must be Phillipsburg coming into view! He couldn’t mistake
that high, round water tower!
Ah, the tragedy of seeing and knowing this and not being able to
remedy it, of not being able to make oneself over into something like
that! Somehow, Jessica had been betrayed by his bog-fire
resemblance to the thing which she took him to be. He was a bog
fire and nothing more, in so far as she was concerned, all she
thought he was. Yet because he was so hungry, no doubt, for a
woman of her type he had pretended that he was “the real thing,” as
she so liked to describe a gay character, a man of habits, bad or
good, as you choose; one who liked to gamble, shoot, race, and do a
lot of things which he really did not care for at all, but which the
crowd or group with which he was always finding himself, or with
whom he hoped to appear as somebody, was always doing and
liking.
These poor countrymen, always loitering about their village
stations!
And the women they ran with were just like them, like Jessica, like
Idelle—smart, showy and liked that sort of man—and so—
Well, he had pretended to be all that and more, when she
(Jessica) had appeared out of that gay group, petite, blonde (Idelle
was darker), vivacious, drawn to him by his seeming reality as a man
of the world and a gay cavalier. She had actually fallen in love with
him at sight, as it were, or seemed to be at the time—she!—and
then, see what had happened! Those awful months in G—— after
she had returned with him! The agonies of mind and body!
If only that stout traveling man in that gray suit would cease staring
at him! It must be the horn-rimmed glasses he had on which
interested him so! These mid-Western people!
Instantly almost, only a few weeks after they were married, she
seemed to realize that she had made a mistake. It seemed not to
make the slightest difference to her, after the first week or so, that
they were married or that he was infatuated with her or that he was
who he was or that her every move and thought were beautiful to
him. On the contrary, it seemed only to irritate her all the more. She
seemed to sense then—not before—that he was really the one man
not suited to her by temperament or taste or ideas, not the kind she
imagined she was getting, and from then on there were the most
terrible days, terrible—
That pretty girl turning in at that village gate!
Trying, depressing, degrading really. What dark frowns used to
flash across her face like clouds at that time—she was nineteen to
his twenty-four, and so pretty!—the realization, perhaps, that she had
made a mistake. What she really wanted was the gay, anachronistic,
unthinking, energetic person he had seemed to be under the stress
of the life at Ledgebrook’s, not the quiet, reasoning, dreamy person
he really was. It was terrible!
 Tall trees made such shadowy aisles at evening!
Finally she had run away, disappeared completely one morning
after telling him she was going shopping, and then never seeing him
any more—ever—not even once! A telegram from Harrisburg had
told him that she was going to her mother’s and for him not to follow
her, please; and then before he could make up his mind really what
to do had come that old wolf Caldwell, the famous divorce lawyer of
G——, representing her mother, no doubt, and in smooth,
ingratiating, persuasive tones had talked about the immense folly of
attempting to adjust natural human antipathies, the sadness of all
human inharmonies, the value of quiet in all attempts at separation,
the need he had to look after his own social prestige in G——, and
the like, until finally Caldwell had persuaded him to accept a decree
of desertion in some Western state in silence and let her go out of
his life forever! Think of that!
The first call for dinner! Perhaps he had better go at once and
have it over with! He wanted to retire early to-night!
But Jessica—how she had haunted him for years after that! The
whole city seemed to suggest her at times, even after he heard that
she was married again and the mother of two children, so strong was
the feeling for anything one lost. Even to this day certain corners in
G——, the Brandingham, where they had lived temporarily at first;
Mme. Gateley’s dressmaking establishment, where she had had her
gowns made, and the Tussockville entrance to the park—always
touched and hurt him like some old, dear, poignant melody.
How this train lurched as one walked! The crashing couplings
between these cars!
And then, after all these busy, sobering years, in which he had
found out that there were some things he was not and could not be
—a gay, animal man of the town, for instance, a “blood,” a waster;
and some things that he was—a fairly capable financial and
commercial man, a lover of literature of sorts, and of horses, a genial
and acceptable person in many walks of society—had come Idelle.
 Think of the dining-car being crowded thus early! And such
people!
He was just settling down to a semi-resigned acceptance of
himself as an affectional, emotional failure in so far as women were
concerned, when she had come—Idelle—this latest storm which had
troubled him so much. Idelle had brains, beauty, force, insight—more
than Jessica ever had had, or was he just older?—and that was what
made her so attractive to men, so indifferent to women, so ready to
leave him to do all the worshiping. She could understand him,
apparently, at his time of life, with his sober and in some ways sad
experiences, and sympathize with him most tenderly when she
chose, and yet, strangely enough, she could ignore him also and be
hard, cruel, indifferent. The way she could neglect him at times—go
her own way! God!
Not a bad seat, only now it was too dark to see anything outside!
These heavy forks!
But to return to that dreadful pagan youth of hers, almost half-
savage: take that boy who shot himself at the age of sixteen for love
of her, and all because she would not run away with him, not caring
for him at all, as she said, or she would have gone! What a sad case
that was, as she had told it, at least. The boy’s father had come and
denounced her to her parents in her own home, according to her,
and still she denied that it had been her fault. And those other two
youths, one of whom had embezzled $10,000 and spent it on her
and several other boys and girls! And that other one who had stolen
five hundred in small sums from his father’s till and safe and then
wasted it on her and her companions at country inns until he was
caught! Those country clubs! Those little rivers she described, with
their canoes—the automobiles of these youths—the dancing, eating,
drinking life under the moon in the warmth of spring and summer
under the trees! And he had never had anything like that, never!
When one of the boys, being caught, complained of her to his
parents as the cause of his evil ways she had denied it, or so she
said, and did still to this day, saying she really did not know he was
stealing the money and calling him coward or cry-baby. Idelle told
him of this several years ago as though it had some humorous
aspects, as possibly it had, to her—who knows? but with some
remorse, too, for she was not wholly indifferent to the plight of these
youths, although she contended that what she had given them of her
time and youth and beauty was ample compensation. Yes, she was
a bad woman, really, or had been—a bad girl, say what one would, a
child of original evil impulse. One could not deny that really. But what
fascination also, even yet, and then no doubt—terrible! He could
understand the actions of those youths, their recklessness. There
was something about sheer beauty, evil though it might be, which
overcame moral prejudices or scruples. It had done so in his case, or
why was he living with her? And so why not in theirs?
How annoying to have a train stop in a station while you were
eating!
Beauty, beauty, beauty! How could one gainsay the charm or
avoid the lure of it? Not he, for one. Trig, beautiful women, who
carried themselves with an air and swing and suggested by their
every movement passion, alertness, gayety of mind! The church
bells might ring and millions of religionists preach of a life hereafter
with a fixed table of rewards and punishments, but what did any one
know of the future, anyhow? Nothing! Exactly nothing, in spite of all
the churches. Life appeared and disappeared again; a green door
opened and out you went, via a train wreck, for instance, on a night
like this. All these farmers here tilling their fields and making their
little homes and towns—where would they be in forty or fifty years,
with all their moralities? No, here and now was life, here and now
beauty—here and now Idelle, or creatures like her and Jessica.
He would pay his bill and go into the smoker for a change. It would
be pleasant to sit there until his berth was made up.
Then, take that affair of the banker’s son, young Gratiot it was,
whom he knew well even now here in G——, only Gratiot did not
know that he knew—or did he? Perhaps he was still friendly with
Idelle, although she denied it. You could never really believe her. He
it was, according to her, who had captured her fancy with his fine airs
and money and car when she was only seventeen, and then robbed
her (or could you call it robbery in Idelle’s case, seeking, restless
creature that she was?) of her indifferent innocence. No robbery
there, surely, whatever she might say.
Those fascinating coke ovens blazing in the dark beside the track,
mile after mile!
Somehow her telling him these things at first, or rather shortly after
they were married and when she was going to make a clean breast
of everything and lead a better life, had thrown a wonderful glamour
over her past.
“Gay Stories”! What a name for a magazine! And that stout old
traveling man reading it!
What a strange thing it was to be a girl like that—with passions
and illusions like that! Perhaps, after all, life only came to those who
sought it with great strength and natural gifts. But how hard it was on
those who hadn’t anything of that kind! Nevertheless, people should
get over the follies of their youth—Idelle should, anyhow. She had
had enough, goodness knows. She had been one of the worst—
hectic, vastly excited about life, irresponsible—and she should have
sobered by now. Why not? Look at all he had to offer her! Was that
not enough to effect a change? While it made her interesting at
times, this left-over enthusiasm, still it was so ridiculous, and made
her non-desirable, too, either as wife or mother. Yet no doubt that
was what had made her so fascinating to him, too, at this late day
and to all those other men in B—— and elsewhere—that blazing
youthfulness. Strange as it might seem, he could condone Idelle’s
dreadful deeds even now, just as her mother could, if she would only
behave herself, if she would only love him and him alone—but would
she? She seemed so determined to bend everything to her service,
regardless,—to yield nothing to him.
No use! He couldn’t stand these traveling men in this smoking
room! He must have the porter make up his berth!
And then had come Coulstone, the one who was still hanging
about her now, the one with whom she had had that dreadful affair in
Pittsburgh, the affair that always depressed him to think about even
now. Of course, there was one thing to be said in extenuation of that,
if you could say anything at all—which you couldn’t really—and that
was that Idelle was no longer a good girl then, but experienced and
with all her blazing disposition aroused. She had captured the reins
of her life then and was doing as she pleased—only why couldn’t he
have met her then instead of Coulstone? He was alive then. And his
own life had always been so empty. When she had confessed so
much of all this to him afterward—not this Coulstone affair exactly,
but the other things—why hadn’t he left her then? He might have and
saved himself all this agony—or could he have then? He was twice
her age when he married her and knew better, only he thought he
could reform her—or did he? Was that the true reason? Could he
admit the true reason to himself?
“Yes, make it up right away, if you will!” Now he would have to wait
about and be bored!
But to come back to the story of Coulstone and all that hectic life in
Pittsburgh. Coulstone, it seems, had been one of four or five very
wealthy young managing vice-presidents of the Iverson-Centelever
Frog and Switch Company, of Pittsburgh. And Idelle, because her
father had suddenly died after her affair with young Gratiot, never
knowing a thing about it, and her mother, not knowing quite what to
do with her, had (because Idelle seemed to wish it) sent her to stay
with an aunt in Pittsburgh. But the aunt having to leave for a time
shortly after Idelle reached there, a girl friend had, at Idelle’s
instigation, apparently, suggested that she stay with her until the
aunt’s return, and Idelle had then persuaded her mother to agree to
that.
That tall, lanky girl having to sleep in that upper berth opposite!
European sleeping cars were so much better!
Her girl friend was evidently something like Idelle, or even worse.
At any rate, Idelle appeared to have been able to wind her around
her finger. For through her she had found some method of being
introduced to (or letting them introduce themselves) a few of these
smart new-rich men of the town, among them two of these same
vice-presidents, one of whom was Coulstone. According to Idelle, he
was a lavish and even reckless spender, wanting it to appear
generally that he could do anything and have anything that money
could buy, and liking to be seen in as many as a dozen public places
in one afternoon or evening, especially at week-ends, only there
weren’t so many in Pittsburgh at the time.
This must be Centerfield, the state capital of E——, they were now
passing without a pause! These expresses cut through so many
large cities!
From the first, so Idelle said, he had made violent love to her,
though he was already married (unhappily, of course), and she,
caring nothing for the conventions and not being of the kind that
obeys any laws (wilful, passionate, reckless), had received him
probably in exactly the spirit in which he approached her, if not more
so. That was the worst of her, her constant, wilful, pagan pursuit of
pleasure, regardless of anybody or anything, and it still held her in
spite of him. There was something revolting about the sheer
animality of it, that rushing together of two people, regardless. Still, if
it had been himself and Idelle now—
How fortunate that he had been able to obtain a section! At least
he would have air!
There had been a wild season, according to her own admissions
or boastings—he could never quite tell which—extending over six or
seven months, during which time Idelle had pretended to her mother,
so she said, to prefer to live with her girl friend rather than return
home. She had had, according to her, her machine, her servants,
clothes without end, and what-not—a dream-world of luxury and
freedom which he had provided and from which she never expected
to wake, and her mother totally ignorant of it all the while! There had
been everything she wished at her finger tips—hectic afternoons,
evenings and midnights; affairs at country clubs or hotel grills, where
the young bloods of the city and their girls congregated; wild rides in
automobiles; visits to the nearest smartest watering-places, and the
like. Or was she lying? He could scarcely think so, judging by her
career with him and others since.
Ah, what a comfort to fix oneself this way and rest, looking at the
shadowy moonlit landscape passing by!
 Idelle had often admitted or boasted that she had been wildly
happy—that was the worst of it—that she had not quite realized what
she was doing, but that she had no remorse either, even now—that
she had lived! (And why should she have, perhaps? Weren’t all
people really selfish at bottom—or were they?) Only, owing to her
almost insatiable pagan nature, there were other complications right
then and there—think of that!—an older rival millionaire, if you
please, richer by far than Coulstone, and more influential locally ...
and younger ones, too, who sought her but really did not win her,
she having no time or plan for them. As it happened, the older one,
having been worsted in the contest but being partially tolerated by
her, had become frantically jealous and envious, although “he had no
right,” as she said, and had finally set about making trouble for the
real possessor, and succeeded to the extent of exposing him and
eventually driving him out of the great concern with which he was
connected and out of Pittsburgh, too, if you please, on moral
grounds (?), although he himself was trying to follow in Coulstone’s
footsteps! And all for the love or possession of a nineteen-year-old
girl, a petticoat, a female ne’er-do-well! How little the world in general
knew of such things—and it was a blessed thing, too, by George!
Where would things be if everybody went on like that?
The rhythmic clack of these wheels and trucks over these sleeper
joints—a poetic beat, of sorts!
But Idelle was so naïve about all this now, or pretended to be, so
careless of what he or any one else might think in case they ever
found out. She did not seem to guess how much he might suffer by
her telling him all this, or how much pain thinking about it afterward
might cause him. She was too selfish intellectually. She didn’t even
guess, apparently, what his mood might be toward all this, loving her
as he did. No—she really didn’t care for him, or any one else—
couldn’t, or she couldn’t have done anything like that. She would
have lied to him rather. She had been, and was—although now
semi-reformed—a heartless, careless wastrel, thinking of no one but
herself. She had not cared about the wives of either of those two
men who were pursuing her in B——, or what became of them, or
what became of any of the others who had pursued her since. All
she wanted was to be danced attendance on, to be happy, free,
never bored. The other fellow never counted with Idelle much. In this
case the wife of the younger lover, Coulstone, had been informed,
the conservatives of the city appealed to, as it were. Coulstone,
seeing the storm and being infatuated with his conquest, suggested
Paris or a few years on the Riviera, but, strangely enough, Idelle
would have none of it, or him, then. She wouldn’t agree to be tied
down for so long! She had suffered a reversal of conscience or mood
—even—or so she said,—went to a priest, went into retirement here
in G——, having fled her various evil pursuers.
How impressive the outlying slopes of these mountains they were
just entering!
And yet he could understand that, too, in some people, anyhow,—
the one decent thing in her life maybe, a timely revolt against a too
great and unbroken excess. But, alas, it had been complicated with
the fact that she wasn’t ready to leave her mother or to do anything
but stay in America. Besides things were becoming rather
complicated. The war on J—— C—— threatened to expose her.
Worse yet,—and so like her, life had won her back. Her beauty, her
disposition, youth and age pursuing her—one slight concession to
indulgence or pleasure after another and the new mood or bent
toward religiosity was entirely done away with. Her sensual sex
nature had conquered, of course.
That little cabin on that slope, showing a lone lamp in the dark!
And then—then—
Morning, by George! Ten o’clock! He had been asleep all this time!
He would have to hurry and dress now!
But where was he in regard to Idelle? Oh yes!... How she haunted
him all the time these days! Coulstone, angered at her refusal to
come with him again (she could not bring herself to do that, for all
her religiosity, she said, not caring for him so much any more), but
frightened by the presence of others, had eventually transferred all
his interests from Pittsburgh to G——, and at this very time, on the
ground of some form of virtue or duty—God only knows what!—five
years later, indeed—was here in G—— with his wife and attempting
to persuade her that she ought to give him a divorce in order to
permit him to marry Idelle and so legitimize her child! And he,
Garrison, already married to her! The insanity of mankind!
He must be hurrying through his breakfast; they would soon be
nearing G—— now ... and he must not forget to stop in at Kiralfy’s
when he reached G—— and buy some flowers for her!
But Idelle was not to be taken that way. She did not care for J——
C—— any more, or so she said. Besides nothing would cure her
varietism then or now but age, apparently. And who was going to
wait for age to overtake her? Not he, anyhow. Why, the very event
that threw her into his arms—couldn’t he have judged by that if he
had had any sense? Wasn’t that just such another affair as that of
Coulstone and old Candia, only in this case it concerned much
younger men—wasters in their way, too—one of whom, at least, was
plainly madly in love with her, while the other was just intensely
interested. Why was it that Idelle’s affairs always had to be a
complex of two or more contending parties?
The condition of these washrooms in the morning!
According to her own story, she had first fallen in love, or thought
she had, with the younger of the two, Gaither Browne, of the
Harwood Brownes here in G—— and then while he was still dancing
attendance on her (and all the while Coulstone was in the
background, not entirely pushed out of her life) young Gatchard
Keene had come along with his motor cars, his yacht, his stable of
horses, and she had begun to flirt with him also. Only, by then—and
she didn’t care particularly for him, either—
What a crowded breakfast car—all the people of last
night, and more from other cars attached since, probably!
—she had half promised young Browne that she would marry him,
or let him think she might; had even confessed a part of her past to
him (or so she said) and he had forgiven her, or said it didn’t matter.
But when Keene came along and she began to be interested in him
Browne did not like this new interest in the least, became furiously