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Advanced Nanomaterials for Catalysis
and Energy
This page intentionally left blank
 Advanced Nanomaterials for
Catalysis and Energy
Synthesis, Characterization and Applications
Edited by
Vladislav A. Sadykov
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Novosibirsk State University, Novosibirsk, Russia
Elsevier
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The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, United Kingdom
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Contents
Contributors....................................................................................................xiii
Preface...........................................................................................................xvii
Chapter 1: Synthesis of Nano-Catalysts in Flow Conditions Using Millimixers...........1
Changdong Li, Maoshuai Li, Andre C. van Veen
Case Study One: Design and Optimization of Multistage Flow Synthesis
Configurations to Prepare Zn-Cr Hydrotalcites......................................................2
1.1.1 Synthesis Methodology.......................................................................................3
1.1.1.1 Materials.......................................................................................................3
1.1.1.2 Flow Synthesis Configuration......................................................................4
1.1.1.3 Comparative Co-Precipitation Method........................................................7
1.1.1.4 Characterization Methods............................................................................8
1.1.1.5 Properties of Co-Precipitation Made as Comparative Materials................8
1.1.2 Properties of Materials Made by Flow Synthesis..............................................9
1.1.2.1 Effect of Total Aging Time (Coil Time).....................................................9
1.1.2.2 Effects of Temperature and Bore Size of Millimixer...............................13
1.1.3 Conclusions.......................................................................................................18
Acknowledgments.......................................................................................................19
References...................................................................................................................19
Case Study Two: Preparation of the Precursor for Ba0.5Sr0.5Co0.2Fe0.8O32 δ
Perovskites and Comparison of Performance in a Membrane Application................20
1.2.1 Synthesis and Characterization of Materials....................................................21
1.2.2 Comparison of Oxygen Permeation Performances..........................................25
1.2.3 Conclusion.........................................................................................................27
Acknowledgments.......................................................................................................27
References...................................................................................................................27
Chapter 2: Influence of Hydrodynamics on Wet Syntheses of Nanomaterials...........29
Nicholas Jose, Alexei Lapkin
2.1 Introduction..........................................................................................................30
2.1.1 Nanoparticle Formation....................................................................................31
2.2 Mixing Effects......................................................................................................33
2.2.1 Theory...............................................................................................................33

v
Contents

2.2.2 Experimental Studies........................................................................................36

2.3 Flow-Induced Structuring....................................................................................41
2.3.1 Theory...............................................................................................................41
2.3.2 Experimental Studies........................................................................................46
2.4 Molecular Clustering: Nucleation, Crystallization, and Polymorphism.............50
2.5 Conclusions..........................................................................................................53
Acknowledgments.......................................................................................................54
References...................................................................................................................54
Chapter 3: Advanced Size-Selected Catalysts Prepared by Laser Electrodispersion...61
Tatiana N. Rostovshchikova, Ekaterina S. Lokteva, Elena V. Golubina, Konstantin I. Maslakov,
Sergey A. Gurevich, Denis A. Yavsin, Vladimir M. Kozhevin
3.1 Introduction..........................................................................................................61
3.2 Principles of LED Method for the Synthesis of Metal Nanoparticles................62
3.3 LED Metal-Containing Systems in Catalysis......................................................70
3.3.1 Copper Catalysts...............................................................................................70
3.3.2 Nickel Catalysts on Carbon and Oxide Supports............................................75
3.3.3 Palladium-Containing Catalysts.......................................................................82
3.3.4 Bimetallic Materials.........................................................................................86
3.4 Discussion: The Reasons of High Catalytic Efficiency of LED Systems..........89
3.5 Concluding Remarks............................................................................................93
Acknowledgments.......................................................................................................94
References...................................................................................................................94
Chapter 4: Ruthenium Nanomaterials: An Overview of Recent Developments
in Colloidal Synthesis, Properties, and Potential Applications................................99
Irina L. Simakova, Dmitry Yu. Murzin
4.1 Introduction........................................................................................................100
4.2 Surfactant-Assisted Routes for NPs Preparation...............................................101
4.2.1 Microemulsion Technique..............................................................................101
4.2.2 Сolloidal Method............................................................................................103
4.3 Preparation of Supported Metal Catalysts on the Basis of Colloidal NPs.......110
4.3.1 Deposition of NPs From ME.........................................................................110
4.3.2 Immobilization of NPs From Colloids..........................................................111
4.4 Role of a Protecting Agent................................................................................111
4.5 Ru NPs Application in Catalysis.......................................................................114
4.5.1 Catalytic Application of Ru NPs Prepared by the ME.................................116
4.5.2 Catalytic Application of Ru NPs Prepared by Colloidal Synthesis..............117
4.5.3 Catalytic Applications of Ru NPs..................................................................118
4.5.4 Examples of Catalytic Applications of Supported Colloidal
Ru NPs............................................................................................................125
4.6 Concluding Remarks and Outlook.....................................................................133
Acknowledgments.....................................................................................................134
References.................................................................................................................135

vi
 Contents

Chapter 5: Ag-Containing Nanomaterials in Heterogeneous Catalysis:

Advances and Recent Trends............................................................................143
Olga V. Vodyankina, Grigory V. Mamontov, Valery V. Dutov, Tamara S. Kharlamova,
Mikhail A. Salaev
5.1 Introduction........................................................................................................143
5.2 Surface Chemistry of Ag-Based Materials in Oxidation Catalysis..................145
5.2.1 Silver-Oxygen Interactions.............................................................................145
5.2.2 Effect of Promoters on Reactivity of Active Species on Ag Surface...........148
5.2.3 Silver-Support Interactions.............................................................................149
5.2.4 Structure-Activity Relationship......................................................................159
5.3 Concluding Remarks and Outlook.....................................................................164
Acknowledgment.......................................................................................................165
References.................................................................................................................165
Chapter 6: How Does the Surface Structure of Ni-Fe Nanoalloys Control
Carbon Formation During Methane Steam/Dry Reforming?................................177
Stavros Alexandros Theofanidis, Hilde Poelman, Guy B. Marin, Vladimir V. Galvita
6.1 Introduction........................................................................................................177
6.1.1 Methane Reforming Processes.......................................................................177
6.1.2 Carbon Formation...........................................................................................180
6.2 Synthesis of Ni-Fe Catalysts..............................................................................181
6.3 Role of Fe...........................................................................................................181
6.3.1 Structural Features of Ni-Fe Nanoalloys.......................................................183
6.3.2 Activity During Methane Decomposition......................................................184
6.3.3 Activity During Methane Reforming.............................................................188
6.3.4 Regeneration Ability......................................................................................191
6.3.5 Control of Carbon Formation on Ni-Fe Nanoalloy Catalysts.......................193
6.3.6 Carbon Removal From Ni-Fe Nanoalloy Catalysts.......................................196
6.4 Novel Fe-Modified Magnesium Aluminate Support for Control of
Carbon Formation..............................................................................................209
6.4.1 MgFexAl2
xO4 Synthesis...............................................................................209
6.4.2 Structural and Textural Features of MgFexAl2
xO4 Support.......................209
6.4.3 Ni-Fe Nanoalloy Supported on MgFexAl2
xO4............................................212
6.4.4 Stability and Carbon Formation of Ni-Fe Nanoalloy Supported on
MgFexAl2
xO4...............................................................................................215
6.5 Concluding Remarks and Outlook.....................................................................217
References.................................................................................................................218
Chapter 7: Recent Applications of Nanometal Oxide Catalysts in Oxidation
Reactions.......................................................................................................227
V. Cort
es Corberán, V. Rives, V. Stathopoulos
7.1 Introduction........................................................................................................228
7.1.1 Oxide Catalysts: Specific Features................................................................228
7.1.2 Scope of the Chapter......................................................................................229

vii
Contents

7.2 Synthesis Methods for Nanoscale and Morphology..........................................230

7.3 Ceria-Based Systems..........................................................................................231
7.3.1 Pure Ceria.......................................................................................................231
7.3.2 Binary CedZr Oxides...................................................................................233
7.3.3 Binary CuOdCeO2 Catalysts........................................................................236
7.3.4 Binary MndCe Oxides..................................................................................240
7.3.5 Binary CodCe Oxide Catalysts....................................................................242
7.3.6 Other Mixed Oxide Catalysts.........................................................................244
7.4 Co, Mn, and Fe Oxide-Based Systems..............................................................247
7.4.1 Cobalt-Based Systems....................................................................................247
7.4.2 Iron-Based Systems........................................................................................255
7.4.3 Manganese-Based Catalysts...........................................................................258
7.5 Other Oxide-Based Systems..............................................................................265
7.5.1 Vanadium Oxide-Based Catalysts..................................................................265
7.5.2 Molybdenum Oxide-Based Catalysts.............................................................268
7.5.3 Titania-Based Catalysts..................................................................................271
7.5.4 Nickel Oxide-Based Catalysts........................................................................273
7.5.5 Copper Oxide-Based Catalysts......................................................................274
7.5.6 Chromium Oxide-Based Catalysts.................................................................276
7.5.7 Miscellaneous Oxide Catalysts......................................................................277
7.6 Concluding Remarks and Outlook.....................................................................279
References.................................................................................................................281
Chapter 8: Particle-Size Effect in Catalytic Oxidation Over Pt Nanoparticles........295
Alexandr Yu. Stakheev, Dmitry A. Bokarev, Igor P. Prosvirin, Valerii I. Bukhtiyarov
8.1 Introduction........................................................................................................295
8.2 Total Alkane Oxidation......................................................................................296
8.2.1 Particle Size Effect and Oxygen Coverage...................................................296
8.2.2 Oxidation of Pt Nanoparticles........................................................................302
8.2.3 Effect of PtOx Formation on Catalytic Activity............................................304
8.2.4 PtOx Formation Upon Reaction Conditions..................................................305
8.3 Particle Size Effect in CO Oxidation................................................................308
8.4 Particle Size Effect in NO Oxidation................................................................310
8.5 Conclusions........................................................................................................314
References.................................................................................................................316
Chapter 9: Novel Zeolite Catalysts for Methanol to Hydrocarbon
Transformation..............................................................................................321
Evgeny Rebrov, Guannan Hu
9.1 Introduction........................................................................................................321
9.2 Reaction Mechanism..........................................................................................323
9.3 Synthesis of ZSM-5 Coatings on Structured Substrates...................................327
9.3.1 Synthesis of Microporous Zeolites................................................................327
9.3.2 Catalyst Stability............................................................................................333

viii
 Contents

9.3.3 Ion-Exchange..................................................................................................337
9.3.4 Hierarchical H-ZSM-5 Structure....................................................................340
9.4 MTH Process......................................................................................................346
9.5 Concluding Remarks and Outlook.....................................................................348
References.................................................................................................................349
Further Reading.........................................................................................................356
Chapter 10: Semiconductor Photocatalysts Based on Nanostructured
Cd12 xZnxS Solid Solutions in the Reaction of Hydrogen Evolution From
Aqueous Solutions of Inorganic Electron Donors Under Visible Light....................357
Ekaterina A. Kozlova, Valentin N. Parmon
10.1 Introduction......................................................................................................357
10.2 Synthesis and Photocatalytic Properties of Cd1
xZnxS Solid Solutions........360
10.2.1 Characteristics of the Cd1
xZnxS Samples...............................................361
10.2.2 The Kinetics of Photocatalytic Hydrogen Evolution................................364
10.3 The Synthesis of Composite Materials Containing CdS or Cd1
xZnxS and
Conductors With a Wider Band Gap...............................................................366
10.4 Deposition of Cocatalysts on the Cadmium Sulfide Surface..........................371
10.4.1 Deposition of Copper Sulfide on the Cd0.3Zn0.7S Surface.......................373
10.4.2 Synthesis and Study of Cu/Cd0.3Zn0.7S and Cu(OH)2/Cd0.3Zn0.7S
Photocatalysts.............................................................................................378
10.4.3 Synthesis of NiS/Cd0.3Zn0.7S, NizCd0.3Zn0.7S1+ z, Ni/Cd0.3Zn0.7S, and
Ni(OH)2/Cd0.3Zn0.7S Photocatalysts..........................................................379
10.4.4 Synthesis and Study of Au, Pt, Pd/Cd0.3Zn0.7S Photocatalysts................382
10.5 Synthesis of Catalysts With Cadmium Sulfide Deposited on a Porous
Support With the 3D Structure........................................................................383
10.6 Concluding Remarks and Outlook...................................................................387
Acknowledgment.......................................................................................................388
References.................................................................................................................388
Сhapter 11: Nanocomposite Alkali-Ion Solid Electrolytes....................................393
Nikolai F. Uvarov, Artem S. Ulihin, Yulia G. Mateyshina
11.1 Introduction......................................................................................................393
11.2 Interface Phenomena in CSE...........................................................................394
11.2.1 Point Defects on Surfaces or Grain Boundaries of Ionic Crystals...........394
11.2.2 Point Defects on Interfaces and Interface Interaction...............................396
11.2.3 Size Effects in Nanocomposite Solid Electrolytes....................................400
11.3 Molecular Dynamics Simulations....................................................................404
11.4 Estimation of Transport Properties of CSE.....................................................406
11.4.1 General Approaches...................................................................................406
11.4.2 Generalized Mixing Equation....................................................................407
11.4.3 Estimation of Conductivity of Composites of Other Types......................410
11.5 Transport Properties of Alkali Ion CSE..........................................................412
11.5.1 Lithium Halide Based CSE........................................................................412
11.5.2 CSE Based on Other Alkali Halide Salts..................................................414

ix
Contents

11.5.3 CSE Based on Li2SO4, Li2CO3, and Li2O................................................415

11.5.4 Alkali Nitrate CSE.....................................................................................417
11.5.5 Composites Based on Alkali Perchlorates.................................................420
11.5.6 Composites Based on Alkali Nitrites.........................................................423
11.5.7 Polymer and Glass-Ceramic Composite Lithium-Ion Electrolytes...........426
11.6 Applications of Alkali-Ion Nanocomposte Solid Electrolytes........................426
11.7 Conclusions......................................................................................................428
References.................................................................................................................429
Further Reading.........................................................................................................434
Chapter 12: Advanced Materials for Solid Oxide Fuel Cells and Membrane
Catalytic Reactors..........................................................................................435
Vladislav A. Sadykov, Natalia V. Mezentseva, Lyudmila N. Bobrova, Oleg L. Smorygo,
Nikita F. Eremeev, Yulia E. Fedorova, Yulia N. Bespalko, Pavel I. Skriabin, Alexey V. Krasnov,
Anton I. Lukashevich, Tamara A. Krieger, Ekaterina M. Sadovskaya, Vladimir D. Belyaev,
Alexander N. Shmakov, Zakhar S. Vinokurov, Vladimir A. Bolotov, Yuri Yu. Tanashev,
Mikhail V. Korobeynikov, Mikhail A. Mikhailenko
12.1 Introduction......................................................................................................436
12.2 Synthesis and Deposition Techniques.............................................................440
12.2.1 Methods for the Material Synthesis...........................................................440
12.2.2 Sintering Techniques..................................................................................442
12.3 Novel Methods of Studying Functional Characteristics of Materials.............444
12.3.1 Relaxation Techniques...............................................................................444
12.3.2 Isotope Exchange Techniques....................................................................446
12.3.3 Temperature Programmed Desorption of Oxygen....................................448
12.4 Anode Materials for IT SOFC and Oxygen/Hydrogen Separation
Membranes.......................................................................................................449
12.4.1 External Reforming for SOFC. Catalysts and Reforming Chemistry.......452
12.4.2 Structured Substrates, Catalysts and Reactors...........................................458
12.4.3 Performance of Structured Catalysts and Reactors in Reforming
of Real Feeds..............................................................................................459
12.4.4 Oxygen Separation Membranes Tests.......................................................465
12.4.5 Start-Up Characteristics and Modeling......................................................470
12.4.6 Effect of Fuel External Reforming/Prereforming on SOFC Performance...472
12.4.7 Internal Reforming for SOFC. Screening Tests of Promoted
Ni/YSZ Composites in Fuels Steam Reforming.......................................473
12.4.8 Layers of Promoted Ni/YSZ Composites on Anode/Structured
Substrates: Performance and Stability.......................................................475
12.4.9 Kinetics of Methane Steam Reforming.....................................................476
12.4.10 SOFC Tests With Internal Reforming.....................................................478
12.5 Cathode Materials for IT SOFC......................................................................480
12.5.1 Perovskites and Nanocomposites Based on Them....................................481
12.5.2 Ruddlesden—Popper Phases......................................................................490

x
 Contents

12.6 Solid Electrolytes and Oxides With a High Ionic Conductivity for IT
SOFC and Permselective Membranes.............................................................492
12.6.1 Apatites.......................................................................................................494
12.6.2 Ceria—Zirconia Mixed Oxides..................................................................495
12.7 Concluding Remarks and Outlook...................................................................499
Acknowledgments.....................................................................................................501
References.................................................................................................................502
Chapter 13: Mixed Ionic-Electronic Conducting Perovskites as Nanostructured
Ferroelastics..................................................................................................515
Irina V. Belenkaya, Olga A. Bragina, Alexander P. Nemudry
13.1 Introduction......................................................................................................515
13.2 MIEC Perovskites as Ferroelastics..................................................................518
13.3 Study of the Domain Structure of Brownmillerite SrCo0.8Fe0.2O2.5..............520
13.3.1 Theoretical Consideration..........................................................................520
13.3.2 Electron Microscopy Study........................................................................522
13.3.3 Domain Reorientation Under Mechanical Load........................................526
13.3.4 In Situ High-Temperature X-Ray Diffraction Studies of the
Dynamics of “Perovskite-Brownmillerite” Phase Transition in
SrCo0.8Fe0.2O2.5..........................................................................................528
13.4 Effect of Doping With Ferroactive Highly Charged Cations on the
Structure, Phase Transitions, and Microstructure of SrCo0.8
xFe0.2MxO3
δ
(M ¼ Nb, Ta, W, Mo).......................................................................................530
13.4.1 Studies of the Structure and Microstructure of the Low-Temperature
Phases SrCo0.8-xFe0.2MxO2.5+ y (M ¼ Nb, Ta; 0 < x  0.1)........................531
13.4.2 Study of the Phase Transition “Perovskite-Brownmillerite” and
the Structure of the High-Temperature Phases SrCo0.8
xFe0.2MxO3
δ
(M ¼ Nb, Ta; 0 < x < 0.1)..........................................................................535
13.4.3 Study of the Structure of the HT Phase SrCo0.77Fe0.2Ta0.03O2.5 y
With the Help of In Situ High-Temperature M€ossbauer Spectroscopy....539
13.4.4 Study of the Structure and Microstructure of SrCo0.8-xFe0.2MxO2.5+ y
(M ¼ W, Mo; 0 < x  0.2)..........................................................................540
13.4.5 Nanostructured Ferroelastics as Electrode and Membrane Materials for
SOFC/CMR With High Transport and Operational Properties................544
13.5 Concluding Remarks and Outlook...................................................................548
References.................................................................................................................550
Further Reading.........................................................................................................555
Index.............................................................................................................557

xi
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Contributors
Irina V. Belenkaya Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of
Russian Academy of Sciences, Novosibirsk, Russia
Vladimir D. Belyaev Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Yulia N. Bespalko Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Lyudmila N. Bobrova Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Dmitry A. Bokarev Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
Vladimir A. Bolotov Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Olga A. Bragina Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of
Russian Academy of Sciences, Novosibirsk, Russia
Valerii I. Bukhtiyarov Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
V. Cortes Corberán Institute of Catalysis and Petroleumchemistry (ICP), CSC, Madrid, Spain
Valery V. Dutov Laboratory of Catalytic Research, Tomsk State University, Tomsk, Russia
Nikita F. Eremeev Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Yulia E. Fedorova Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Vladimir V. Galvita Laboratory for Chemical Technology, Ghent University, Ghent, Belgium
Elena V. Golubina Chemistry Department, Lomonosov Moscow State University, Moscow, Russia
Sergey A. Gurevich Ioffe Physical-Technical Institute of the Russian Academy of Sciences, St.
Petersburg, Russia
Guannan Hu School of Engineering, University of Warwick, Coventry, United Kingdom
Nicholas Jose Department of Chemical Engineering and Biotechnology, University of Cambridge,
Cambridge, United Kingdom; Cambridge Centre for Advanced Research and Education in Singapore
Ltd., Singapore, Singapore
Tamara S. Kharlamova Laboratory of Catalytic Research, Tomsk State University, Tomsk, Russia
Mikhail V. Korobeynikov Budker Institute of Nuclear Physics SB RAS, Novosibirsk, Russian
Federation
Vladimir M. Kozhevin Ioffe Physical-Technical Institute of the Russian Academy of Sciences, St.
Petersburg, Russia
Ekaterina A. Kozlova Boreskov Institute of Catalysis, Novosibirsk, Russian Federation
Alexey V. Krasnov Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Tamara A. Krieger Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia
Alexei Lapkin Department of Chemical Engineering and Biotechnology, University of Cambridge,
Cambridge, United Kingdom; Cambridge Centre for Advanced Research and Education in Singapore
Ltd., Singapore, Singapore

xiii
Contributors

Changdong Li University of Warwick, Warwick, United Kingdom

Maoshuai Li University of Warwick, Warwick, United Kingdom
Ekaterina S. Lokteva Chemistry Department, Lomonosov Moscow State University, Moscow,
Russia
Anton I. Lukashevich Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Grigory V. Mamontov Laboratory of Catalytic Research, Tomsk State University, Tomsk, Russia
Guy B. Marin Laboratory for Chemical Technology, Ghent University, Ghent, Belgium
Konstantin I. Maslakov Chemistry Department, Lomonosov Moscow State University, Moscow,
Russia
Yulia G. Mateyshina Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of
the Russian Academy of Sciences, Novosibirsk, Russia
Natalia V. Mezentseva Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia
Mikhail A. Mikhailenko Budker Institute of Nuclear Physics SB RAS, Novosibirsk, Russian
Federation
Dmitry Yu. Murzin Process Chemistry Centre, Åbo Akademi University, Turku, Finland
Alexander P. Nemudry Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of
Russian Academy of Sciences, Novosibirsk, Russia
Valentin N. Parmon Boreskov Institute of Catalysis, Novosibirsk, Russian Federation
Hilde Poelman Laboratory for Chemical Technology, Ghent University, Ghent, Belgium
Igor P. Prosvirin Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Evgeny Rebrov School of Engineering, University of Warwick, Coventry, United Kingdom;
Department of Biotechnology and Chemistry, Tver State Technical University, Tver, Russia
V. Rives GIR-QUESCAT, Department of Inorganic Chemistry, University of Salamanca,
Salamanca, Spain
Tatiana N. Rostovshchikova Chemistry Department, Lomonosov Moscow State University,
Moscow, Russia
Ekaterina M. Sadovskaya Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia
Vladislav A. Sadykov Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia
Mikhail A. Salaev Laboratory of Catalytic Research, Tomsk State University, Tomsk, Russia
Alexander N. Shmakov Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia; Budker Institute of Nuclear Physics SB RAS, Novosibirsk, Russian Federation
Irina L. Simakova Boreskov Institute of Catalysis, Novosibirsk, Russia
Pavel I. Skriabin Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
Oleg L. Smorygo Powder Metallurgy Institute, Minsk, Belarus
Alexandr Yu. Stakheev Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia
V. Stathopoulos Laboratory of Chemistry and Materials Technology, School of Technological
Applications, Technological Educational Institute of Sterea Ellada, Greece
Yuri Yu. Tanashev Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia

xiv
 Contributors

Stavros Alexandros Theofanidis Laboratory for Chemical Technology, Ghent University, Ghent,
Belgium
Artem S. Ulihin Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the
Russian Academy of Sciences, Novosibirsk, Russia
Nikolai F. Uvarov Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the
Russian Academy of Sciences, Novosibirsk, Russia
Andre C. van Veen University of Warwick, Warwick, United Kingdom
Zakhar S. Vinokurov Boreskov Institute of Catalysis SB RAS; Novosibirsk State University,
Novosibirsk, Russia
Olga V. Vodyankina Laboratory of Catalytic Research, Tomsk State University, Tomsk, Russia
Denis A. Yavsin Ioffe Physical-Technical Institute of the Russian Academy of Sciences, St.
Petersburg, Russia

xv
This page intentionally left blank
Preface
Nanomaterials now play tremendous role in dealing with the problems of renewable energy
generation and environment protection being used in the design of catalysts for a variety of
related chemical/photochemical processes, solid oxide fuel cells, membranes for oxygen/
hydrogen separation, rechargeable power sources, solar panels, etc. Any progress in these fields
is based upon understanding fundamental factors controlling functional properties of these
materials determined by their chemical composition and real/atomic structure depending on
their genesis and evolution due to interaction with environment. Hence, approaches, methods,
and techniques of materials science, surface science, reaction kinetics, and engineering are to be
combined to deal with these problems and achieve a practical success in the design of efficient
devises. Main aspects of this concept are illustrated in presented book based upon the
experience of the team of authors in frames of a broad international collaboration promoted by
EC FP6 and FP7 programs, Russian Ministry of Education and Science, Russian Fund of Basic
Research, and Russian Scientific Foundation.
A broad range of nanomaterials considered in this book includes Ru colloid nanoparticles; Ag,
Pt, Pd, Ru, and Ni nanoparticles and nanoalloys on a variety of supports; simple oxides (Co3O4,
Mn3O4, Fe3O4 and Fe2O3, TiO2, CeO2, ZrO2, Cu2O, and rare-earth oxides); mixed oxides
(ZrO2-CeO2, doped ceria, doped zirconia, doped ceria-zirconia, Fe-V-doped titania, Zn-Cr
hydrotalcites, spinels, perovskites, doped La silicates with apatite structure, and zeolite
H-ZSM-5); supported oxides (MnO/CeO2, NiO/YSZ, V2O5-WO3 over TiO2 nanotubes, etc.);
and nanocomposites (V2O5-WO3 over TiO2 nanotubes, Cd1
xZnxS loaded with CuS or NiS,
perovskite-doped ceria or zirconia nanocomposites for SOFC cathodes and oxygen separation
membranes, alkali-ion conducting composites CsCl-Al2O3, etc.).
Advantages of new approaches to synthesis of nanomaterials were discussed with a due regard
for synthesis in flow conditions (including supercritical alcohols); laser electrodispersion of
single metals or alloys on carbon, silicon, or oxide supports; mechanochemistry; sonochemical
procedures; microwave or radiation-thermal treatment; sol-gel routes; selective adsorption
of silver cations on oxide supports in specific conditions, etc. These procedures allow to obtain
systems with a narrow particle size distribution, controlled metal-support interaction, and
nanocomposites with uniform spatial distribution of domains of different phases even in dense
sintered materials.

xvii
Preface

Specificity of the real structure and surface properties of nanomaterials characterized by

advanced methods (X-ray synchrotron radiation diffraction, neutronography, transmission/
scanning electron microscopy with elemental analysis, solid-state nuclear magnetic resonance,
in situ high-temperature M€ ossbauer spectroscopy, X-ray photoelectron spectroscopy,
infrared and electron spin resonance spectroscopies of adsorbed test molecules, etc.) as well
as of their transport properties characterized by impedance spectroscopy and oxygen isotope
heteroexchange were considered. Effects of nanosystem composition, bulk and surface
properties, metal-support interaction, redistribution of elements between nanodomains in
metal-oxide and oxide-oxide nanocomposites, particle size and morphology, deposition
density, etc. on their functional properties (reactivity, transport characteristics, catalytic
activity, and reaction mechanism) with a due regard for the high-temperature sintering, catalyst
interaction with the reaction media leading to change of the phase composition, aging, etc.
were analyzed.
The scope of considered catalytic reactions includes transformation of fuels into syngas and
hydrogen; photocatalytic reactions of hydrogen evolution from aqueous solutions of inorganic
electron donors under visible light; methanol-to-hydrocarbon transformation on zeolite
catalysts; total oxidation of hydrocarbons, formaldehyde, ethanol, CO, and NO; and oxidative
dehydrogenation and selective oxidation of light alkanes and oxygenates. Unique catalytic
properties of extremely low-loaded (less than 0.01 mass%) monometallic (Cu, Ni, and Pd) and
bimetallic (NiPd and NiAu) systems prepared by laser electrodispersion method in
isomerization, hydrogenation, hydrodechlorination reactions were demonstrated. For
colloid-derived Ru NPs, such reactions as CO2 hydrogenation to formic acid; selective
hydrogenation of unsaturated aldehydes (citral); asymmetrical hydrogenation of aromatic
ketones to secondary alcohols; hydrogenation of a keto group of pyruvic acid; hydrogenation of
C]O or C]C bonds in substituted acetophenones, ethylpyruvate, methyl-2-
acetamidoacrylate and m-methylanisole, and galactose and glucose to corresponding galactitol
and sorbitol; and direct hydrogenolysis of cellobiose into polyols were shown to be efficiently
catalyzed as well.
Nanocomposites composed of complex oxides (La- or Pr-doped ceria-zirconia solid solutions,
complex perovskite La0.8Pr0.2Mn0.2Cr0.8O3, and their combinations with YSZ or NiO/YSZ)
promoted by Pt, Ru, Ni, or their combination, selected by results of short-term screening tests in
diluted feeds as promising catalysts for the transformation of gas and liquid fuels into syngas,
were shown to retain their activity and coking/sintering stability when supported on structured
substrates (metallic, cermet, and ceramic) and tested in real feeds at high temperatures and
reagent concentrations in pilot-scale installations. This is provided by the optimization of their
composition and preparation procedures ensuring developed interfaces between components
activating fuel molecules (Ni and Ni-Pt/Ru alloys) and oxidant (O2, H2O, and CO2) molecules
(complex oxides with perovskite and fluorite structures). No cracking or detachment of layers
from substrates after reaction was observed. For steam reforming of methane, the most

xviii
 Preface

promising results were obtained for nanocomposite active component

La0.8Pr0.2Mn0.2Cr0.8O3 + NiO + YSZ promoted by Ru and supported on compressed Ni-Al foam
substrate and corundum layer protected Fecralloy gauzes. For the transformation of CH4 and
liquid fossil fuels (decane and gasoline) into syngas via fast selective oxidation at short
contact times and for oxysteam reforming of biofuels (ethanol and acetone), the most promising
type of active component is composed of Pr-doped ceria-zirconia solid solution promoted by
LaNi(Pt)O3. A radial-type reactor combining layers composed of structured heat-conducting
catalytic elements and high-surface-area microspherical catalysts appears to be the most
attractive for selective oxidation of fuels into syngas due to internal heat recuperation. Basic
kinetic features of methane partial oxidation and steam reforming on nanocomposite active
components were elucidated and applied for modeling of structured catalyst performance
in pilot reactors. Performance of structured catalysts in CH4 internal reforming mode meets the
targets of SOFC design by area-specific resistance, activity, and power density.
For materials used in the design of SOFC, membranes, batteries, etc., important role played by
domain boundaries/interfaces was reliably demonstrated. Thus, for alkali-ion conducting
composites, the most strong interface interaction was observed for lithium salts resulting in the
highest ionic conductivity, making them promising for the practical applications in solid-state
batteries and supercapacitors.
For ferroelastic perovskites with mixed conductivity such as SrCo0.8
xFe0.2MxO3
δ (M ¼ Nb,
Ta, W, and Mo), promising as electrode materials for SOFCs and membrane materials, an
increase in the compositional disorder due to doping with ferroactive cations Nb/Ta (V) and
Mo/W (VI) was accompanied by diffusing of the perovskite-brownmillerite phase transition
due to local transformations in the perovskite matrix with the formation of randomly
oriented 90° nanosized domains. A significant difference in the charge of B cations upon
doping with Mo/W (VI) results in the local ordering with the formation of domains with a
double perovskite structure. Nanostructuring resulted in the suppression of undesirable phase
transitions and a high density of interfaces between coherently joined domains favorably
affects the thermomechanical and oxygen transport properties of doped materials.
In nanocomposites of perovskites (doped manganites, nickelates, cobaltites, etc.) with solid
electrolytes (doped ceria, zirconia, etc.), enhanced oxygen mobility along perovskite-fluorite
interfaces and generation of new active sites for oxygen exchange on the surface of the
electrolyte domains due to cation redistribution make such materials promising for using in IT
SOFC cathodes and oxygen separation membranes.
A high power density of single thin-film fuel cells in the intermediate temperature range with
nanocomposite cathodes was reached. Asymmetrical supported oxygen and hydrogen
separation membranes with nanocomposite permselective layers on Ni-Al foam substrate
demonstrated promising and stable performance/high permeation flaxes due to fast ionic
transport and high catalytic activity of the materials concerned.

xix
Another random document with
no related content on Scribd:
Thou Dorothea remembered that perhaps Dolly did not
render herself attractive to Edred.

"I have seen her look lovely—as you say."

Dorothea gave him an eager glance, trying to read further.

Did he really feel no more than he showed? At the same
moment Mervyn and Dolly swept past again, nearer and
more slowly than before. Dolly lifted her blue eyes, and
gazed full at Dorothea, with a heart-sick reproachful gaze.
Dorothea was startled, even confounded, by it. The look
was such as she might have received from one whom she
had deeply injured. But how could she have injured Dolly?
Was she not studiously keeping aloof from Mervyn, for
Dolly's sake, forbearing to give him a needless smile?

Edred seemed not to have noticed the little interlude. He

went on without a break: "If one wanted mere prettiness,
and nothing more—"

"Oh!" cried Dorothea indignantly. "You don't mean Dolly!

You are not speaking of Dolly!"

Edred made no answer. Dorothea was hurrying forward,

under the strength of her own feelings.

"You have known her so many years, and I only two days,—
but to think of accusing Dolly of mere prettiness! You can't
know Dolly really. You can't have seen her in her home,
with her father and mother and her sisters. And I fancied
that you—"

Dorothea paused, and Edred's usually impassive face was

aglow. "Thanks," he said abruptly. "Yes, I—I think I do know
her. Forget what I said just now," and his voice showed
agitation. "Forget everything, except that she—that no one
in the world can ever be to me what Dolly is."
"I thought so," murmured Dorothea. "But why—?"

"Why do I not seek her? What is the use? Cannot you see
for yourself. Have I a grain of hope to work upon?"

Dorothea could not say that he had. She could only say,—"If
I were a man, I would not give in so easily."

"If you were a man, I suppose you would do as a man

does," he observed drily. "I don't know what has made me
say so much to you, Miss Tracy. Pray consider it to be
strictly in confidence—and pray forget the whole."

"I shall not forget; and I shall not repeat it," said Dorothea.
"But I still think that if I were you, I would try to win her."

Both Dorothea and Edred were too deeply interested in their

subject to pay much attention to what went on around.
Edred's eyes were bent downward, and Dorothea's were
occupied in studying him. They were skating round a tiny
islet which lay at one end of the pond, carelessly keeping to
the left of the narrow ice-belt, and calmly oblivious of the
fact that other people might choose to round the islet from
the opposite direction.

"Hallo!" A warning shout from Mervyn recalled their

wandering minds to the present. But the shout came too
late. Mervyn and Dolly, skimming lightly one way, met
Edred and Dorothea in full career. The four went down
together, and Dolly was underneath.

The two young men were up instantly; and almost before

Dorothea knew what had happened, she found herself again
on her feet, helped up by Mervyn's strong hands. Dolly
alone lay white and still on the hard ice.
"You are not hurt? You are sure you are not hurt?" Mervyn
was saying anxiously to Dorothea, while Edred was
endeavouring to lift Dolly. "You are quite sure?"

A keen throb of joy passed through Dorothea. She could not

but see that Mervyn's first thought was of her; his chief
solicitude was for her. Then she thrust the joy fiercely aside.

"O no, no; not in the least. But Dolly,—poor Dolly! Don't
think of me! Only think of Dolly," she implored.

CHAPTER XX
CUTTING THE KNOT

NEARLY ten days had gone by, and nothing would induce
Colonel Tracy to prolong his stay at the Woodlands. He
enjoyed being there immensely, he avowed; and the old
reconciled comrades were well-nigh inseparable.
Nevertheless, the Colonel confessed to Dorothea a private
craving for his town-life, his quiet room, his solitary candle
and musty books. He "wasn't made to live in a crowd," he
said. Dorothea could not echo his sentiments, but she
acquiesced.

Edred had prolonged his stay at the Park, and Mervyn was
there still, instead of taking flight with his usual speed. Both
brothers now, however, talked of leaving: Edred at the same
time as the Tracys—Mervyn a day or two later.

For more than a week, ever since the skating, Dolly had
been upstairs, invisible. Her poor little bruised face was at
first in no state to be seen: and also, she had been too
unwell to leave her room. The shock of her fall had perhaps
only given a finishing stroke to long previous strain. From
one cause or another, she was thoroughly weak and low,
disposed to tears on the slightest pretext, and unable to
rally.

Dorothea had had no easy part to play. She found herself

very much in request with both brothers: with Mervyn
plainly for her own sake; with Edred as plainly for Dolly's
sake. Edred liked to get Dorothea alone, and to hear her
talk about Dolly; only nobody except Dorothea was aware of
this explanation. She was very willing to talk to him of
Dolly, and she was very anxious to do her duty to Dolly in
keeping Mervyn at arm's length. But the latter task was by
no means easy; partly because she was doing violence to
her own inclinations—partly because Mervyn was of a
nature not to be easily checked.

Matters had developed fast in these few days. When

Dorothea first came to Craye, she liked Mervyn, and she
knew that she could like him very much more. The potential
had now become the positive. Dorothea not only liked him
very much more, but she felt that for her, he stood alone as
the man who was unlike all other men. This means
something far beyond mere liking; yet for Dolly's sake
Dorothea strove hard to hide what she felt, to treat him as
a mere acquaintance.

Perhaps she was less successful in veiling her true feelings

than she imagined. Perhaps Mervyn had a keener insight
into woman's nature than Edred. The more Dorothea
endeavoured to hold aloof, the more persistently he came
after her. Both young men were constantly in and out of the
house all through that week, and both appeared to come
mainly for the purpose of talking to Dorothea. There was no
appearance of jealousy between them; perhaps because the
sunny-tempered Mervyn was not given to jealousy, perhaps
because Edred felt too secure. So, at least, people
conjectured. It might easily be thought by a looker-on that
she gave encouragement to Edred. She was more at her
ease with him than with Mervyn.

And poor little Dolly all this while was hors de combat,
unable to fight her own battle. It did seem hard to the elder
sisters; both of whom had now a pretty clear understanding
of the state of Dolly's mind, and neither of whom supposed
Dorothea to be fighting Dolly's battle for her—only through
ignorance fighting it wrongly. Isabel and Margot had seen
with pleasure Mervyn's evident fancy for Dorothea; and
they would have been equally pleased to see the "fancy"
returned. Attentions from Edred were another matter, and
that his attentions should be apparently well received, while
those of Mervyn were more or less rebuffed, exercised the
sisters greatly.

"I think it is too bad—quite too bad!—and I wish they had

never come to Woodlands at all," Isabel declared hotly.

Margot could have echoed the wish. "But that is hardly fair,"
she said. "Edred might never have cared for Dolly in any
case,—and I am sure Dorothea does not know how things
are."

"Then she ought to know! People ought to use their eyes,"

said unreasonable Isabel.

"Some people haven't the gift," remarked Margot, thinking

how slow Isabel herself had been.

"Why shouldn't one give her a hint, Margot? I'll do it."

Margot shook her head. She had a great dread of interfering

in such matters. Simple blundering Isabel, who had done
damage before by her outspokenness, pondered the matter
for a whole half-hour, and came to the conclusion that this
was a case for open speech. People like Isabel who meddle
in everything, do harm nine times out of ten; but the tenth
time they occasionally manage to set wrong right, thereby
gaining encouragement to proceed in the same course. The
nine times are forgotten—the one is remembered.

Twice a day Dorothea was allowed to see Dolly for a chat.

She would gladly have stayed longer than the stipulated
fifteen or twenty minutes; but no encouragement to do so
was given. Dorothea was keenly aware that, Dolly did not
care to have her. A barrier seemed to divide them; and not
all Dorothea's efforts could do away with it. "And yet we
ought to be friends," she said often to herself.

Mervyn and Edred had each promised separately to look in

late that last afternoon—Mervyn to say good-bye to the
Tracys, Edred to say good-bye to the Erskines. "About tea-
time," both had said; and there was some idea of Dolly
coming down for the first time; but though perhaps well
enough, she seemed to shrink from the exertion.

The matter was still undecided at four o'clock. "Will she

come!" Dorothea asked eagerly, meeting Isabel on the
stairs. Isabel gazed absently, with wrinkled brow, and asked
"Who?"

"I mean Dolly. Margot said she might be able. Wouldn't it do

her good?—to be downstairs, I mean."

Isabel was too much absorbed with one idea to have room
in her mind for any other train of thought. "Yes,—no,—I am
not sure. Dolly isn't sure yet, I believe," she said vaguely,
moving towards the nearest open door on the next landing,
with the air of one expecting to be followed. "I have been
thinking that I—I—there is something I should rather like to
ask you."

Dorothea walked after her into the bedroom, and waited.

Isabel carefully closed the door, and then fidgeted to the

fireplace.

"Dolly seems so depressed just now, doesn't she! Has she

not seemed so to you?"

"Yes; I wish she did not. But perhaps in a few days she will
be better."

"She is getting over the fall. It is not only that now: at

least, I believe not. I am speaking privately—I mean I
shouldn't like what I say repeated to anybody—but—but—"
blundered Isabel, "you see, we seem to know you pretty
well now. And you have seen a great deal of the
Claughtons."
"Yes, a good deal." Dorothea could not restrain a slight
blush.

"And I thought I would just ask—I thought I could just put a

little question. I should like so much to know whether it has
struck you—whether you have an impression that either of
them cares at all for Dolly,—cares very particularly, I
mean."

Dorothea was silent. If she had had merely an "impression,"

she could have told it at once; but how could she betray
Edred's confidence to Isabel?

"You see I am asking for Dolly's sake. One can't help

noticing,—and I dare say you have noticed that she does
seem to—well, to have a particular liking for one of them—
more than just friendship."

Dorothea said "Yes" again.

"I was sure you couldn't help seeing. At one time we really
thought something was coming of it,—but lately I have felt
doubtful. He doesn't seem to take the same pains,—and I
do believe that is why poor little Dolly is so down-hearted.
Of course, one can't do anything: and, as Margot says,
things must be left to take their own course. Still, I thought
I might just ask you, as a friend, whether you have noticed
—"

Dorothea liked to be treated as a friend, and she had

noticed a great deal; but she was puzzled what response to
make.

"I can't imagine for my part what has made him so stiff and
cold," said Isabel, knitting her brows. "Of course, he never
is very lively—still, he used not to be like this. Margot says
—but I don't believe—"
Dorothea broke into the confused sentences.

"Mr. Mervyn Claughton stiff and cold!"

"Mervyn! I'm speaking of Edred, of course. You haven't

supposed that I meant Mervyn all the while!"

Dorothea stood mute; her eyes unwontedly bright.

"You didn't think Dolly cared for Mervyn!" exclaimed Isabel.

"You couldn't—possibly!"

"I suppose it was stupid of me, but I really did!"

Isabel stood looking with puzzled eyes. "I don't know what I
have said to make you so happy," she said.

"Don't ask me anything, please," begged Dorothea in

answer. "Don't say any more. Only let me see Dolly for a
few minutes,—and if I can persuade her to go into the study
for an hour, don't put any difficulties in the way. I have my
reasons: and I must not explain."

"Dolly to go into the study!"

"Yes. It will be all right, only please just let it be so. I want
to see Dolly alone. I will not repeat a word that you have
said."

Two minutes later, Dorothea, vividly conscious that Isabel

had cut a Gordian knot, was kneeling beside Dolly's couch.

"Dolly, I have something to propose," she said softly. "Dolly,

listen to me. Margot thought you were too tired to come
down among us all to-day. But I want you not to mind being
tired. I want you to manage just to get to the study sofa for
an hour."
"What for?" asked Dolly languidly.

"Because—" and she lowered her voice,—"Mr. Edred

Claughton will be so disappointed if he cannot see you once
more before he goes."

If Dorothea had any doubts remaining, the glow which leapt

to Dolly's white face was enough to do away with them.

"He and I feel so guilty about this week," Dorothea went on.
"It was all our fault,—your being laid up, I mean. If we had
not both been so stupidly full of what we were talking
about, we should have had our wits about us, and there
need have been no collision."

"It can't be helped."

"I almost think you would forgive us both, if you knew what
it was that interested us so much. Guess! What do you
think it could be?"

"I don't know."

"It was—Dolly, of course. What else could be so

engrossing?"

Dolly's cheeks became brighter still.

"I don't think I ought to say much more. I would not say so
much to any one except you. But—I do know that he is
longing to see you before he goes; and I thought—if you
could get down to the study, that might be the best way.
And, Dolly—" very softly—"darling, don't be too cold. He has
been so hopeless,—and I don't think he has much pluck."

Dolly said not a word in answer. She only put both arms
round Dorothea, and held her fast, as if thus cementing the
friendship which was to have been, but which hardly yet
had begun to be between them.

Five o'clock drew near, and Dolly was in the study. Dorothea
wondered how affairs would fit in. Would Edred be too shy
to use his opportunity? And would Mervyn appear at all?
Her thoughts were in a whirl, but by no means on her own
account only. The last few days had been an education in
unselfishness.

Both Colonels were absent on a long ramble, and Mrs.

Erskine had not appeared from her afternoon repose, when
the two Claughtons marched in together. Isabel fled at the
sound of the front door opening; Margot alone remaining
with Dorothea. The latter could not guess whether this were
a condition of things purposely arranged. She only knew
that it was unusual. Her own face, commonly pale, had
perhaps never been brighter or prettier than now when for
the first time she could venture to meet Mervyn with an
unchecked smile of welcome. She did not seem excited, but
there was a glow in her cheeks, and the placid eyes shone
softly through their glasses.

"Dolly is in the study," Margot remarked, as Edred glanced

round.

Margot had evidently no intention of saying more. She

seated herself, and began to talk to Mervyn, while Edred
showed not the least disposition to act on his own behalf. In
another moment, he too would have subsided into a chair,
but Dorothea stood up, and came close to him.

"Dolly is in the study," she repeated in an undertone, not

meant for the other two. "You told me yesterday that you
wanted to see her."

"Well, yes," assented Edred.

"She is there on the sofa; why not go to her—now?"

"At once!" Edred seemed reluctant. "What is the use?" he

asked despondingly.

"The use! Make it of use. O go, do go!"

The voice, though low, was energetic enough to reach

Margot and Mervyn. Edred actually obeyed without another
word; and as the door closed behind him, Dorothea turned
to meet two smiling faces.

"Never was better advice given," uttered Mervyn. "I have a

mind to follow it myself. Margot—be kind! All the world will
buzz about our ears directly. Don't you think you ought, as
a duty, to keep watch outside the study-door? Just for five
minutes!"

"That would be a double kindness, I suppose! Well—just for

five minutes!" and Margot too left the room.

Dorothea, occupied still with Dolly, did not see through this
move, till she found herself alone with Mervyn, felt her
hands imprisoned in his, and heard him say—

"We have only five minutes! Not a moment to lose!

Dorothea—if anybody in the world understands me, it is
yourself. Do you know me well enough—to—"

Then she knew what was coming, and she did not shrink
from it. Thanks to Isabel's cutting of the tangled knot, she
had no hesitation as to what answer she might or would
give.

Within the specified five minutes, Dorothea had become the

affianced wife of Mervyn; and within half-an-hour, Dolly was
the affianced wife of the less expeditious Edred.
"Nothing could have been better managed. It really is
delightful all round," declared Isabel to Margot, dallying in
her room late that night. "I always knew the Claughtons
would be charmed. Emmeline is hard to please, but she
really does take to Dorothea. And as for Colonel Tracy, I
believe he wants nothing more than to get her off his
hands."

"Now, Issy!"

"You know what I mean. He is an odd man, and he can't

help it, I suppose. But I am sure Dolly and Dorothea look
the picture of happiness. I believe Dorothea will be the
making of Mervyn. He is a nice fellow, though Emmeline
underrates him to such an extent. I wonder what Edred's
friend Mrs. Effingham will say?"

"She has not much to do with the matter. I often wonder

she has not taken more trouble about Dorothea."

"Oh, well—people in London have no time, and she is

always in a bustle. But isn't this a curious finale to the long
quarrel,—that the two babies, Christened together, and then
never meeting till they are nearly twenty, should marry
brothers, and become almost sisters! Now, Margot, I know I
often seem to you a great deal too outspoken, and perhaps
I am. But just this once, don't you think I was right?"

"Just this once, Issy, I haven't a word to say," Margot

answered.
THE END
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