edited by pascal granger, vasile i. parvulescu, serge ... · edited by pascal granger, vasile i....

Edited by Pascal Granger, Vasile I. Parvulescu, Serge Kaliaguine, and Wilfrid Prellier

Perovskites and Related Mixed Oxides

Concepts and Applications

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Editors

Prof. Pascal Granger Université Lille Unité de Catalyse et de Chimie du Solide Bâtiment C3 59655 Villeneuve d’Ascq Cedex France

Prof. Dr. Vasile I. Parvulescu University of Bucharest Faculty of Chemistry Regina Elisabetha Bld. 4-12 030016 Bucharest Romania

Prof. Serge Kaliaguine Laval University Department of Chemical Engineering 1065, Avenue de la médecine Quebec City, QC G1V 0A6 Canada

Dr. Wilfrid Prellier Université de Caen Laboratoire CRISMAT 6, bvd Maréchal Juin 14050 Caen France

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V

Contents

List of Contributors XXIII Preface XXXV

Volume 1

Part One Rational Design and Related Physical Properties 1

1 From Solid-State Chemistry to Soft Chemistry Routes 3 Vicente Rives

1.1 Introduction 3 1.2 Processes Involving Solids 4 1.2.1 The Ceramic Method 4 1.2.2 Microwave Synthesis 5 1.2.3 Self-Propagating High-Temperature Synthesis (SHS) 6 1.2.4 The Precursor Method 6 1.2.5 Hydrothermal Synthesis 7 1.2.6 High-Pressure Methods 8 1.2.7 Mechanochemistry 8 1.2.8 Other Methods Starting from Solids 9 1.3 Processes Involving Liquids 9 1.3.1 Flux Method 9 1.3.2 Molten Salt Electrolysis 10 1.3.3 Sol–Gel 10 1.3.4 Spray Drying (SD) and Related Methods 13 1.3.4.1 Freeze-Drying 14 1.3.4.2 Spray–Freeze-Drying 14 1.3.5 Molecular Self-Assembling 14 1.3.6 Other Methods Starting from Liquid Reactants

or Solutions 15 1.3.6.1 Ionic Liquids 15 1.3.6.2 The Gel Combustion Method 15 1.3.6.3 Sonication 15

VI Contents

1.3.6.4 Reverse Microemulsion 15 1.4 Processes Involving Gases or Vapors 16 1.4.1 Gas Flame Combustion 16 1.4.2 Chemical Vapor Deposition (CVD) 16 1.5 Single Crystals 16 1.6 Nanoparticles 18 1.7 Films 19 1.8 Conclusions 19

References 20

2 Mechanochemistry 25 Houshang Alamdari and Sébastien Royer

2.1 Introduction 25 2.2 Historical Development 25 2.3 Terminology 28 2.4 Mechanosynthesis Process 29 2.5 Milling Facilities 32 2.5.1 Spex Mills 32 2.5.2 Planetary Mills 34 2.5.3 Attrition Mills 35 2.5.4 Zoz Mills 36 2.6 Mechanosynthesis of Perovskites 37 2.6.1 Looking for an Alternative Route to Synthesize

New Compositions 38 2.6.2 Lowering Sintering Temperature 38 2.6.3 Reducing Crystallite Size and Modifying Particle

Morphology 39 2.6.4 Increasing Specific Surface Area 40 2.7 Concluding Remarks 42

References 43

3 Synthesis and Catalytic Applications of Nanocast Oxide-Type Perovskites 47 Mahesh Muraleedharan Nair and Serge Kaliaguine

3.1 Introduction 47 3.2 Perovskite Structure 48 3.3 Evolution of Perovskite Synthesis 49 3.4 General Principles of Nanocasting 51 3.5 Nanocasting of Perovskites 52 3.6 Catalytic Studies 56 3.6.1 Total Oxidation of Methane 56 3.6.2 Reduction of NO to N2 57 3.6.3 Chemical Looping Combustion 58 3.6.4 Total Oxidation of Methanol 59 3.6.5 Dry Reforming of Methane 60

VII Contents

3.7 Conclusions and Perspectives 63 References 64

4 Aerosol Spray Synthesis of Powder Perovskite-Type Oxides 69 Davide Ferri, Andre Heel, and Dariusz Burnat

4.1 Introduction 69 4.2 Flame Spray Synthesis 71 4.2.1 Methane Flame 72 4.2.2 Acetylene Flame 75 4.3 Flame Hydrolysis 80 4.4 Ultrasonic Spray Synthesis 82 4.4.1 General Particle Properties 83 4.4.2 Citric Acid Assisted Synthesis 85

References 87

5 Application of Microwave and Ultrasound Irradiation in the Synthesis of Perovskite-Type Oxides ABO3 91 Juan C. Colmenares, Agnieszka Magdziarz, and Paweł Lisowski

5.1 Introduction 91 5.2 Microwave Methodology 92 5.2.1 Basic Concepts of Microwave Chemistry 92 5.2.2 Microwave Heating in Combination with Traditional

Synthesis Methods 93 5.2.2.1 Microwave-Assisted Hydrothermal Method (HTMW) 93 5.2.2.2 Other Microwave-Assisted Methods 100 5.3 Ultrasound Methodology 101 5.3.1 Basic Concepts of Ultrasound Chemistry 101 5.3.2 Ultrasound-Assisted Coprecipitation Method 102 5.3.3 Ultrasound-Assisted Sol–Gel Method 103 5.3.4 Ultrasound Spray Pyrolysis 105 5.3.5 Other Ultrasound-Assisted Methods 107 5.4 Concluding Remarks and Outlook 108

Acknowledgments 108 References 109

6 Three-Dimensionally Ordered Macroporous (3DOM) Perovskite Mixed Metal Oxides 113 Masahiro Sadakane and Wataru Ueda

6.1 Introduction 113 6.2 3DOM Materials 114 6.2.1 Preparation of 3DOM Materials 114 6.2.1.1 Colloidal Crystal Templates 114 6.2.1.2 Infiltration of Precursors in the Voids of Templates 122 6.2.1.3 Removal of Templates 122 6.2.2 Structure of 3DOM Materials (Inverse Opal Structures) 122

VIII Contents

6.3 Preparation of 3DOM Perovskite Mixed Metal Oxides 123

6.3.1 Precursor Solution 123 6.3.2 Selection of Sphere Templates 126 6.3.3 Synthesis Methods and Applications of 3DOM Perovskite

Mixed Metal Oxides 127 6.3.4 Preparation of 3DOM LaFeO3 with Different

Pore Sizes 131 6.3.4.1 Preparation of Polymer Spheres and Colloidal Crystal

Templates 131 6.3.4.2 Synthesis of 3DOM LaFeO3 134 6.3.4.3 Characterization of 3DOM LaFeO3 134 6.3.4.4 Formation Mechanism 136 6.4 Conclusions 138

References 138

7 Thin Films and Superlattice Synthesis 143 Carmela Aruta and Antonello Tebano

7.1 Introduction 143 7.2 Thin Films and Superlattices Growth 145 7.2.1 Deposition Techniques 145 7.2.1.1 MBE 145 7.2.1.2 PLD 149 7.2.1.3 Sputtering 153 7.2.2 In Situ Monitoring: RHEED and Plume

Analysis 156 7.2.2.1 RHEED 156 7.2.2.2 Plume Analysis 159 7.3 Concluding Remarks 162


8 Perovskite and Derivative Compounds as Mixed Ionic–Electronic Conductors 169 Caroline Pirovano, Aurélie Rolle, and Rose-Noëlle Vannier

8.1 Introduction 169 8.2 Perovskite as Mixed Ionic–Electronic Conductors 170 8.2.1 The Perovskite: A Flexible Structure for Mixed Ionic–Electronic

Conductivity 170 8.2.2 Cobaltites: Among the Best MIEC Materials 173 8.2.3 MIEC Electrochemical Performances as SOFC or SOEC

Electrodes 173 8.3 Conductivity and Oxygen Transport Properties in Mixed

Ionic- and Electronic-Conducting Perovskites 176 8.3.1 Electrical Conductivity 177

IX Contents

8.3.2 Diffusion Coefficients 177 8.3.3 Surface Exchange Coefficients 179 8.3.4 Perovskite Materials and Related Compounds

Oxygen Transport Parameters 180 8.4 Conclusions 183

References 184

9 Perovskite and Related Oxides for Energy Harvesting by Thermoelectricity 189 Sascha Populoh, O. Brunko, L. Karvonen, L. Sagarna, G. Saucke, P. Thiel, M. Trottmann, N. Vogel-Schäuble, and A. Weidenkaff

9.1 Introduction to Thermoelectricity 189 9.2 CaMnO3-Based Compounds 190 9.3 EuTiO3 and Related Compounds 196 9.4 SrCoO3�δ and Related Phases 199 9.5 ZnO for Thermoelectric Applications 200 9.6 Thermoelectric Oxide Modules and Their Characterization 202 9.7 Concluding Remarks 204

References 204

10 Piezoelectrics and Multifunctional Composites 211 Ranjith Ramadurai and Vijayanandhini Kannan

10.1 History 211 10.2 Piezoelectricity: An Introduction 211 10.3 Piezoelectric Materials: An Overview 214 10.4 Lead-Free Piezoelectrics 215 10.4.1 BaTiO3–CaTiO3–BaZrO3 Solid Solutions 216 10.4.2 Structural Phase Diagram of BZT–BCT 217 10.4.3 Piezoelectric Properties of BCT–BZT 218 10.4.4 (Na0.5Bi0.5)TiO3 219 10.5 Piezoelectric Polymers 221 10.5.1 Polyvinylidene Fluoride 222 10.6 Piezoelectric Composites 223 10.7 Polymer–Ceramic Hybrid Piezoelectric Composites 225 10.8 Multifunctional Piezoelectric Composites 226 10.9 Summary 229

References 230

11 Microstructure and Nanoscale Piezoelectric/Ferroelectric Properties in Ln2Ti2O7 (Ln = Lanthanide) Thin Films with Layered Perovskite Structure 233 Sébastien Saitzek, ZhenMian Shao, Alexandre Bayart, Pascal Roussel, and Rachel Desfeux

11.1 Introduction and Overview of Layered Perovskite Structures 233 11.2 Ln2Ti2O7 Compounds 236

X Contents

11.2.1 Structural Properties of Ln2Ti2O7 with Ln = Lanthanide 236 11.2.2 Synthesis Way 237 11.2.3 Scope and Properties of the Ln2Ti2O7 Oxides 238 11.3 Growth and Structural Characterization of Ln2Ti2O7

Thin Films 239 11.3.1 Growth on (100)-Oriented SrTiO3 Substrates 239 11.3.2 Growth on (110)-Oriented SrTiO3 Substrates 242 11.3.3 Limit of Stability of the Layered Perovskite Structure 243 11.4 Piezo- and Ferroelectric Properties of Ln2Ti2O7 Thin Films 244 11.4.1 Experimental Setup 244 11.4.2 Ln2Ti2O7 (Ln = La, Pr, and Nd) Thin Films Grown on (110)-Oriented

SrTiO3 Substrates 246 11.4.3 Ln2Ti2O7 (Ln = La, Pr, and Nd) Thin Films Grown on (100)-Oriented

SrTiO3 Substrates 247 11.4.4 Metastable Ln2Ti2O7 (Ln = Sm, Eu, and Gd) Thin Films Grown on

(110)-Oriented SrTiO3 Substrates 249 11.5 Conclusion 250


12 Pigments Based on Perovskite 259 Matteo Ardit, Giuseppe Cruciani, Michele Dondi, and Chiara Zanelli

12.1 Introduction 259 12.2 Perovskite Pigments 259 12.2.1 Red and Orange 261 12.2.2 Yellow 261 12.2.3 Brown to Light Brown 262 12.2.4 Magenta to Pink 263 12.2.5 Blue 263 12.2.6 Black 263 12.3 (Y, REE) Aluminate Perovskites: Crystal Chemistry and Structural

Principles 263 12.3.1 Crystal Structure of Ideal and Distorted Ternary ABO3

Perovskites 263 12.3.2 Lattice Parameters, A Site Coordination, and Bond Valence Analysis in

(Y,REE) Orthoaluminates 264 12.3.3 Tilting of Octahedral Framework and Tolerance Factor 268 12.4 Chromium Incorporation: Basic Concepts and the YAlO3–YCrO3

Case Study 269 12.4.1 Local Bond Distances 269 12.4.2 Structural Relaxation Coefficient 270 12.4.3 Comparison with Other Al–Cr Solid Solutions 271 12.4.4 Polyhedral Bond Valence Method 272 12.4.5 The (La,Nd)(Ga1�xCrx)O3 Case Study 274

XI Contents

12.5 Origin of Color in (Y, REE) Orthoaluminates 279 References 284

13 Electrolyte Materials 289 Viorica Parvulescu

13.1 Introduction 289 13.2 Properties of Solid Electrolyte Materials 290 13.2.1 Synthesis Methods and Properties of Mixed Oxides

Electrolytes 290 13.2.2 The Crystalline Phases and Conductivity 294 13.3 Mixed Oxides with Ionic Conductivity 295 13.3.1 Solid Electrolytes Based on ZrO2 296 13.3.2 Solid Electrolytes Based on CeO2 298 13.4 Mixed Oxides with Mixed Conductivity 301 13.5 Applications of Mixed Oxides as Electrolytes and Mixed

Conductors 303 13.6 Conclusions 306

References 306

14 CO2 Capture Using Dense Perovskite Membranes: Permeation Models 311 Marc Pera-Titus

14.1 MIEC Membranes for Gas Separation 311 14.2 Background for Mass Transfer Modeling in Perovskite

Membranes 312 14.3 Gas Permeation Models for Perovskite Membranes 315 14.3.1 Single-Phase Perovskite Membranes 316 14.3.1.1 Models for O2 Semipermeation 318 14.3.1.2 Models for H2 Semipermeation 322 14.3.2 Dual-Phase Perovskite Membranes 325 14.3.2.1 Models for H2 Semipermeation within Supported Ni/Perovskite

DFMs 326 14.3.2.2 Models for H2 Semipermeation in Ni-Cermets DFMs 326 14.3.2.3 Models for CO2 Semipermeation in Infiltrated MC/Perovskite

DPMs 327 14.4 Measurement of Diffusion and Surface Exchange Coefficients 329 14.4.1 Semipermeation Coupled to Electrical Potential Measurements 329 14.4.2 Isotopic Exchange Depth Profile (IEDP) 331 14.4.3 Electrical Conductivity Relaxation (ECR) 333 14.4.4 Electrochemical Impedance Spectroscopy (EIS) 333 14.4.5 Diffusion and Surface Exchange Coefficients: Structure–Property

Correlations 334 14.5 Conclusions 334

Glossary 335

XII Contents

Greek Symbols 336 Subscripts 336 Superscripts 337 Acronyms 337 References 337

15 Introduction to Rational Molecular Modeling Approaches 343 Randy Jalem and Masanobu Nakayama

15.1 Introduction 343 15.2 Theoretical Background on Ab Initio Calculation 343 15.2.1 Brief Review of Elementary Quantum Chemistry 343 15.2.2 Density Functional Theory 346 15.3 Simulation Model Construction 347 15.4 Electronic Structure 349 15.5 Ionic Transport 351 15.6 Atomic Arrangement, Phase Stability, and Transition 354 15.7 Conclusions and Outlook 359

References 360

Volume 2

Part Two Perovskite and Related Mixed Oxides in Catalysis: From the Structure to the Catalytic Properties 367

16 Methane Combustion on Perovskites 369 Athanasios Ladavos and Philippos Pomonis

16.1 Perovskites as a Diverse and Active Class of Materials 369 16.1.1 Structural Diversity, Tolerance Factor, and Thermodynamic

Stability 370 16.2 Mixed Valences in Perovskites 371 16.2.1 Mixed Valences Due to Anion Deficiencies 371 16.2.2 Mixed Valences Due to Isostructural Substitution

of Cations 373 16.3 The Reversed Uptake of Oxygen and Its Different

Sources 373 16.4 The Mechanism of Methane Combustion 376 16.5 Kinetics of Methane Combustion 378 16.5.1 Rideal–Eley kinetics 379 16.5.2 First-Order Kinetics 380 16.5.3 The Power Law Kinetics 384 16.5.4 The Two Term Kinetics 385 16.6 Conclusions 386


XIII Contents

17 Total Oxidation of Volatile Organic Compounds 389 Vasile I. Parvulescu

17.1 Introduction 389 17.2 Specificity of Perovskites for Total Oxidation of VOCs 391 17.3 Morphology of Perovskites Investigated for Total Oxidation of

VOCs 395 17.4 Total Oxidation of VOCs under Thermal Activation

Conditions 397 17.5 Total Oxidation of Light Hydrocarbons 399 17.6 Total Oxidation of Oxygenated Organic Compounds 401 17.7 Total Oxidation of Halogenated Organic Compounds 402 17.8 Total Oxidation under Plasma Activation Conditions

in Gas 404 17.9 Photocatalytic Destruction of VOC 406 17.10 Conclusions 407

References 408

18 Total Oxidation of Heavy Hydrocarbons and Aromatics 413 Vasile I. Parvulescu and Pascal Granger

18.1 Introduction 413 18.2 Perovskites and Oxygen Vacancy 414 18.3 Total Oxidation under Thermal Activation Conditions 416 18.4 Total Oxidation of Aromatic Hydrocarbons 417 18.5 Total Oxidation of Polycyclic Aromatic Hydrocarbons 424 18.6 Total Oxidation of Soot 425 18.7 Total Oxidation of Halogenated Hydrocarbons 426 18.8 Total Oxidation under Plasma Activation Conditions 428 18.9 Total Oxidation of Aromatics 429 18.10 Total Oxidation of Soot 431 18.11 Conclusions 431

References 432

19 Progresses on Soot Combustion Perovskite Catalysts 437 Agustín Bueno-López

19.1 Introduction 437 19.2 Particular Aspects of the Soot Combustion Reactions 438 19.3 Soot Combustion Perovskite Catalysts: Effect of Partial Substitution of

Cations in the Perovskite Oxide 439 19.4 Kinetic and Mechanistic Studies 442 19.5 Three-Dimensionally Ordered Macroporous Soot Combustion

Perovskite Catalysts 444 19.6 Study of Soot Combustion Perovskite Catalysts in Real Diesel

Exhausts 445 19.7 Microwave-Assisted Perovskite-Catalyzed Soot

Combustion 446

XIV Contents

19.8 Deactivation of Soot Combustion Catalysts by Perovskite Structure Formation 446

19.9 Conclusions 446 Acknowledgments 447 References 447

20 Low-Temperature CO Oxidation 451 Oscar H. Laguna, Luis F. Bobadilla, Willinton Y. Hernández, and Miguel Angel Centeno

20.1 Overview 451 20.2 Low-Temperature CO Oxidation Reaction 453 20.2.1 LaBO3-Type Perovskites 454 20.2.2 La1�xAxB1�yB´

yO3±δ-Type Perovskites 456 20.2.3 Noble Metal–Perovskite Hybrid Materials 456 20.3 H2 Purification-Related CO Oxidations: Water-Gas Shift (WGS) and

PROX Reactions 459 20.3.1 Perovskites for the Water-Gas Shift Reaction 460 20.3.2 Perovskites for the Preferential CO Oxidation in the Presence of H2

(PROX) 464 20.4 Concluding Remarks 468


21 Liquid-Phase Catalytic Oxidations with Perovskites and Related Mixed Oxides 475 Viorica Parvulescu

21.1 Introduction 475 21.2 Active Sites and Oxidants 476 21.3 Catalytic Reactions with Green Oxidants 480 21.3.1 Perovskites Catalysts 480 21.3.2 Microporous Mixed Oxide Catalysts 483 21.3.3 Mesoporous Mixed Oxide Catalysts 486 21.4 Heterogeneous Photo-Fenton Oxidation 488 21.4.1 Photo-Fenton Reactions with Perovskites 490 21.4.2 Photo-Fenton Reactions with Porous Mixed Oxides 491 21.5 Photocatalytic Ozonation Reactions 492 21.6 Conclusions 493

References 494

22 Dry Reforming of Methane 501 Catherine Batiot-Dupeyrat

22.1 Introduction 501 22.2 LaNiO3 as Catalyst Precursor for Carbon Dioxide Reforming of

Methane 502 22.3 Influence of the Substitution of Nickel in the Perovskite

LaNi1�yByO3 506

XV Contents

22.4 Influence of the Substitution of Lanthanum in the Perovskite La1�xAxNi1�yByO3 507

22.5 Perovskite as Support of Active Sites in the Dry Reforming of Methane 510

22.6 Supported Perovskite for Dry Reforming of Methane 510 22.7 Conclusion 512

References 512

23 Recent Progress in Oxidative Conversion of Methane to Value-Added Products 517 Evgenii V. Kondratenko and Uwe Rodemerck

23.1 Methane: Sources and Feedstock for Chemical Industry 517 23.2 Oxidative Coupling of Methane 519 23.2.1 OCM Reactors and Modes of Operation 520 23.2.2 OCM Process Concepts 522 23.2.3 Strategies for Developing New OCM Catalysts 526 23.3 Methane to Methanol and Its Derivatives 528 23.4 Methane to Acetic Acid 530 23.5 Conclusions 532

References 533

24 Steam Reforming of Alcohols from Biomass Conversion for H2

Production 539 Florence Epron, Nicolas Bion, Daniel Duprez, and Catherine Batiot-Dupeyrat

24.1 Introduction 539 24.2 Generalities on Alcohol Steam Reforming 539 24.2.1 Types of Alcohols Used 539 24.2.2 Reactions Involved and Thermodynamic Data 540 24.2.2.1 Ethanol Steam Reforming 540 24.2.2.2 Glycerol Steam Reforming 542 24.3 Catalysts 544 24.3.1 Types of Catalysts Used 544 24.3.1.1 Noble Metal Catalysts 545 24.3.1.2 Non-Noble Metal Catalysts 545 24.3.1.3 Effect of the Support 546 24.3.2 Why Perovskite-Type Catalysts are Good Candidates? 547 24.3.3 General Assessement 549 24.4 Catalytic Performances of Perovskite-Type Catalysts for

H2 Production from Alcohols 549 24.4.1 Ethanol Steam Reforming 549 24.4.2 Glycerol Steam Reforming 551 24.5 Summary and Outlook 552

References 553

XVI Contents

25 Three-Way Catalysis 559 Ioannis V. Yentekakis and Michalis Konsolakis

25.1 Three-Way Catalytic Converters (TWCs): An Introduction 559 25.2 Three-Way Catalytic Materials: Potentials/Aptitudes,

Limitations, and Future Trends 563 25.3 Three-Way Catalysis by Ceria and Ceria-Based Mixed Oxides 565 25.3.1 CO Oxidation 567 25.3.2 Oxidation of Hydrocarbons 568 25.3.3 NO Reduction by CO or HCs 568 25.3.4 Simulated Stoichiometric Exhaust Conditions 568 25.4 Application of Perovskites in Exhaust Emission Control 570 25.4.1 Model Reactions 572 25.4.1.1 CO Oxidation 572 25.4.1.2 N2O Decomposition 573 25.4.1.3 NO Reduction by CO 573 25.4.1.4 NO Reduction by Propene 575 25.4.2 Simulated Exhaust Conditions 576 25.5 Conclusions and Guidelines 579

References 580

26 Lean Burn DeNOx Applications: Stationary and Mobile Sources 587 Angelos M. Efstathiou and Vasilis N. Stathopoulos

26.1 Scope 587 26.2 Introduction 588 26.2.1 Hydrogen-Selective Catalytic Reduction (H2-SCR) 588 26.2.2 Lean NOx After Treatment of Diesel Engine Emissions 590 26.3 Case Studies 594 26.3.1 H2-SCR of NO 594 26.3.2 Lean NOx Trap 601 26.3.3 Simultaneous NOx Reduction and Soot Oxidation 605 26.4 Concluding Remarks 605

References 606

27 Catalytic Abatement of N2O from Stationary Sources 611 Pascal Jean-Philippe Dacquin and Christophe Dujardin

27.1 Introduction 611 27.2 The Abatement of N2O From Nitric Acid Plant:

A Case Study 613 27.2.1 Different Possible Scenarios 613 27.2.2 High-Temperature Decomposition of N2O 615 27.2.3 Medium-Temperature Decomposition of N2O 618 27.2.4 End-of-Pipe Technologies 622 27.3 Conclusion 626

References 627

XVII Contents

28 Perovskites as Catalyst Precursors for Fischer–Tropsch Synthesis 631 Anne-Cécile Roger and Alain Kiennemann

28.1 Introduction 631 28.2 Alcohols Synthesis 632 28.2.1 Methanol Synthesis 633 28.2.2 Higher Alcohols Synthesis 638 28.2.2.1 Ethanol Synthesis 638 28.2.2.2 C1–Cn Alcohols Synthesis 639 28.3 Hydrocarbons Synthesis 644 28.4 Conclusions 654

References 654

29 FexZr1 − xO2 and Ce1 − xFexO2 − δ Mixed Oxide Catalysts: DRIFTS Analyses of Synthesis Gas and TPSR of Propane Dry Reforming 659 Rodrigo Brackmann, Ricardo Scheunemann, Andre Luiz Alberton, and Martin Schmal

29.1 Introduction 659 29.2 FexZr1�xO2 and Ce1�xFexO2�δ Mixed Oxide Systems 659 29.2.1 Part 1: DRIFTS Analyses with FexZr1�xO2 Mixed Oxides 661 29.2.1.1 CO Adsorption 661 29.2.1.2 Adsorption of CO + O2 + He 663 29.2.1.3 Adsorption of CO + O2 + H2 + He 664 29.2.2 Part 2: TPSR of Propane Oxidation with CO2 on Ce1�xFexO2�δ Mixed

Oxides 667 29.2.2.1 Thermodynamics 667 29.2.2.2 Temperature-Programmed Surface Reaction 667 29.3 Conclusions 671

References 672

30 Photocatalytic Assisted Processes 675 Bogdan Cojocaru and Vasile I. Parvulescu

30.1 Introduction 675 30.2 Titanates 677 30.2.1 Calcium Titanates 677 30.2.2 Strontium Titanates 678 30.2.3 Barium Titanates 683 30.2.4 Lanthanum Titanates 684 30.2.5 Iron Titanates 685 30.2.6 Other Titanates 685 30.2.7 Bismuth Titanates 686 30.3 Ferrites 686 30.3.1 Calcium Ferrites 686 30.3.2 Strontium Ferrites 686 30.3.3 Barium Ferrites 687

XVIII Contents

30.3.4 Yttrium Ferrites 687 30.3.5 Rare Earth Ferrites 688 30.3.6 Other Ferrites 689 30.4 Conclusions 690

References 690

Part Three Future Prospects from Synthesis to Reactor Design 699

31 Mesoporous TM Oxide Materials by Surfactant-Assisted Soft Templating 701 Altug S. Poyraz, Yongtao Meng, Sourav Biswas, and Steven L. Suib

31.1 Introduction 701 31.1.1 Use of a Hard Template 701 31.1.2 Mesoporous Oxide Materials by Chemical

Transformation 702 31.1.3 Mesoporous Oxide Materials by Soft Micelle Templating 703 31.2 Surfactant and Micelleization 705 31.2.1 Types of Surfactants 705 31.2.2 Inorganic Additives 705 31.2.3 Organic Additives 706 31.3 Surfactant–Inorganic (S–I) Interactions 707 31.3.1 Thermodynamics of Mesostructured Materials 707 31.3.2 Surfactant–Inorganic (ΔGinter) Interactions 707 31.3.2.1 Coulombic S–I Interactions for Mesoporous TM Oxides 708 31.3.2.2 Covalent S–I Interactions for Mesoporous TM Oxides 709 31.3.2.3 S to I Charge Transfer Interactions for Mesoporous TM Oxides 710 31.3.2.4 Hydrogen-Bonding (S–I) Interactions for Mesoporous

TM Oxides 711 31.4 Stability of a Mesoporous TM Oxide 712 31.4.1 Template Removal 713 31.5 Summary and Future Prospects 713

References 714

32 Development of Robust Mixed-Conducting Membranes with High Permeability and Stability 719 Tomás Ramirez-Reina, José Luis Santos, Nuria García-Moncada, Svetlana Ivanova, and José Antonio Odriozola

32.1 Overview 719 32.2 Mechanical Robustness 721 32.3 Chemical Robustness 725 32.3.1 Tolerance Toward CO2 725 32.3.2 Tolerance Toward SO2 729 32.3.3 Tolerance Toward Reducing Environments 731 32.4 Future Applications 732

References 732

XIX Contents

33 Catalytic Reactors with Membrane Separation 739 Fausto Gallucci and Jon Zuniga

33.1 Introduction 739 33.2 Types of Reactors 740 33.2.1 Packed Bed Membrane Reactors 740 33.2.2 Fluidized Bed Membrane Reactors 744 33.3 Membranes for O2 Separation 753 33.3.1 Membrane Sealing 755 33.4 Membrane Reactors with O2 Membranes 758 33.5 Conclusions 768

References 768

34 The Development of Millistructured Reactors for High Temperature and Short Time Contact 773 Ana Raquel de la Osa, Anne Giroir-Fendler, and Jose Luis Valverde

34.1 Introduction 773 34.2 Classification of Microreactors 774 34.2.1 Capacity 775 34.2.2 Material 775 34.2.3 Reaction Phase 776 34.2.3.1 Reactions Involving Liquids 776 34.2.3.2 Gas Phase 776 34.2.3.3 Catalytic Reactions Involving Three Phases 777 34.2.4 Catalytic System 777 34.2.5 Other Configurations 778 34.3 Applications and Possible Scale-up 778 34.3.1 Ammonia Oxidation 779 34.3.2 Diesel Particulate Combustion 779 34.3.3 Ethylene Oxide Synthesis 779 34.3.4 Oxidative Coupling of Methane 779 34.3.5 Hydrogenation Reactions 780 34.3.5.1 Hydrogenation of Benzene to Cyclohexene 780 34.3.5.2 Hydrogenation of Cyclohexene 780 34.3.6 Dehydrogenation Reactions 780 34.3.6.1 Dehydrogenation of Methylcyclohexane 780 34.3.6.2 Dehydrogenation of Cyclohexane 780 34.3.6.3 Oxidative Dehydrogenation of Methanol 781 34.3.6.4 Dehydrogenation of Alkanes 781 34.3.7 Synthesis Gas Production 781 34.3.7.1 Steam Methane Reforming 781 34.3.7.2 Partial Oxidation of Methane 781 34.3.8 Fuel Production 781 34.3.8.1 Direct Partial Oxidation of Methane to C1 Oxygenates 781 34.3.8.2 Total Syngas Methanation to Synthetic Natural Gas 782 34.3.8.3 Fischer–Tropsch Synthesis 782

XX Contents

34.3.8.4 Synthesis of Methanol and Ethanol 783 34.3.8.5 Synthesis of Dimethyl Ether 783 34.3.8.6 Biodiesel Production 783 34.3.8.7 Hydrogen Production 784 34.4 Simulation Case 785 34.5 Conclusions 789

References 791

35 Single Brick Solution for Lean-Burn DeNOx and Soot Abatement 797 Sonia Gil, Jesus Manuel Garcia-Vargas, Leonarda F. Liotta, Philippe Vernoux, and Anne Giroir-Fendler

35.1 Introduction 797 35.2 Diesel Posttreatment 799 35.2.1 Specificity of Diesel Engine 799 35.2.2 Diesel Unburned Hydrocarbon and Carbon Monoxide

Oxidation 799 35.2.3 Treatment of Soot 801 35.2.4 DeNOx Reduction 803 35.2.4.1 Urea and NH3 Selective Catalytic Reduction 804 35.2.4.2 Single Brick Solution for Lean-Burn DeNOx and Soot

Abatement 807 35.3 Conclusion 810

References 811

36 Tools for the Kinetics of Fast Reactions 817 Gregory Biausque, Marie Rochoux, David Farrusseng, and Yves Schuurman

36.1 Introduction 817 36.2 Oxygen Interaction 817 36.2.1 Oxygen Nonstoichiometry 818 36.2.2 Oxygen Isotopic Exchange Techniques 819 36.2.3 Secondary Ion Mass Spectrometry 819 36.2.4 Steady-State Isotopic Transient Oxygen Exchange 819 36.2.5 Case Study: Prediction of the Oxygen Permeation Flux through a Thin

Ceramic Membrane from Powder Measurements 820 36.2.6 Conclusions 823 36.3 Measurement of Kinetics of Fast Reactions 823 36.3.1 Annular Reactor 824 36.3.2 Modeling of Annular Reactors 825 36.3.3 Case Study: Kinetics of High-Temperature Ammonia Oxidation in an

Annular Reactor 827 36.3.4 TAP Reactor 830 36.3.5 Case Study: TAP Experiments for Ammonia Oxidation over

LaCoO3 831 36.3.6 Conclusions 833

References 833

XXI Contents

37 Perovskites as Oxygen Carrier-Transport Materials for Hydrogen and Carbon Monoxide Production by Chemical Looping Processes 839 Lori Nalbandian and Vassilis Zaspalis

37.1 Introduction 839 37.1.1 Chemical Looping Combustion 839 37.1.2 Oxygen Carriers 840 37.1.3 Chemical Looping Reforming 841 37.1.4 Chemical Looping Water Splitting and Chemical Looping

Carbon Dioxide Splitting 842 37.1.5 Thermochemical Water or Carbon Dioxide Splitting 842 37.1.6 Chemical Looping in Dense Membrane Reactors 843 37.2 Perovskites for H2 and CO Production by Chemical Looping

Processes 844 37.2.1 Powdered Perovskites: Chemical Looping Processes 845 37.2.1.1 Reduction by an Oxidizable Compound 845 37.2.1.2 Reduction by Solar Radiation 849 37.2.2 Perovskites as Dense Membranes 850 37.2.3 Perovskites Used as Supports 856 37.3 Conclusions 857

References 857

38 Perovskites and Related Mixed Oxides for SOFC Applications 863 Steven S.C. Chuang and Long Zhang

38.1 Introduction 863 38.2 Fuel Cells 864 38.3 Perovskites 870 38.3.1 Perovskite as a Cathode Material 870 38.3.2 Low-Temperature Cathodes 873 38.4 Anode Materials 874 38.5 Summary and Future R&D 875

References 876

39 Perovskite Membranes for CO2 Capture: Current Trends and Future Prospects 881 Marc Pera-Titus and Anne Giroir-Fendler

39.1 Introduction 881 39.2 Pre-, Post-, and Oxy-combustion CO2 Capture: High- versus

Low-Temperature Membrane Technologies 882 39.2.1 Low-Temperature Membranes: Porous Inorganic Membranes 883 39.2.2 High-Temperature Membranes: Mixed Ionic–Electronic Conducting

Membranes Based on Perovskites 885 39.3 R&D Membrane Concepts for High-Temperature CO2 Capture 889 39.3.1 Perovskite Membranes for O2 Separation 889 39.3.1.1 O2 Separation and Combustion 889 39.3.1.2 Gasification Systems Combined with Combustion 890

XXII Contents

39.3.2 Perovskite Membranes for H2 Separation and Steam Dosing 891 39.3.3 Perovskite-Containing Membranes for CO2 Separation 892 39.4 Recent Membrane Developments for CO2 Capture 893 39.4.1 General Criteria for Membrane Design 893 39.4.2 Perovskite Membranes for Selective O2 Permeation 895 39.4.2.1 Co-Containing Perovskites 895 39.4.2.2 Co-Free Perovskites 901 39.4.2.3 Dual-Phase Membranes 902 39.4.3 Perovskite Membranes for Selective H2 Permeation 904 39.4.3.1 Ce-Containing Perovskites (Cerates) 904 39.4.3.2 Dual-Phase Metal Cerates: Cermets 905 39.4.3.3 Ce-Free Formulations 909 39.4.4 Molten Carbonate/Perovskite Membranes for Selective CO2

Permeation 910 39.5 Conclusions and Perspectives 913

Glossary 915 Greek Symbols 915 Subscripts 915 Acronyms 915 References 916

Index 929

XXIII

List of Contributors

Houshang Alamdari Laval University Department of Mining, Metallurgical and Materials Engineering 1065 avenue de la médecine Quebec City, QC G1V 0A6 Canada

Andre Luiz Alberton Federal University of Rio de Janeiro/COPPE Department of Chemical Engineering/NUCAT Av.Horacio Macedo 2030 CEP 21941-972 Centro de Tecnologia Bl.G – 121 Cidade Universitária Rio de Janeiro Brazil

Matteo Ardit University of Ferrara Department of Physics and Earth Sciences Via Saragat 1 44122 Ferrara Italy

Carmela Aruta National Research Council CNR-SPIN Via del Politecnico 1 00133 Rome Italy

Catherine Batiot-Dupeyrat Université de Poitiers Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP) ENSIP, UMR CNRS 7285 1 rue Marcel Doré, TSA 41105 86073 Poitiers Cedex 9 France

Alexandre Bayart Université d’Artois Faculté des Sciences Jean Perrin Unité de Catalyse et de Chimie du Solide (UCCS) CNRS UMR 8181 Rue Jean Souvraz – SP 18 62307 Lens France

XXIV List of Contributors

Gregory Biausque Université Lyon 1 Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON) CNRS UMR 5256 2 avenue Albert Einstein 69626 Villeurbanne Cedex France

Nicolas Bion Université de Poitiers Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP) CNRS UMR 7285 4 rue Michel Brunet, TSA 51106 86073 Poitiers Cedex 9 France

Sourav Biswas University of Connecticut Departments of Chemistry and Chemical Engineering and Institute of Materials Science U-3060, 55 North Eagleville Road Storrs, CT 06269 USA

Luis F. Bobadilla Institute of Chemical Research of Catalonia Heterogeneous catalysis and In Situ/Operando Spectroscopy Avda. Països Catalans, 16 43007 Tarragona Spain

Rodrigo Brackmann Federal University of Rio de Janeiro/COPPE Department of Chemical Engineering/NUCAT Av. Horacio Macedo 2030 CEP 21941-972 Centro de Tecnologia Bl.G – 121 Cidade Universitária Rio de Janeiro Brazil

Oliver Brunko Swiss Federal Laboratories for Materials Science and Technology (Empa) Laboratory for Solid State Chemistry and Catalysis Überlandstrasse 129 8600 Dübendorf Switzerland

Agustín Bueno-López University of Alicante Department of Inorganic Chemistry Carretera de San Vicente s/n 03080 Alicante Spain

Dariusz Burnat Swiss Federal Laboratories for Materials Science and Technology (Empa) Materials for Energy Conversion Überlandstrasse 129 8600 Dübendorf Switzerland

and

University of Applied Sciences (ZHAW) School of Engineering Institute of Materials and Process Engineering (IMPE) Technikumstrasse 9, 8600 Winterthur Switzerland

Miguel Angel Centeno Centro mixto CSIC-Universidad de Sevilla Instituto de Ciencia de Materiales de Sevilla Avda. Americo Vespucio 49 41092 Sevilla Spain

XXV List of Contributors

Steven S.C. Chuang The University of Akron Department of Polymer Science FirstEnergy Advanced Energy Research Center 170 University Avenue Akron, OH 44325-3909 USA

Bogdan Cojocaru University of Bucharest Faculty of Chemistry Department of Organic Chemistry, Biochemistry and Catalysis Bd. Regina Elisabeta 4–12 030018 Bucharest Romania

Juan C. Colmenares Polish Academy of Sciences Institute of Physical Chemistry ul. Kasprzaka 44/52 01-224 Warsaw Poland

Giuseppe Cruciani University of Ferrara Department of Physics and Earth Sciences via Saragat 1 44122 Ferrara Italy

Jean-Philippe Dacquin Université Lille 1, Sciences et Technologies Unité de Catalyse et de Chimie du Solide – UMR 8181 Bâtiment C3 59650 Villeneuve d’Ascq Cedex France

Ana Raquel de la Osa Universidad de Castilla-La Mancha Facultad de Ciencias y Tecnologías Químicas Departamento de Ingeniería Química Avenida de Camilo José Cela, 12 13071 Ciudad Real Spain

Rachel Desfeux Université d’Artois Faculté des Sciences Jean Perrin Unité de Catalyse et de Chimie du Solide (UCCS) CNRS UMR 8181 Rue Jean Souvraz – SP 18 62307 Lens France

Michele Dondi Institute of Science and Technology for Ceramics CNR-ISTEC via Granarolo 64 48018 Faenza Italy

Christophe Dujardin Université Lille 1, Sciences et Technologies Unité de Catalyse et de Chimie du Solide – UMR 8181 Bâtiment C3 59650 Villeneuve d’Ascq Cedex France

Daniel Duprez Université de Poitiers Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP) CNRS UMR 7285 4 rue Michel Brunet, TSA 51106 86073 Poitiers Cedex 9 France

XXVI List of Contributors

Angelos M. Efstathiou University of Cyprus Chemistry Department Heterogeneous Catalysis Laboratory 1 University Avenue, University Campus 1678 Nicosia Cyprus

Florence Epron Université de Poitiers Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP) CNRS UMR 7285 4 rue Michel Brunet, TSA 51106 86073 Poitiers Cedex 9 France

David Farrusseng Université Lyon 1 Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON) CNRS UMR 5256 2 avenue Albert Einstein 69626 Villeurbanne Cedex France

Davide Ferri Paul Scherrer Institut (PSI) 5232 Villigen Switzerland

Fausto Gallucci Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Chemical Process Intensification P.O. Box 513, STE 038 5612 AZ Eindhoven, The Netherlands

Nuria García-Moncada Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla Centro mixto US-CSIC Departamento de Química Inorgánica Avda. Américo Vespucio 49 41092 Seville Spain

Jesús Manuel Garcia-Vargas Université Lyon 1 Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON) CNRS UMR 5256 2 avenue Albert Einstein 69626 Villeurbanne Cedex France

Sonia Gil Université Lyon 1 Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON) CNRS UMR 5256 2 avenue Albert Einstein 69626 Villeurbanne Cedex France

Anne Giroir-Fendler Université Claude Bernard Lyon 1 Institut de recherches sur la catalyse et l’environnement de Lyon (IRCELYON) CNRS UMR 5256 2 avenue Albert Einstein 69622 Villeurbanne Cedex France

XXVII List of Contributors

Pascal Granger University of Lille Unité de Catalyse et de Chimie du Solide UMR CNRS 8181 Batiment C3 59655 Villeneuve d’Ascq Cedex France

Andre Heel Swiss Federal Laboratories for Materials Science and Technology (Empa) Materials for Energy Conversion Überlandstrasse 129 8600 Dübendorf Switzerland

and

University of Applied Sciences (ZHAW) School of Engineering Institute of Materials and Process Engineering (IMPE) Technikumstrasse 9, 8600 Winterthur Switzerland

Willinton Y. Hernández Ghent University Department of Inorganic and Physical Chemistry Krijgslaan 281, S3 9000 Ghent Belgium

Svetlana Ivanova Universidad de Sevilla e Instituto de Ciencias de Materiales de Sevilla Centro mixto US-CSIC Departamento de Química Inorgánica Avda. Américo Vespucio 49 41092 Seville Spain

Randy Jalem Kyoto University Unit of Elements Strategy Initiative for Catalysts & Batteries (ESICB) Katsura, Saikyo-ku Kyoto 615-8520 Japan

and

Nagoya Institute of Technology Department of Materials Science and Engineering Gokiso, Showa, Nagoya Aichi 466-8555 Japan

Serge Kaliaguine Université Laval Department of Chemical Engineering 1065, Avenue de la médecine Quebec City, QC G1V 0A6 Canada

Vijayanandhini Kannan GITAM University GITAM School of Technology Department of Physics Hyderabad 502329 Telangana India

Lassi Karvonen Swiss Federal Laboratories for Materials Science and Technology (Empa) Laboratory for Solid State Chemistry and Catalysis Überlandstrasse 129 8600 Dübendorf Switzerland

XXVIII List of Contributors

Alain Kiennemann ICPEES Group “Energie et Carburants pour un Environnement Durable” CNRS UMR 7515 25, rue Becquerel 67087 Strasbourg France

Evgenii V. Kondratenko Catalyst Discovery and Reaction Engineering Leibniz-Institut für Katalyse e.V. an der Universität Rostock Albert-Einstein-Str. 29a 18059 Rostock Germany

Michalis Konsolakis Technical University of Crete School of Production Engineering and Management University Campus, Kounoupidiana 73100 Chania, Crete Greece

Athanasios Ladavos University of Patras Department of Business Administration of Food and Agricultural Enterprises G. Seferi 2 Agrinio 30100 Greece

Oscar H. Laguna Centro mixto CSIC-Universidad de Sevilla Instituto de Ciencia de Materiales de Sevilla Avda. Americo Vespucio 49 41092 Sevilla Spain

Leonarda F. Liotta Université per Lo Studio dei Materiali Nanostrutturati (ISMN)-CNR via Ugo La Malfa 153 90146 Palermo Italy

Paweł Lisowski Polish Academy of Sciences Institute of Physical Chemistry ul. Kasprzaka 44/52 01-224 Warsaw Poland

Agnieszka Magdziarz Polish Academy of Sciences Institute of Physical Chemistry ul. Kasprzaka 44/52 01-224 Warsaw Poland

Yongtao Meng University of Connecticut Departments of Chemistry and Chemical Engineering and Institute of Materials Science U-3060, 55 North Eagleville Road Storrs, CT 06269 USA

Mahesh Muraleedharan Nair Université Laval Department of Chemistry 1065, avenue de la médecine Quebec City, QC G1V 0A6 Canada

Masanobu Nakayama Kyoto University Unit of Elements Strategy Initiative for Catalysts & Batteries (ESICB) Katsura, Saikyo-ku Kyoto 615-8520 Japan

edited by pascal granger, vasile i. parvulescu, serge ... · edited by pascal granger, vasile i....

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