Preface ................................................. XVII
List of Contributors ..................................... XXI
Part I Introduction ............................................ 1
1 Insights into Hierarchically Structured Porous Materials:
From Nanoscience to Catalysis, Separation, Optics,
Energy, and Life Science ................................... 3
Bao-Lian Su, Clément Sanchez, and Xiao-Yu Yang
1.1 Introduction ............................................... 3
1.2 Synthesis Strategies to Hierarchically Structured Porous
Materials .................................................. 8
1.3 Emerging Applications of Hierarchically Structural
Porous Materials .......................................... 16
1.4 Conclusions ............................................... 20
Acknowledgments ........................................... 20
References ................................................ 21
2 Hierarchy in Natural Materials ............................ 29
Peter Fratzl and Marie Madeleine Giraud Guille
2.1 Natural Materials as a Source of Inspiration in
Materials Science ......................................... 29
2.2 Hierarchies Based on Fiber Architectures .................. 31
2.3 Liquid Crystalline Assemblies, Clues to Mimic
Hierarchical Structures ................................... 33
2.4 Mineralized Biological Tissues, Models for Hybrid
Materials ................................................. 34
2.5 Concluding Remarks ........................................ 37
References ................................................ 37
Part II Synthesis Strategies to Hierarchically Structured
Porous Materials ............................................... 41
3 Hierarchically Structured Porous Materials by Dually
Micellar Templating Approach .............................. 43
Özlem Sei and Bernd M. Smarsly
3.1 Introduction .............................................. 43
3.2 Nanocasting - True Liquid Crystalline Templating .......... 43
3.2.1 Surfactants and Block Copolymer Mesophases as
Templates .......................................... 45
3.2.2 Ionic Liquids as Templates ......................... 45
3.3 Basics of Micellization ................................... 46
3.3.1 The Driving Force for Micellization - Hydrophobic
Effect ............................................. 47
3.3.2 Thermodynamics of Micelle Formation ................ 48
3.4 Mixed Surfactant Solutions ................................ 49
3.4.1 Mixed Surfactant Systems at Higher Concentrations .. 49
3.5 Hierarchical Self-Assembly of Concentrated Aqueous
Surfactant Mixtures - Hierarchical Mesoporous Structures .. 50
3.6 Conclusions ............................................... 52
References ................................................ 52
4 Colloidal Crystal Templating Approaches to Materials
with Hierarchical Porosity ................................ 55
Nicholas D. Petkovich and Andreas Stein
4.1 Introduction and Historical Overview ...................... 55
4.1.1 Opals and Colloidal Crystals ....................... 56
4.1.2 Inverse Opals and Three-Dimensionally Ordered
Macroporous Materials .............................. 58
4.2 The Preparation of 3DOM Materials ......................... 61
4.2.1 Monodisperse Colloidal Spheres ..................... 61
4.2.2 Methods to Assemble Colloidal Crystals ............. 63
4.2.3 Infiltration and Processing Routes ................. 66
4.3 3DOM Materials with Intrinsic Secondary Porosity .......... 69
4.3.1 Porosity Produced in Sol-Gel Syntheses ............. 69
4.3.2 Textural Mesopores in Nanocrystalline Walls ........ 72
4.3.3 Porosity in Carbon Materials ....................... 75
4.3.4 Using Nanocomposites to Generate Porosity .......... 76
4.3.5 Porosity in 3DOM Clay Minerals ..................... 76
4.4 Hierarchical Materials from Multimodal Colloidal Crystal
Templates ................................................. 77
4.4.1 Templates from Combinations of Polymer Spheres
with Similar Sizes ................................. 78
4.4.2 Templates from Combinations of Polymer Spheres
and Small Silica Colloids .......................... 81
4.4.3 Heterostructured Colloidal Crystal Templates ....... 83
4.5 Hierarchical Materials from Combinations of Soft and
Colloidal Crystal Templating .............................. 84
4.5.1 Colloidal Crystal Templated Zeolites ............... 86
4.5.2 Introduction to Soft Templating of Mesopores ....... 86
4.5.3 Hierarchical Silica Structures ..................... 88
4.5.3.1 Cationic Surfactant Templates ............. 88
4.5.3.2 Nonionic Surfactant Templates ............. 89
4.5.3.3 Ionic-Liquid Surfactant Templates ......... 92
4.5.4 Hierarchical Carbon-Containing Structures .......... 92
4.5.4.1 Pure Carbon Structures .................... 92
4.5.4.2 Carbon-Silica Composites and Derived
Structures ................................ 93
4.5.5 Hierarchical Alumina Structures .................... 96
4.5.6 Hierarchical Structures Containing Other
Compounds .......................................... 97
4.5.7 Structures Synthesized via Multiple Hard and Soft
Templates .......................................... 98
4.5.8 Formation and Structure of Mesopores Confined in
Colloidal Crystals ................................ 100
4.5.9 Disassembly and Reassembly of 3DOM/m Materials .... 101
4.6 Hierarchical Opals and Related Structures ................ 103
4.6.1 Monodisperse Mesoporous Silica Spheres ............ 103
4.6.2 Self-Assembled Hierarchical Silica, Carbon, and
Tin Oxide Opals ................................... 104
4.6.3 3DOM Zeolites from Hierarchical Silica Opals ...... 107
4.6.4 Encapsulated Non-Close-Packed Hierarchical Opal ... 108
4.6.5 Inverse Opals as Templates for Hierarchical
Opals ............................................. 209
4.7 Conclusions and Outlook .................................. 112
Acknowledgments .......................................... 113
References ............................................... 114
5 Templating of Macroporous or Swollen Macrostructured
Polymers ................................................. 131
Maryline Chee Kimling and Rachel A. Caruso
5.1 Introduction ............................................. 131
5.2 Macroporous Polymer Gels Formed in Amphiphile Solutions .. 133
5.3 Macroporous Starch or Agarose Gels ....................... 136
5.4 Polymer Foams ............................................ 140
5.5 Polymeric Films and Fibrous Mats ......................... 151
5.6 Polymer Spheres .......................................... 159
5.7 Closing Remarks .......................................... 166
References ............................................... 168
6 Bioinspired Approach to Synthesizing Hierarchical
Porous Materials ......................................... 173
Tian-Yi Ma and Zhong-Yong Yuan
6.1 Introduction ............................................. 173
6.2 Hierarchical Porous Materials from Biotemplates .......... 176
6.2.1 Plant Parts as Templates .......................... 176
6.2.2 Cell and Bacteria as Templates .................... 181
6.2.3 Saccharide as Templates ........................... 185
6.2.4 Diatomaceous Earth as Templates ................... 188
6.2.5 Eggshell as Templates ............................. 193
6.3 Hierarchical Porous Materials from the Biomimetic
Process .................................................. 194
6.4 Conclusions and Perspectives ............................. 201
References ............................................... 202
7 Porous Materials by Templating of Small Liquid Drops ..... 209
Haifei Zhang
7.1 Introduction ............................................. 209
7.2 Emulsion Templating ...................................... 210
7.2.1 HIPE Templating for Hydrophilic Polymers and
Related Materials ................................. 212
7.2.1.1 O/W HIPEs ................................ 212
7.2.1.2 C/W HIPEs ................................ 214
7.2.1.3 Related Materials ........................ 216
7.2.2 Microemulsion Templating .......................... 218
7.2.3 Freeze-Drying of Emulsions ........................ 221
7.3 Breath Figures Templating ................................ 223
7.3.1 Breath Figures .................................... 224
7.3.2 Polymer ........................................... 226
7.3.2.1 General Polymers ......................... 226
7.3.2.2 Proteins Related ......................... 228
7.3.2.3 Modification of Film Casting and
Evaporation Process ...................... 230
7.3.3 Particles ......................................... 231
7.3.3.1 Polymer + Nanoparticles .................. 231
7.3.3.2 Nanoparticles Only ....................... 231
7.3.4 Posttreatment of BF-Templated Films ............... 234
7.3.4.1 Cross-linking ............................ 234
7.3.4.2 Carbonization ............................ 235
7.3.4.3 Calcination .............................. 235
7.4 Conclusions .............................................. 236
Acknowledgment ........................................... 237
References ............................................... 237
Further Reading .......................................... 239
8 Hierarchically Porous Materials by Phase Separation:
Monoliths ................................................ 241
Kazuki Nakanishi
8.1 Introduction ............................................. 241
8.2 Background and Concepts .................................. 242
8.2.1 Polymerization-Induced Phase Separation in Oxide
Sol Gels .......................................... 242
8.2.2 Structure Formation Paralleled with Sol-Gel
Transition ........................................ 246
8.2.3 Macropore Control ................................. 247
8.2.4 Mesopore Control .................................. 247
8.3 Examples of Materials with Controlled Macro/Mesopores .... 248
8.3.1 Pure Silica ....................................... 248
8.3.1.1 Typical Synthesis Conditions ............. 248
8.3.1.2 Additional Mesopore Formation by Aging ... 249
8.3.1.3 Hierarchically Porous Monoliths .......... 250
8.3.1.4 Supramolecular Templating of Mesopores ... 251
8.3.1.5 Applications ............................. 252
8.3.2 Siloxane-Based Organic-Inorganic Hybrids .......... 253
8.3.2.1 Network from Precursors Containing the
Trialkoxysilyl Group ..................... 253
8.3.2.2 Hierarchical Pores in an MTMS-Derived
Network .................................. 253
8.3.2.3 Network from Bridged Alkoxysilanes ....... 254
8.3.2.4 Conversion into Porous SiC Ceramics and
Carbon Monoliths ......................... 254
8.3.3 Titania and Zirconia .............................. 255
8.3.3.1 Choice of Starting Compounds ............. 255
8.3.3.2 Controls over Reactivity ................. 256
8.3.3.3 Applications ............................. 257
8.3.4 Alumina and Aluminates from an Ionic Source ....... 258
8.3.4.1 Epoxide-Mediated Gel Formation into
Macroporous Monoliths .................... 258
8.3.4.2 Extension to Complex Oxides .............. 259
8.3.4.3 Extension to Phosphates .................. 259
8.3.5 Highly Cross-linked Organic-Polymer System ........ 260
8.3.5.1 Divinylbenzene Monoliths ................. 260
8.3.5.2 Acrylates and Other Networks ............. 261
8.3.5.3 Conversion into Carbon Monoliths ......... 261
8.4 Summary .................................................. 262
Acknowledgments .......................................... 263
References ............................................... 263
9 Feature Synthesis of Hierarchically Porous Materials
Based on Green Easy-Leaching Concept ..................... 269
Ge Tian, Li-Hua Chen, Xiao-Yu Yang, and Bao-Lian Su
9.1 Introduction ............................................. 269
9.2 Hierarchically Structured Porous Materials Synthesized
by Easy-Leaching Air Templates ........................... 270
9.3 Hierarchically Structured Porous Materials Synthesized
by Easy-Leaching Ice Template ............................ 272
9.3.1 Ceramics .......................................... 273
9.3.2 Polymer ........................................... 274
9.3.3 Hydrogels (Silica) ................................ 274
9.3.4 Composites ........................................ 275
9.3.5 Development of Methodology ........................ 277
9.4 Hierarchically Structured Porous Materials Synthesized
by Easy Selective-Leaching Method ........................ 283
9.5 Other Easy-Leaching Concepts in the Synthesis of
Hierarchically Structured Porous Materials ............... 290
9.5.1 Three-Dimensional Meso-Macrostructured
Spongelike Silica Membranes by Inorganic Salts .... 290
9.5.2 Biomodal Mesoporous Silicas by Dilute
Electrolytes ...................................... 290
9.5.3 Hierarchical Bioactive Porous Silica Gels by Gas
Templating ........................................ 293
9.5.4 Hierarchically Porous Materials by Chemical
Etching ........................................... 294
9.5.5 Hierarchically Porous Materials by Sublimation .... 294
9.6 Summary .................................................. 296
Acknowledgments ............................................... 296
References .................................................... 296
10 Integrative Chemistry Routes toward Advanced Functional
Hierarchical Foams ....................................... 301
Hervé Deleuze and Rénal Backov
10.1 Introduction ............................................. 301
10.2 Organic-Inorganic PolyHIPEs Prepared from Water-in-Oil
Emulsions ................................................ 304
10.2.1 Non-Chemically Bonded (Class I) Hybrid PolyHIPEs .. 304
10.2.1.1 Inorganic Precursor in the HIPE Aqueous
Phase .................................... 304
10.2.1.2 Metal Particle Generation onto PolyHIPE
Surface .................................. 305
10.2.1.3 Nanocomposites ........................... 308
10.2.1.4 Organic-Inorganic Interpenetrating
Networks ................................. 313
10.2.1.5 Hard Template Replica .................... 313
10.2.2 Chemically Bonded (Class II) Hybrid PolyHIPEs ..... 313
10.2.2.1 Inorganic-Organic Precursor's
Copolymerization ......................... 313
10.2.2.2 Organic-Organometallic Precursors
Copolymerization ......................... 314
10.2.2.3 Organometallic PolyHIPE
Functionalization ........................ 316
10.3 Organic-Inorganic PolyHIPEs Prepared from Direct
Emulsions ................................................ 316
10.3.1 Functional Organic-Inorganic PolyHIPEs ............ 316
10.3.1.1 Silica Foams (Si-HIPE) ................... 316
10.3.1.2 Eu3+@Organo-Si(HIPE) Macro-Mesocellular
Hybrid Foams Generation and Photonic
Properties ............................... 317
10.3.1.3 Pd@Organo-Si(HIPE) Hybrid Monoliths:
Generation Offering Cycling Heck
Catalysis Reactions ...................... 318
10.3.1.4 Enzyme@Organo-Si(HIPE) Hybrid
Monoliths: Highly Efficient
Biocatalysts ............................. 321
10.3.2 Si(HIPE) as Hard Template to Carbonaceous Foams
and Applications .................................. 324
10.3.2.1 From Si(HIPE) to Carbon(HIPE) and Their
Use as Li-Ion Negative Electrodes ........ 325
10.3.2.2 From Carbon(HIPE) to LiBH4@Carbon(HIPE)
for Hydrogen Storage and Release
Properties ............................... 326
10.4 Particles-Stabilized PolyHIPE ............................ 328
10.4.1 Water-in-Oil Pickering Emulsions .................. 329
10.4.2 Oil-in-Water Pickering Emulsion ................... 329
10.5 Conclusion and Perspectives .............................. 330
References .................................................... 331
11 Hierarchically Structured Porous Coatings and Membranes .. 335
Cedric Boissiere, Eric Prouzet, David Grosso, and
Clément Sanchez
11.1 Introduction ............................................. 335
11.2 The Multiple Templating Strategy ......................... 336
11.2.1 Hierarchical Inorganic Nanopatterning ............. 337
11.2.2 Ionic Liquid (IL)/Block Copolymer Soft-Soft
Templating ........................................ 338
11.2.3 Polymer/Block Copolymer Soft-Soft Templating ...... 338
11.2.4 Block Copolymer/Latex Beads Soft-Hard Templating
for Hierarchical Metallic Thin Films .............. 339
11.3 Dynamic Templating ....................................... 340
11.3.1 Controlled Phase Separation ....................... 340
11.3.2 Breath Figures as Smart Templates ................. 341
11.4 Building Block Assemblies for Photonic Band Gap
Materials ................................................ 343
11.4.1 The Latex Games ................................... 343
11.4.2 Multilayer Deposition of PO MTF ................... 344
11.5 Ink-Jet Printing and Cooperative Self-Assembly ........... 345
11.6 Foaming Processes ........................................ 345
11.6.1 2D Mesomacrocellular .............................. 345
11.7 Filtration Membranes ..................................... 347
11.7.1 Microporous Hierarchical Membranes ................ 348
11.7.1.1 Mesostractured Hierarchical Membranes
Generated into the Porous Substrate ...... 351
11.7.2 Mesostructured Hierarchical Membranes Generated
by EISA ........................................... 353
11.8 Conclusion ............................................... 357
References .................................................... 358
12 Self-Formation Phenomenon to Hierarchically Structured
Porous Materials ......................................... 363
Xiao-Yu Yang, Ge Tian, Li-Hua Chen, and Bao-Lian Su
12.1 Introduction ............................................. 363
12.2 History of Self-Formation Phenomenon ..................... 364
12.3 Features of Self-Formation Phenomenon .................... 367
12.4 Structural Features of Hierarchical Porous Materials
Based on the Self-Formation Phenomenon ................... 368
12.5 The Mechanism of Self-Formation Procedure ................ 373
12.5.1 Surfactant-Templating Mechanism ................... 373
12.5.2 Aggregation Mechanism for the Formation of
Mesoporous Structures ............................. 375
12.5.3 Microphase-Separated Mechanism for the Formation
of Macroporous Structures ......................... 376
12.5.4 Porogen Mechanism ................................. 376
12.6 Controlled Synthesis Based on the Self-Formation
Phenomena ................................................ 384
12.6.1 The Effect of Metal Alkoxide ...................... 384
12.6.2 The Effect of Surfactant .......................... 388
12.6.3 The Effect of pH Values ........................... 390
12.6.4 The Effect of Solvent ............................. 392
12.6.5 The Effect of Hydrothermal Synthesis .............. 394
12.7 Development of Synthesis Methodology ..................... 396
12.7.1 Combination of Self-Formation and Templating
Strategy .......................................... 396
12.7.2 Combination of Self-Formation and Template
Replicate ......................................... 396
12.7.3 Combination of Self-Formation and Zeolitic
Crystallization Procedures: Perspectives .......... 399
12.8 Applications and Hierarchical Catalysis .................. 399
12.9 Summary .................................................. 402
Acknowledgments .......................................... 403
References ............................................... 403
13 Auto-Generated Hierarchical Meso-Macroporous
Aluminosilicate Materials with High Tetrahedral AI
Content from the Single-Molecular Alkoxy-Precursor
(SMAP) Strategy .......................................... 407
Arnaud Lemaire and Bao-Lian Su
13.1 Introduction ............................................. 407
13.2 Hierarchically Structured Meso-Macroporous
Aluminosilicates ......................................... 409
13.2.1 Single-Molecular Alkoxy Precursor (SMAP): Effect
of pH ............................................. 409
13.2.2 Single-Molecular Alkoxy Precursor: Effect of
Chelating Agents .................................. 413
13.2.3 Single-Molecular Alkoxy Precursor: Effect of
TMOS .............................................. 416
13.2.3.1 General Features of Materials Obtained ... 426
13.2.3.2 Direct Observation of Macropore
Formation by an Optical Microscope ....... 418
13.2.3.3 Conclusions .............................. 423
13.2.4 Single-Molecular Alkoxy Precursor: Effect of
TAOS .............................................. 423
13.2.4.1 General Features of Materials Obtained ... 423
13.2.4.2 Mechanistic Considerations ............... 425
13.2.4.3 Conclusions .............................. 425
13.3 Conclusion ............................................... 426
Acknowledgment ........................................... 426
References ............................................... 427
Further Reading .......................................... 433
14 Zeolites with Hierarchically Porous Structure:
Mesoporous Zeolites ...................................... 435
Feng-Shou Xiao and Xiangju Meng
14.1 Introduction ............................................. 435
14.2 Mesoporous Zeolites Formed by Posttreatments ............. 437
14.3 Mesoporous Zeolites Created by Solid Templates ........... 438
14.4 Mesoporous Zeolites Created by Soft Templates ............ 442
14.5 Functionalization of Mesoporous Zeolites ................. 449
14.6 Perspectives in the Synthesis of Ordered Mesoporous
Zeolites ................................................. 452
References ............................................... 453
15 Micro-Macroporous Structured Zeolite ..................... 457
Ya-Hong Zhang, Li-Hua Chen, Yi Tang, Xiao-Yu Yang, and
Bao-Lian Su
15.1 Introduction ............................................. 457
15.2 Hollow Micro-Macroporous Structure ....................... 457
15.3 Micro-Macroporous Monoliths .............................. 465
15.4 Conclusion and Remarks ................................... 471
References ............................................... 475
Part III Emerging Applications of Hierarchically Structured
Porous Materials .............................................. 481
16 Hierarchically Porous Materials in Catalysis ............. 483
Toshiyuki Yokoi and Takashi Tatsumi
16.1 Introduction ............................................. 483
16.2 Acid Catalyst ............................................ 484
16.2.1 Alkali Posttreatment of Zeolite ................... 484
16.2.2 Synthesis of Micro-and Mesoporous Composites ...... 486
16.2.3 Creation of Intracrystalline Mesoporosity by
Using Hard Template ............................... 486
16.2.3.1 Use of Silane-Functionalized Polymer ..... 487
16.2.3.2 Al-SВA-15/Carbon Composite ............... 488
16.2.3.3 Use of Cationic Polymer .................. 490
16.2.4 Use of Amphiphilic Surfactant ..................... 491
16.2.5 Zeolite Nanosheets ................................ 493
16.2.6 Pillaring and Delamination ........................ 498
16.2.6.1 Delamination of the Zeolitic-Layered
Precursor ................................ 498
16.2.6.2 Interlayer-Expanded Zeolite .............. 499
16.3 Titanosilicates .......................................... 500
16.3.1 TS-1-Based Material ............................... 500
16.3.2 MWW-Based Material ................................ 502
16.3.3 Hierarchical Mesoporous Titanosilicate ............ 506
16.4 Conclusions and Outlook .................................. 511
References .................................................... 511
17 Hierarchically Structured Porous Materials: Application
to Separation Sciences ................................... 517
Kazuki Nakanishi
17.1 Introduction ............................................. 517
17.2 Separation Medium for HPLC ............................... 517
17.2.1 Particle-Packed Columns as Separation Media for
HPLC .............................................. 517
17.2.2 Monolithic Silica for HPLC Columns ................ 518
17.2.3 Comparison between Monolithic and Particle-
Packed Columns .................................... 520
17.2.3.1 Backpressure ............................. 520
17.2.3.2 Efficiency ............................... 521
17.2.3.3 Robustness ............................... 522
17.2.3.4 Cladding and Pore Homogeneity ............ 522
17.3 Variations in Column Format and Pore Structures .......... 523
17.3.1 Long Capillary Columns with High Permeability ..... 523
17.3.2 Columns with Finer Domains ........................ 525
17.3.3 Monoliths with Fully Templated Mesopores .......... 526
17.4 Products ................................................. 526
17.4.1 Preconcentration Devices .......................... 526
17.4.2 Bioreactors and DNA Purifiers ..................... 527
17.4.3 Therapeutic Apheresis Device ...................... 527
17.5 Summary .................................................. 527
Acknowledgments ............................................... 528
References .................................................... 528
18 Colloidal Photonic Crystals: Fabrication and
Applications ............................................. 531
Qingfeng Yan, Jie Yu, Zhongyu Cai, and X. S. Zhao
18.1 Photonic Crystals ........................................ 531
18.2 Colloidal Self-Assembly Approach to Photonic Crystals .... 532
18.2.1 Sedimentation ..................................... 533
18.2.2 Spin Coating ...................................... 535
18.2.3 Physical Confinement .............................. 536
18.2.4 Vertical Deposition ............................... 537
18.2.5 Horizontal Deposition ............................. 539
18.2.6 Spray Coating and Printing ........................ 540
18.2.7 Layer-by-Layer Method ............................. 540
18.2.8 Other Methods ..................................... 541
18.3 Optical Doping in Colloidal Photonic Crystals ............ 542
18.3.1 Line Defect Engineering ........................... 544
18.3.2 Planar Defect Engineering ......................... 549
18.3.3 Point Defect Engineering .......................... 553
18.4 Band-Gap Engineering in Colloidal Photonic Crystals ...... 557
18.4.1 Heterostructures .................................. 558
18.4.2 Superlattices ..................................... 560
18.4.3 Other Hierarchical Colloidal Photonic Crystal
Structures ........................................ 560
18.5 Photonic Devices Based on Colloidal Photonic Crystals .... 562
18.5.1 Lasing in 3D Colloidal Photonic Crystals .......... 562
18.5.2 Sensors Based on 3D Colloidal Photonic Crystals ... 564
18.5.3 Waveguide in 3D Colloidal Photonic Crystals ....... 564
18.5.4 Structural Color and Display Devices .............. 566
18.6 Outlook .................................................. 569
Acknowledgments .......................................... 571
References ............................................... 571
19 Hierarchically Structured Porous Materials for Energy
Conversion and Storage ................................... 577
Bao-Lian Su
19.1 Introduction ............................................. 577
19.2 Hierarchically Structured Porous Materials for Energy
Conversion ............................................... 579
19.2.1 Sunlight Conversion to Chemicals and Electricity .. 579
19.2.1.1 Hierarchically Structured Porous
Materials for Light Harvesting,
Photochemical H2 Production, and
Photocatalysis ........................... 579
19.2.1.2 Hierarchically Structured Porous
Materials for Dye-Sensitized Solar
Cells (DSSCs) ............................ 583
19.2.1.3 Hierarchically Structured Porous
Materials for Immobilization of
Photosynthetic Species ................... 585
19.2.2 Hierarchically Structured Porous Materials for
Fuel Cells (FCs) .................................. 588
19.3 Hierarchically Structured Porous Materials for Energy
Storage .................................................. 591
19.3.1 Hierarchically Structured Porous Materials for
Li Batteries ...................................... 591
19.3.2 Hierarchically Structured Porous Materials for
Supercapacitors ................................... 594
19.4 Conclusion and Outlook ................................... 597
References ............................................... 597
20 Hierarchically Structured Porous Materials-Applications
in Biochemistry: Bioceramics, Life Science, and Drug
Delivery ................................................. 602
Maria Vallet-Regí and Miguel Manzano
20.1 Introduction ............................................. 601
20.2 Bioceramics .............................................. 601
20.2.1 First Generation: Bio-Inerts ...................... 603
20.2.2 Second Generation: Bioactives and Resorbables ..... 603
20.2.3 Third Generation: Driving Living Tissue
Regeneration ...................................... 603
20.3 Life Science ............................................. 603
20.3.1 Bone Tissue Engineering ........................... 603
20.3.2 Porous Calcium Phosphates ......................... 606
20.3.3 Porous Bioglasses ................................. 606
20.3.4 Silica Mesoporous Materials ....................... 608
20.4 Drug Delivery ............................................ 610
20.4.1 Silica Mesoporous Materials ....................... 611
20.4.2 Templated Glasses ................................. 613
20.4.3 Stimuli-Responsive Drag Delivery Systems .......... 614
20.5 Three-Dimensional Scaffolds .............................. 616
References .................................................... 616
21 On the Optimal Mechanical Properties of Hierarchical
Biomaterials ............................................. 621
H.X. Zhu, Т.X. Fan, and D. Zhang
21.1 Introduction ............................................. 621
21.2 Mechanics of Materials of First-Level Hierarchy .......... 622
21.2.1 Young's Modulus E1 ................................ 623
21.2.2 Tensile Strength S1 ............................... 625
21.2.3 Flaw Tolerance .................................... 627
21.2.4 Toughness ......................................... 627
21.3 Mechanics of Materials of the Higher Level Hierarchy ..... 628
21.4 Results and Discussion ................................... 629
References ............................................... 630
Part IV Conclusion ........................................... 633
22 Concluding Remarks ....................................... 635
Bao-Lian Su, Clement Sanchez, and Xiao-Yu Yang
22.1 Looking Back ............................................. 635
22.2 Looking Forward .......................................... 636
Index .................................................... 639
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