Hybrid Organic-Inorganic Interfaces E-Book
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- Herausgeber: Wiley-VCH Verlag GmbH & Co. KGaA
- Kategorie: Fachliteratur
- Sprache: Englisch
Hybrid organic-inorganic materials and the rational design of their interfaces open up the access to a wide spectrum of functionalities not achievable with traditional concepts of materials science. This innovative class of materials has a major impact in many application domains such as optics, electronics, mechanics, energy storage and conversion, protective coatings, catalysis, sensing and nanomedicine. The properties of these materials do not only depend on the chemical structure, and the mutual interaction between their nano-scale building blocks, but are also strongly influenced by the interfaces they share.
This handbook focuses on the most recent investigations concerning the design, control, and dynamics of hybrid organic-inorganic interfaces, covering: (i) characterization methods of interfaces, (ii) innovative computational approaches and simulation of interaction processes, (iii) in-situ studies of dynamic aspects controlling the formation of these interfaces, and (iv) the role of the interface for process optimization, devices, and applications in such areas as optics, electronics, energy and medicine.
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Seitenzahl: 2013
Veröffentlichungsjahr: 2017
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Table of Contents
Cover
Title Page
Title Page
Copyright
Preface
Chapter 1: Clay–Organic Interfaces for Design of Functional Hybrid Materials
1.1 Introduction
1.2 Analytical and Measuring Tools in Clay–Organic Hybrid Interfaces
1.3 Nanoarchitectures from Organic–Clay Interfaces
1.4 Clay-Supported Biointerfaces and Biomedical Applications
1.5 Clay Interfaces for Environmental Protection
1.6 Concluding Remarks
List of Abbreviations
References
Chapter 2: Hybrid Nanocomposites Based on Prussian Blue-Type Nanoparticles Included into Polysaccharides Matrices
2.1 Introduction
2.2 Synthesis of the Prussian Blue-Type Nanoparticles Included in the Chitosan and the Alginate
2.3 Magnetic Properties of the Nanocomposites
2.4 Photoluminescence of the Nanocomposites
2.5 Monovalent Cation Sorption: Application for Decontamination of Cs
+
2.6 Conclusion
List of Abbreviations
References
Chapter 3: Self-Healing Thermosetting Composites: Concepts, Chemistry, and Future Advances
3.1 Introduction
3.2 Self-Healing Process by Microencapsulation
3.3 Fiber-Based Self-Healing Mechanisms
3.4 Self-Healing Interfaces by the Combination of Organic and Inorganic Reinforcements
3.5 Chemistry of Vascular- and Capsule-Based Self-Healing Systems
3.6 Future Advances in Self-Healing of Interphases/Interfaces in Composites
List of Abbreviations
References
Chapter 4: Silica–Polymer Interface and Mechanical Reinforcement in Rubber Nanocomposites
4.1 Introduction
4.2 Silica–Rubber Composites
4.3 Filler–Filler and Filler–Rubber Interactions and Silica–Rubber Interface
4.4 Conclusions
List of Abbreviations
References
Chapter 5: Sustainable Organic–Inorganic Interfaces in Energy Applications
5.1 Introduction
5.2 Poly(Ionic Liquid)-Based Hybrid Materials
5.3 Polysaccharide-Based Hybrids
5.4 Protein-Based Hybrids
5.5 Concluding Remarks
List of Abbreviations
References
Chapter 6: Hybrid Conjugated Polymer–Inorganic Objects: Elaboration of Novel Organic Electronic Materials
6.1 Introduction
6.2 Polymer Brushes: General Features
6.3 Surface-Initiated Polymerization of Conjugated Monomers
6.4 Surface Functionalization via the “Grafting Through” Methodology
6.5 “Grafting Onto” Coupling Techniques
6.6 Conjugated Polymer Brushes Applications
6.7 Conclusion
List of Abbreviations
References
Chapter 7: Hybrid Organic–Inorganic Nanostructures for Spin Switching and Spintronic Applications
7.1 Introduction
7.2 Fundamentals of Spintronics
7.3 Hybrid Organic–Inorganic Spin Valves and Magnetic Tunnel Junctions
7.4 Preparation Methods of Organic Semiconductor Thin Films for Spintronics
7.5 Inorganic Ferromagnet–Organic Interface
7.6 Spin Crossover Nanomaterials
7.7 Conclusion and Future Perspective
List of Abbreviations
References
Chapter 8: Application of Sol–Gel Method to Synthesize Organic–Inorganic Hybrid Coatings to Minimize Corrosion in Metallic Substrates
8.1 Introduction
8.2 Evolution of the Sol–Gel Process and Its Main Applications
8.3 General Synthesis Strategies for Hybrid Materials: Chemistry Background
8.4 Hybrid Sol–Gel Coatings: Applications and Coating Methods
8.5 OIH Sol–Gel Coatings for Corrosion Mitigation
8.6 Physical OIH Gel Materials and Characterization of Metal/Coating Interface by Electrochemical Methods
References
Chapter 9: Gas-Organic and Gas-Inorganic Interfacial Effects in Gas/Adsorbent Interactions: The Case of CO2/CH4 Separation
9.1 Introduction
9.2 Selective CO
2
Capture Adsorbents
9.3 Organic–Inorganic Porous Materials for CO
2
/CH
4
Separation
9.4 Future Projections
Acknowledgements
List of Abbreviations
References
Chapter 10: Design and Characterization of MOFs (Metal–Organic Frameworks)
10.1 Introduction
10.2 Synthesis
10.3 Characterization and Innovative Applications
10.4 Conclusions and Perspectives
List of Abbreviations
References
Chapter 11: Nanocarbon–Ionic Liquid Hybrid Materials for Heterogeneous Catalysis
11.1 Introduction
11.2 Ionic Liquids
11.3 Nanocarbon–Ionic Liquids Formation by Physical Confinement
11.4 Nanocarbon–Ionic Liquids Formation by Covalent Anchoring
11.5 Ionic Liquids as Precursor-Derived Carbon Materials
11.6 Nanocarbon–Ionic Liquid Hybrid-Derived Carbon Materials
11.7 Applications of Nanocarbon–Ionic Liquid Hybrids
11.8 Conclusions
Acknowledgment
List of Abbreviations
References
Chapter 12: Tough Hydrogels: Toughening Mechanisms and Their Utilization in Stretchable Electronics and in Regenerative Medicines
12.1 Introduction
12.2 A Review of Fracture Toughness
12.3 Designing Tough Hydrogels
12.4 Sticky Hydrogels
12.5 Integrating Hard Materials and Devices in Tough Hydrogels
12.6 Application of Tough Hydrogels in Stretchable Electronics, Energy Devices, and Soft Machines
12.7 Application of Tough Hydrogels in Biomedical Applications
12.8 Conclusion
List of Abbreviations
References
Chapter 13: Ionic Liquids for the Synthesis and Design of Hybrid Biomaterials and Interfaces
13.1 Introduction
13.2 Dissolution of Biopolymers in ILs
13.3 Ionic Liquid-Assisted Synthesis of Functionalized Polysaccharides and Polysaccharide Composites
13.4 Applications of ILs in the Biomaterials Field
List of abbreviations
References
Chapter 14: Interface Engineering with Self-Assembled Monolayers in Biosensors
14.1 Introduction
14.2 Fabrication of Biosensors Based on Metallic Transducers
14.3 Preparation of Biosensors Based on Nonmetallic Transducers
14.4 Conclusion
List of Abbreviations
References
Chapter 15: Coordination Polymers for Medical Applications: Amorphous versus Crystalline Materials
15.1 Introduction
15.2 Synthesis of Coordination Polymer Nanomaterials
15.3 Loading of Active Species
15.4 Adequacy of NMOFs/NCPs for Theranostic Applications
15.5 Conclusions and Perspectives
List of Abbreviations
References
Chapter 16: High Pressure Hydrothermal Procedure: A Tool for Surface Modification of Superparamagnetic Nanostructured Materials for Medical Applications
16.1 Introduction
16.2 Synthesis
16.3 Biocompatible Properties
16.4 Conclusions
Acknowledgments
List of Abbreviations
References
Chapter 17: Silica-Based Organic–Inorganic Hybrid Nanomaterials for Optical Bioimaging
17.1 Introduction to Hybrid Nanomaterials for Bioimaging
17.2 Fluorescent Silica Nanoparticles
17.3 Mesoporous Silica-Based Nanoparticles
17.4 Zeolites
List of Abbreviations
References
Chapter 18: Design of Biohybrid Structures for Enzyme–Electrode Interfaces
18.1 Introduction and Background
18.2 Sol–Gel Synthesis
18.3 Sol–Gel Materials in Biofuel Cells
18.4 Mediated Transfer in EFCs
18.5 Direct Electron Transfer in EFCs
18.6 Direct Electron Transfer in GOx–NanoAu–M13 Bacteriophage for EFCs
18.7 Summary and Future Outlook
Acknowledgments
References
Chapter 19: In Situ and Ex Situ Electrochemical Measurements: Spectroelectrochemistry and Atomic Force Microscopy
19.1 Introduction
19.2 Spectroelectrochemistry
19.3
In Situ
Electrochemical AFM Technique
19.4 Geometry Aspects of
In Situ
Cells
19.5 Conclusions
Acknowledgment
List of Abbreviations
References
Chapter 20: Nuclear Magnetic Resonance as a Tool for the Investigation of Interfaces and Textures in Nanostructured Hybrid Materials
20.1 Introduction
20.2 Study of the Functionalization of Nano-objects in Solution with DOSY NMR
20.3 Solid-State NMR as a Tool of Analysis of Organic–Inorganic Interfaces
20.4 NMR Studies of the Texture and Porosity of Hybrid Materials
20.5 Combined Experimental: Computational Approaches for the Study of Hybrid Interfaces
20.6 Conclusion
List of Abbreviations
References
Chapter 21: Electrostatic Force Microscopy Techniques for Interphase Characterization
21.1 Introduction
21.2 Atomic Force Microscopy
21.3 Electrostatic Force Microscopy
21.4 Characterization of Hybrid Interface
List of Abbreviations
References
Chapter 22: The Use of EPR Spectroscopy for the Study of Hybrid Materials and Interphases
22.1 Introduction
22.2 Fundamentals of EPR Spectroscopy
22.3 Transition Metal Ions in Hybrid Materials
22.4 Electron Transfer Processes in Hybrid Materials
22.5 Nitroxide Radicals and Other Radicals as
In Situ
Probes of Hybrid Interfaces
22.6 Conclusions
List of Abbreviations
References
Chapter 23: Josephin Domain Dimerization on a Gold Surface: Evidences for a Double-Step Binding Pathway
23.1 Introduction
23.2 Materials and Methods
23.3 Results
23.4 Discussion
List of Abbreviations
References
Chapter 24: SANO Methodology for Simulating Self-Assembly Patterns of Organic Molecules over Metal Surfaces
24.1 Introduction
24.2 Description of the SANO Methodology
24.3 Examples of Applications
24.4 Final Remarks and Future Perspectives
List of Abbreviations
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Preface
Begin Reading
List of Illustrations
Chapter 1: Clay–Organic Interfaces for Design of Functional Hybrid Materials
Figure 1.1 Schematic representation of clays structure with (a) layered habit (montmorillonite) showing on the right column the cross section of the silicate layers and (b) fibrous morphology (sepiolite) showing the organization of silicate fiber dimension.
Figure 1.2 Distribution of application fields of organoclays elaborated with data from the ISI Web of Science (Thomson Reuters) accessed on July 13, 2016.
Figure 1.3 Adsorption of the cationic pharmaceutical chlorpheniramine (CP) on SWy-2 clay (triangles), SWy-2 with inefficient separation between the colloids and the supernatant due to low centrifugal acceleration (squares), and CP adsorbed on a neutral organoclay based on SWy-2 modified with TPP (full rhombus).
Figure 1.4 Amount of olive oil adsorbed on clays and organoclays at several mass to mass ratios: montmorillonite (MMT), poly-DADMAC-modified MMT (MMT + PD), hectorite (SHCa1), palygorskite (PFl-1), sepiolite (S9), and chitosan–sepiolite nanocomposite (NH9).
Figure 1.5 SEM images of the pristine SWy-2 clay (a) and a formulation of the herbicide pendimethalin (PM) prepared on difenzoquat (DZ)/SWy-2 organoclay.
Figure 1.6 Particle size distribution of untreated and treated cowshed effluents.
Figure 1.7 Schematic representation of the use of organoclay interfaces in the formation of diverse clay-based nanoarchitectures: (a) use of PEO-based surfactants to produce PILC, (b) use of organoclays incorporating amines to prepare PCHs, and (c) use of organoclays as interfaces for controlling hydrolysis–polycondensation of silicon and metal alkoxides in the formation of delaminated clay heterostructured materials.
Figure 1.8 TEM images of Fe
3
O
4
-smectite (a) and of ZnO–smectite (b) heterostructures prepared by assembly of Fe
3
O
4
–oleic acid NP and ZnO NP to an organo-smectite. (González
et al
. 2011 [196] and Akkari
et al
. 2016 [197]. Reproduced with permission of John Wiley and Sons and Elsevier.)
Figure 1.9 (a) Schematic representation of use of organo-fibrous clay interfaces for
in situ
formation of NP from alkoxides and FE-SEM images of diverse SiO
2
–sepiolite nanoarchitectures prepared by
in situ
growing of SiO
2
NP from TMOS on organic–inorganic interfaces of sepiolite modified with propylammonium (b), hexadecyltrimethylammonium (c), didodecyldimethylammonium (d), and stadistic methylbenzyl-bis-(hydrogenated tallow alkyl)quaternary ammonium ions (e) described in Ref. [240].
Figure 1.10 TEM image of a yeast cell coated with halloysite clay nanotubes (a) and an SEM image of the calcinated halloysite shell replicating yeast cell morphology (b). (Konnova
et al
. 2013 [272]. Reproduced with permission of Royal Society of Chemistry.)
Figure 1.11 Schematic illustration of the preparation of the pectin@chitosan/LDH-5ASA system, showing the pectin coating in the FE-SEM image of a bead cross section. (Ribeiro
et al
. 2014 [314]. Reproduced with permission of Elsevier.)
Figure 1.12 Diverse uses of clay minerals in regenerative medicine: reinforcing fillers of biodegradable polymers (a), release of biomolecules (b), enhancement of cell adhesion (c), and proliferator and differentiator of stem cells to bone cells (d). (Ghadiri
et al
. 2015 [292]. Reproduced with permission of Royal Society of Chemistry.)
Figure 1.13 Relationship between the amount of the organocation thiamin (vitamin B1) adsorbed on SWy-2 montmorillonite and the charge of the resulting hybrid material.
Figure 1.14 Adsorption capacity of a chitosan–vermiculite bionanocomposite foam toward cadmium ions (II).
Chapter 2: Hybrid Nanocomposites Based on Prussian Blue-Type Nanoparticles Included into Polysaccharides Matrices
Figure 2.1 (a) Lacunar and (b) non-lacunar structures of the respective formulas M[M′(CN)
6
]
2/3
(or Fe[Fe(CN)
6
]
3/4
for PB) and AM[M′(CN)
6
].
Figure 2.2 Schematic representation of the applications of nanocomposites containing PB-type nanoparticles inserted into polysaccharides.
Figure 2.3 (a) Chemical structure of chitosan and (b) chemical structure of mannuronate (M) and guluronate (G) residues of Na-alginate.
Figure 2.4 (a) Schematic representation of the M
n
+
/[M′(CN)
m
]
3−
/chitosan nanocomposites (M
n
+
= Ni
2+
, Cu
2+
, Fe
2+
, Mn
2+
, Eu
3+
; M′ = Fe, Cr) design; photograph of (b) the pristine chitosan beads and (c) the Fe
4
[Fe(CN)
6
]
3
/chitosan nanocomposite.
Figure 2.5 (a) Schematic representation of the M
n
+
/[M′(CN)
m
]
3−
/alginate nanocomposites (M
n
+
= Ni
2+
, Cu
2+
, Fe
2+
, Mn
2+
, Eu
3+
; M′ = Fe, Cr) design; photograph of the Ni
2+
/alginate beads or film (b) and the Ni
2+
/[Fe(CN)
6
]
3−
/alginate beads or film nanocomposites (c).
Figure 2.6 SEM images of the Fe
2+
/[Fe(CN)
6
]
3−
/chitosan (a–c) and the Ni
2+
/[Fe(CN)
6
]
3−
/alginate (d–f) beads nanocomposites showing (a, d) whole bead, (b, e) external surface, (c, f) internal surface.
Figure 2.7 (a) Internal view of a cleaved nanocomposite bead Ni
2+
/[Fe(CN)
6
]
3−
/chitosan by scanning electronic microscopy (SEM) measurements. The arrow represents the line (total length = 438 µm) along which the profile curves were obtained; (b) EDS profile curves for Ni and Fe; and (c) representative single point EDS analysis obtained along the arrow drawn in (a).
Figure 2.8 TEM micrographs of Ni
2+
/[Fe(CN)
6
]
3−
/chitosan (average size = 2.8 ± 0.8 nm) (a) and Ni
2+
/[Fe(CN)
6
]
3−
/alginate nanoparticles (average size = 6.5 ± 2.0 nm) (b) obtained after solubilization of the corresponding matrices.
Figure 2.9 Photographs of different nanosized PBA encapsulated into chitin beads. (a) Fe
2+
/[Fe(CN)
6
]
3−
/chitosan, (b) Ni
2+
/[Fe(CN)
6
]
3−
/chitosan, (c) Zn
2+
/[Fe(CN)
6
]
3−
/chitosan, (d) Cu
2+
/[Fe(CN)
6
]
3−
/chitosan, and (e) Co
2+
/[Fe(CN)
6
]
3−
/chitosan.
Figure 2.10 TEM images of nanometric or micrometric sized particles of PBAs (a) Fe
2+
/[Fe(CN)
6
]
3−
/chitosan, (b) Ni
2+
/[Fe(CN)
6
]
3−
/chitosan, (c) Zn
2+
/[Fe(CN)
6
]
3−
/chitosan, (d) Cu
2+
/[Fe(CN)
6
]
3−
/chitosan, and (e) Co
2+
/[Fe(CN)
6
]
3−
/chitosan [113].
Figure 2.11 SEM–EDS analysis Cu
2+
/[Fe(CN)
6
]
3−
/chitosan nanocomposite beads [113].
Figure 2.12 Photograph and SEM pictures of Ni
2+
/[Fe(CN)
6
]
3−
/chitin foams.
Figure 2.13 (a) ZFC/FC magnetization curves performed for the Ni
2+
/[Fe(CN)
6
]
3−
nanoparticles inserted into the chitosan (▸), alginate film (•), and alginate beads (▪) matrix. (b) Hysteresis loops for Ni
2+
/[Fe(CN)
6
]
3−
nanoparticles performed for the Ni
2+
/[Fe(CN)
6
]
3−
nanoparticles inserted into the chitosan (▸), alginate film (•), and alginate beads (▪) matrix at 1.8 K.
Figure 2.14 Temperature dependence of in-phase χ′ (a) and of out-of-phase χ″ (b) components of the AC susceptibility with zero direct current (DC) magnetic field for Ni
2+
/[Fe(CN)
6
]
3−
/chitosan. Frequencies: 1 Hz (•), 9.98 Hz (▪), 125 Hz (▪), 499 Hz (▪), and 998 Hz (▴).
Figure 2.15 (a) Emission spectra (10 K) for Eu
3+
/[Mo(CN)
8
]
3−
/alginate nanocomposite film excited at 282 nm (solid line and solid circles) and at 394 nm (solid line); (b) magnification of the intra-4f
6
transitions at 10 K (black solid line) and at room temperature (purple solid line) excited at 394 nm and (c) emission decay curves monitored within the
5
D
0
→
7
F
2
(612 nm, solid circles) and
5
D
0
→
7
F
4
(700 nm, open squares) transitions and excited at 393 nm. The solid lines represent the data best fit using a single exponential function. (d) Fit regular residual plots (χ
2
red
∼ 10
−6
).
Figure 2.16 Cs
+
sorption isotherms for M
n
+
/[Fe(CN)
6
]
3−
/chitin beads (M
n
+
= Fe
3+
, Ni
2+
, Zn
2+
, Co
2+
, and Cu
2+
) [113].
Figure 2.17 Cs
+
sorption isotherms for Fe
3+
/[Fe(CN)
6
]
4−
/chitin beads with different amount of the inserted PB nanoparticles ((Δ) 20 wt% of nanoparticles, (□) 10 wt% of nanoparticles, and (○) 6.6 wt% of nanoparticles).
Figure 2.18 The Cs
+
sorption isotherm using Ni
2+
/[Fe(CN)
6
]
3−
/chitin foams showing the comparison of the Langmuir and the Langmuir bi-site equations for the modeling sorption isotherms [120].
Figure 2.19 Comparison of Cs
+
uptake kinetic for encapsulated M
n
+
/[Fe(CN)
6
]
3−
/chitin beads (a) and the related bulk materials (b) under comparable experimental conditions (i.e., identical amount of the PBA) (
C
0
: 10 mg Cs l
−1
; sorbent dosage: 20 mg l
−1
of ion-exchanger or 100 mg l
−1
composite) [113].
Figure 2.20 Breakthrough curve (BC) for Cs(I) sorption using fixed-bed column filled with Ni-HCNFe/chitin disks – the solid line represents the fit of experimental BC with the Clark model (
C
0
: 10 mg Cs l
−1
(0.01 M NaNO
3
); sorbent amount: 0.5 g) [120].
Chapter 3: Self-Healing Thermosetting Composites: Concepts, Chemistry, and Future Advances
Figure 3.1 Schematic representation of self-healing concept: (a) the incorporation of self-healing fibers into a polymer matrix, (b) crack formation within the matrix due to the external load and consequent rupture of healing fibers, (c) the discharge of healing agent into the crack area followed by its polymerization upon getting in contact with either the pre-dispersed catalyst in the outer layer of fibers or the hardener released along with the healing epoxy, and (d) healing of crack region. (Monfared 2015 [3]. Reproduced with permission of Royal Society of Chemistry.)
Figure 3.2 The autonomic healing concept. A microencapsulated healing agent is embedded in a structural composite matrix containing a catalyst capable of polymerizing the healing agent. (a) Cracks form in the matrix wherever damage occurs; (b) the crack ruptures the microcapsules, releasing the healing agent into the crack plane through capillary action; (c) the healing agent contacts the catalyst, triggering polymerization that bonds the crack faces closed. (White
et al
. 2001 [9]. Reproduced with permission of Nature Publishing Group.)
Figure 3.3 Illustration of encapsulation through Pickering emulsion templating process. (Li
et al
. 2014 [28]. Reproduced with permission of American Chemical Society.)
Figure 3.4 Schematic diagram of the vacuum-assisted capillary action filling technique developed for filling composite panels. (Bleay
et al
. 2001 [44]. Reproduced with permission of Elsevier.)
Figure 3.5 Microvascular scaffold fabrication. (a) Square-spiral tower structure (yellow) embedded within the 3D microvascular network (blue). The red square denotes the top view shown in (e). (b) Robotic deposition of the fugitive organic ink (blue) through a cylindrical nozzle onto a moving
x–y
stage. (c) Optical image (top view) of a 2D patterned feature within the microvascular scaffold. Scale bar = 1.0 mm. (d) Ink filaments produced from different nozzle diameters (10–250 µm). (e) Optical image (top view) of microvascular (16-layer) scaffold. Scale bar = 0.50 mm. (Therriault
et al
. 2003 [8]. Reproduced with permission of Nature Publishing Group.)
Figure 3.6 (a) Schematic view of epoxy coating/substrate architecture with embedded interpenetrating microvascular networks. Two of these networks house epoxy resin (blue) and hardener (red), while the third network provides thermal control (green) to accelerate healing kinetics after damage occurs. (b) Corresponding optical image of this novel self-healing system fabricated by direct-write assembly and then imaged with different fluorescent dye solutions within each network. (Hansen
et al
. 2011 [53]. Reproduced with permission of John Wiley and Sons.)
Figure 3.7 SEM images of (a) the as-spun core–shell bead-on-string morphology and (b) healing agent released from the capsules when ruptured by mechanical scribing. (c) Fluorescent optical microscopic image of sequentially spun Rhodamine B (red)-doped part A polysiloxane precursor capsules and Coumarin 6 (green)-doped part B capsules. (d) TEM image of as-spun bean-on-fiber core/sheath structure. (Park and Braun 2010 [59]. Reproduced with permission of John Wiley and Sons.)
Figure 3.8 Optical images of the core–shell fibers obtained by emulsion solution blowing. Panels (a) and (b) show core–shell fibers obtained from emulsion of DCPD in PAN and DMF, while panels (c) and (d) show core–shell fibers obtained from emulsion of PAN and isophorone diisocyanate in DMF. The scale bar in all images is 10 µm. (Sinha-Ray
et al
. 2012 [33]. Reproduced with permission of Royal Society of Chemistry.)
Figure 3.9 (a) Schematic representation of triaxial electrospinning setup and (b) the high-speed camera image of Taylor cone composed of PMMA as an outer layer and PAAm as a middle layer. (Zanjani
et al
. 2015 [58]. Reproduced with permission of Elsevier.)
Figure 3.10 SEM images of electrospun multiwalled hollow PMMA/PAAm fibers fabricated by different outer wall solvents (a) DMF, (b) EA, and (c) THF. (Zanjani
et al
. 2015 [58]. Reproduced with permission of Elsevier.)
Figure 3.11 Interfacial healing concept. Maleimide functionalization (blue triangles) of glass fiber within a furan-functionalized (red notched trapezoids) polymer network will result in a thermoreversible, and healable, fiber–network interface. (Peterson
et al
. 2011 [71]. Reproduced with permission of Elsevier.)
Figure 3.12 Chemical structures of different norbornene monomers. (Larin
et al
. 2006 [82]. Reproduced with permission of John Wiley and Sons.)
Chapter 4: Silica–Polymer Interface and Mechanical Reinforcement in Rubber Nanocomposites
Figure 4.1 (a) Relevant dimension in silica–rubber interactions and (b) silanol and siloxane species on silica surface.
Figure 4.2 Reaction mechanism of silanization with TESPT: (a) hydrolysis and condensation, (b) intermolecular condensation, and (c) reaction between rubber and silica functionalized with TESPT.
Figure 4.3 Examples of SCA.
Figure 4.4 Frequency (a) and temperature (b) dependence of the shear
G
′ and loss
G
″ modulus for a typical viscoelastic polymer.
Figure 4.5 (a) Graphic representation of the Payne effect.
Figure 4.6 TEM images of SiO
2
-NR NCs obtained by nonaqueous sol–gel method containing (a) 15 phr, (b) 30 phr, (c) 45 phr, and (d) 60 phr of silica. (e) Plot of storage modulus at low strain
G
′
0
versus silica volume fraction for (O) SiO
2
-NR NCs obtained by nonaqueous sol
–
gel method compared with (□) SiO
2
-NR obtained by aqueous sol
–
gel method and (▴) a master batch obtained mixing NR with commercial silica Zeosil MP1165. The plots are compared with the trend of Guth-Smallwood equation due only to hydrodynamic effect (♦).
Figure 4.7 Sketch of NPs in suspension (a) in the absence and (b) in the presence of a non-interacting polymer. (c) Schematic showing the evolution from individual NPs to isolated aggregates and to percolated filler networks.
Figure 4.8 Scheme of the L–B–N model.
Figure 4.9 Filler particles (a) below and (b) above the gel point, φ*, of the filler network according to the CCA model. (c) Increased volume of a filler aggregate due to a rubber layer immobilized on the filler particles (ξ, aggregate size;
d
, particle size; and Δ, layer thickness).
Figure 4.10 Model of filled rubber from Ref. [121]. Dashed circles indicate the boundaries of the tightly bound rubber region.
Figure 4.11 Model of reinforcement for a silica/TESPT-filled rubber compound. Top: No deformation. Bottom: Under deformation.
Figure 4.12 Description of the morphology of a rubber-filled compound.
Figure 4.13 Real TEM images and digital binary images of no stretched and 50% stretched SBR-cured NCs with precipitated silica (Nipsil AQ) as filler.
F
B
is the area fraction of the black-colored portion, the silica, and the digital images. White-colored portion is SBR.
Figure 4.14 (a,b) 3D height and (a′,b′) 2D amplitude error AFM images of silica–SBR NCs with (a), (a′) spherical (AR = 1), and (b,b′) rodlike (AR = 5) Nps. AFM images of the (c,d) height and (c′,d′
)
phase of the same silica–SBR NCs with (c), (c) spherical (AR = 1) and (d,d′) rodlike (AR = 5) Nps. The insets represent the image analysis of isolated NPs. Particle width from phase (
W
Ph
) and height (
W
He
) images are indicated.
Figure 4.15 Models representing the aggregation of differently shaped particles and the corresponding fractured surfaces in silica–SBR NCs. (a) Spherical NPs (AR = 1) and (b) rodlike NPs (AR = 5). The models are compared with TEM (left) and 2D AFM (right) images concerning the same samples.
Figure 4.16 (a) FIDs of pure PS at different temperatures; the quick decay at low temperatures vanishes heating at
T
>
T
g
. (b) MSE-FIDs of cured PEA pure and filled with 20 vol.% silica surface modified to link the rubber. The FID of filled PEA can be fitted (solid line) by three components of different mobility (broken lines); the blue is the rigid fraction at the filler–rubber interface. (c) Hahn echo FID of cured SBR filled with 80 phr of silica, fitted by two components of different mobility (broken lines).
Figure 4.17 Comparison of the swelling behavior of a rubber NCs (a) without and (b) with interactions between filler particles and rubber matrix.
Figure 4.18 Representation of filler–rubber interface with a gradient of polymer. The polymer mobility gradient is evidenced.
Figure 4.19 Rigid polymer fraction from MSE-NMR as a function of filler volume in SiO
2
-SBR NCs with silica NPs with different AR: (♦) AR = 1, (▪) AR = 2, and (•) AR = 5 at different filler loading (
W
= 12, 20, 25, 35). Error bars (omitted) are ±0.01. Dotted lines are guides for the eye.
Chapter 5: Sustainable Organic–Inorganic Interfaces in Energy Applications
Scheme 5.1 Variety of common cations and anions used for ILs and their polymers. (Yuan and Antonietti 2011 [1]. Reproduced with permission of Elsevier.)
Figure 5.1 (a) Tuning the dispersibility of PIL/SWCNTs by anion exchange. Hydrophobic anions promote dispersion in organic solvents, while hydrophilic anions promote dispersions in water. (b) Formation of a conductive PIL/SWCNT film by
in situ
polymerization of IL monomers with dispersed SWCNTs. (c) Functionalization of SWCNT with Pt nanoparticles by anion exchange of Pt salts and reduction with NaBH
4
. (d) Comparing the electrocatalytic oxidation of methanol performance for nanoparticle-functionalized SWCNTs with and without PIL. (e) A CO
2
sensor comprised of a PIL/SWCNT composite between two gold electrodes. (f) Detection of CO
2
at ppt concentrations for a PIL/SWCNT sensor. ((a) Marcilla
et al
. 2006 [8]. Reproduced with permission of John Wiley and Sons. (b) Fukushima and Aida 2007 [9]. Reproduced with permission of John Wiley and Sons. (c) and (d) Wu
et al
. 2009 [10]. Reproduced with permission of John Wiley and Sons. (e) and (f) Li
et al
. 2012 [11]. Reproduced with permission of Royal Society of Chemistry.)
Figure 5.2 (a) Graphene functionalized with a PIL through a quaternization reaction. (b) Removal of methyl blue from aqueous solution using a PIL/graphene hybrid. (c) Glucose sensor using a PIL/glucose oxidase/graphene hybrid on a glassy carbon electrode. (d) Dopamine sensor using a PILs/poly(pyrrole)/graphene hybrid. (e) Supercapacitor based on a PIL/reduced graphene oxide hybrid. ((a) and (b) Zhao
et al
. 2015 [13]. Reproduced with permission of Elsevier. (c) Zhang
et al
. 2011 [14]. Reproduced with permission of Elsevier. (d) Mao
et al
. 2015 [15]. Reproduced with permission of Elsevier. (e) Kim
et al
. 2011 [16]. Reproduced with permission of ACS.)
Figure 5.3 (a) Synthesis of Pt nanoparticle-functionalized PIL microspheres anion exchange and reduction. (b) Scanning electron microscopy (SEM) images of the PIL/Pt NP-functionalized microspheres. Pt NPs were approximately 2.1 nm in diameter. (c) Synthesis of PIL/Fe
3
O
4
magnetic nanoparticles with acid functionality. (d) Biodiesel synthesis using PIL/Fe
3
O
4
magnetic nanoparticles and waste cooking oil. (e) Sequestration of the La
2
O
2
CO
3
allowing for greater PF6-mobility. (f) Changes in resistance of the PIL/La
2
O
2
CO
3
upon introduction of CO
2
gas. ((a) and (b) Yang
et al
. 2011 [18]. Reproduced with permission of John Wiley and Sons. (c) and (d) Liang 2014 [19]. Reproduced with permission of ACS. (e) and (f) Reproduced from Willa
et al
. 2015 [20]. Reproduced with permission of John Wiley and Sons.)
Figure 5.4 (a) Synthesis of PIL/silica hybrids for chromatography. The long alkyl chain, polar, and ionic charge of the imidazolium allows this material to separate polar, nonpolar, and charged species. (b) Separation of three different nonpolar constitutional isomers using PIL/silica hybrids in (a). (c) Synthesis of PIL brushes on nanosilica using controlled polymerization techniques. (d) SEM image of PIL brushed on nanosilica. The left image shows a disorder resulting from the long brush length, while on the right silicas with shorter brushes are better organized. (e) Synthesis of PIL/silica nanoreactors for the oxidation of benzyl alcohols. ((a) and (b) Qiu
et al
. 2012 [26]. Reproduced with permission of Royal Society of Chemistry. (c) and (d) Morinaga
et al
. 2016 [27], http://www.mdpi.com/2073-4360/8/4/146/htm. Used under CC BY 4.0 https://creativecommons.org/licenses/by/4.0/. (e) Yang
et al
. 2015 [28]. Reproduced with permission of ACS.)
Figure 5.5 (a) Fabrication process of CNF/RGO/CNT electrode. (b) Schematic diagram of the all-solid-state supercapacitor where the polymer–gel electrolyte serves as the electrolyte and the separator. Inset shows the flexibility of the device. (c) Cyclic voltammetry curves of a supercapacitor at different scan rates. (d) Charge–discharge curves of a supercapacitor at different current densities. (e) Dependence of specific capacitance on current density. (f) Nyquist impedance plots of the supercapacitor. Inset is a magnified view of the high-frequency region. (g) Cycling stability of a solid-state device over 1000 cycles at a current density of 1 A g
−1
. Inset shows the galvanostatic charge–discharge curves for the first 20 cycles. (Zheng
et al
. 2015 [39]. Reproduced with permission of ACS.)
Figure 5.6 (a) Schematic illustration of fast assembly of free-standing flexible hybrid film. (b) Field-emission Scanning Electron Microscopy (FESEM) image of the bottom layer containing LTO, CNT, and CNF composites. (c) FESEM image of the top layer containing CNT and CNF network. (d) Transmission electron microscopy (TEM) images of LTO/CNT/CNF conductive slurry. (e) Rate performance of LCC-50, LCC-60, and LCC-70. Galvanostatic charge/discharge curves of (f) LCC-50, (g) LCC-60, and (h) LCC-70 at different current rates. (Cao
et al
. 2015 [72]. Reproduced with permission of ACS.)
Figure 5.7 (a) Scheme of PGO and the proton transfer through CS–PGO interface domain. (b) TEM image of GO. (c) TEM image of PGO. (d) Proton conductivity of CS control and nanohybrid membranes under 100% RH (d and e) and 0% RH (f and g) as a function of temperature. (Bai
et al
. 2015 [99]. Reproduced with permission of Elsevier.)
Figure 5.8 Hierarchical structure of spider silk (a) and snapshots of the deformation of small and large silk crystalline domains (b). (Studart 2012 [124]. Reproduced with permission of John Wiley & Sons.) Structure of the triple helix of collagen along the molecule's axis (c) and side view of the fiber (d). (Fratzl 2008 [125]. Reproduced with permission of Springer.)
Figure 5.9 (A) Schematic representation of the silk–gold NP substrate used for the SERS detection of 4-(dimethylamino)pyridine. (B) Raman spectra of (a) bulk 4-(dimethylamino)pyridine, (b) bare silk film, (c) silk–gold NP film, and (d) 4-(dimethylamino)pyridine adsorbed on AuNP-silk film. (Guo
et al
. 2015 [141]. Reproduced with permission of Royal Society of Chemistry.)
Figure 5.10 (a) LbL fabrication of silk nanocomposites by alternating deposition of silk and MMT layers with or without the addition of a monolayer of Ag nanoparticles. Optical images of the compressed films: (b) (silk)17 and (c) (silk–MMT)17 on Polydimethylsiloxane (PDMS) substrates. The insets show the corresponding 2D Fourier transform (FT) images utilized for the spacing evaluation. (d) The absorbance of the silk10-AgNPL-silk10 film is shown as a dashed line. The films were deposited on quartz slides. (e) Reflectance of a silk10-AgNPL-silk10 film. (Kharlampieva
et al
. 2010 [145]. Reproduced with permission of John Wiley & Sons.)
Figure 5.11 Heat generation from a silk–gold NP hybrid. (a) Depiction of the localized surface plasmon resonance in metallic nanoparticles. (b) Fabrication of the silk–gold NP hybrid and (c) white light irradiation of the hybrid deposited on a Al/Si Schottky diode. The inset shows a cross-sectional TEM image of the silk–SGN hybrid material. Cross-sectional SEM images of the hybrids with a LGN loading of 2.5 wt% (d) and 25 wt% (e). Plots of variation of temperature for the hybrids after an exposure time of 5 min as a function of variation of the loading of SGN and LGN at a light intensity of 1300 mW cm
−2
(f) and as a function of light intensity at a fixed concentration of 25 wt% (g). (h) Current dependence obtained at various halogen lamp intensities for an Al/Si Schottky diode coated with an SGN/SF film. (i) Current gain plotted with respect to time for an Al/Si Schottky diode coated with an SGN/SF film during 10 cycles of halogen lamp exposure at various light intensities. ((a) Kelly
et al
. 2003 [146]. Reproduced with permission of ACS. (b–i) Tsao
et al
. 2015 [147]. Reproduced with permission of ACS.)
Figure 5.12 Electric generation using a silk-based composite. (a) Fabrication procedure of the piezoelectric generators incorporating silk and ferroelectric nanoparticles. (b) Optical transparency of the composite films. (c) Experimental setup to apply a vertical compression force. Output voltage (d) and current density (e) generated from the generator incorporating with 30 wt% KNN:Mn nanoparticles. (Kim
et al
. 2015 [150]. Reproduced with permission of Elsevier.)
Figure 5.13 Components and (a) assembly of the zinc/gel/air battery including the preparation of the gel electrolyte (b). (c) Stability of the voltage output as a function of bending and releasing. (d) Flexibility of the collagen-based electrolyte. (Park
et al
. 2015 [160]. Reproduced with permission of John Wiley & Sons.)
Figure 5.14 Cartoon depicting the preparation route (top) and photographs (down) of collagen fibers (CF) modified with polyphenol (EGCG-CF) and addition of Pd(II) and its reduction to Pd(0). (Wu
et al
. 2010 [163]. Reproduced with permission of Elsevier.)
Chapter 6: Hybrid Conjugated Polymer–Inorganic Objects: Elaboration of Novel Organic Electronic Materials
Figure 6.1 Conjugated polymer brushes in an organic solar cell, employing electrode modification or core–shell nanoparticles in the active layer.
Figure 6.1 Mechanism of Kumada catalyst transfer condensation polymerization with Ni(dppp)Cl
2
.
Figure 6.2 Schematic illustration of the attachment of polymers to surfaces.
Figure 6.3 Polymer brushes conformations versus the grafting density and process.
Figure 6.4 Preparation of SiO
2
–P3HT hybrid particles.
Scheme 6.2 Ligand exchange strategy.
Scheme 6.3 Initiator immobilization using electrochemistry.
Scheme 6.4 Monomers used to create brushes via SI-KCTP.
Scheme 6.5 Representative Stille coupling leading to dithienosilole and benzothiadiazole alternating copolymer.
Figure 6.5 Synthetic methodology of grafting low bandgap polymer from/onto zinc oxide particles.
Scheme 6.6 Representative example of Suzuki–Miyaura polymerizations.
Scheme 6.7 Synthetic strategy of surface-initiated Suzuki coupling polymerization.
Scheme 6.8 Yamamoto polycondensation of spirobifluorene.
Scheme 6.9 Yamamoto surface polymerization.
Scheme 6.10 Example of the use of Sonogashira polymerization.
Scheme 6.11 Sonogashira surface polymerization.
Scheme 6.12 Example Gilch polymerization, leading to a substituted PPV.
Figure 6.6 PL spectra of MEHH-PPV pancakes on a silicon wafer. (
Scheme 6.13 Synthetic strategies to end-functionalize a conjugated polymer made via KCTP.
Scheme 6.14 Synthetic strategies to create thiol- and triethoxysilane-P3HT from allyl-terminated P3HT.
Scheme 6.15 “
In situ
” functionalization of P3HT with an alkyne for further grafting.
Scheme 6.16 Perfluorophenyl-terminated P3HT and its condensation onto TiO
2
nanoparticles.
Scheme 6.17 A typical use of the Heck polymerization technique to prepare PPV derivatives.
Scheme 6.18 Ligand exchange methodology.
Scheme 6.19 CdSe surface functionalization via “click chemistry.”
Scheme 6.20 P3HT brushes using DA and polydopamine.
Scheme 6.21 CNT functionalized with P3HT using esterification.
Figure 6.7 Device performances of CdSe–PSBTBT-NH
2
and blend CdSe/PSBTBT (80/20 weight) with different annealing treatment (solvent annealing with BDT = benzene-1,3-dithiol, or thermal annealing).
Figure 6.8 Solar cell characterization in which ITO is surface modified with P3MT.
Figure 6.9 Electroluminescence spectra of ITO/DB/PF/Al (square) and ITO/DB/CdSe/ZnS/PF/Al (circle) collected at 6 V (Inset: EL picture when the device was operating).
Figure 6.10 Fluorescence quenching of the PF film grafted onto glass in an aqueous solution of Fe
3+
(different concentration). Inset illustrates plot of
I
0
/
I
against varying Fe
3+
concentrations.
Chapter 7: Hybrid Organic–Inorganic Nanostructures for Spin Switching and Spintronic Applications
Figure 7.1 Schematic diagram of a spin valve architecture for parallel and antiparallel alignments of the two ferromagnetic electrodes showing spin-dependent scattering at the two electrodes.
Figure 7.2 (a) GMR response of a typical LSMO/RRP3HT/Co as a function of temperature measured with 100 nA current. (Majumdar and Majumdar 2012 [40]. Reproduced with permission of Elsevier.) (b) Spin diffusion length (λ
S
) of RRaP3HT and RRP3HT, calculated using the modified Júlliere formula, as a function of temperature.
Figure 7.3 (a) Reference SV (without BCP) with non-leaky AlO
x
, (b) 5 nm BCP SV with non-leaky AlO
x
, (c) 5 nm BCP SV with leaky AlO
x
, (d) 10 nm BCP SV with leaky AlO
x
, (e) 30 nm BCP SV with leaky AlO
x
, and (f) 60 nm BCP SV with leaky AlO
x
. The blue and red lines represent the MR value corresponding to voltage sweep from negative to positive and back from positive to negative, respectively.
Figure 7.4 (a) The device schematics of a La
0.7
Sr
0.3
MnO
3
/Alq
3
/Co nanometric-size MTJ. The nanoindent in the Alq
3
layer is realized by a CT-AFM, allowing the control of the organic tunnel barrier thickness. This nanohole is then filled with cobalt, leading to the nanometric-size MTJ. (b) Magnetoresistance curve of the organic MTJ obtained at 2 K and −5 mV. The lower coercive field corresponds to the LSMO magnetic reversal and the higher coercive field to the Co magnetic switching. Inset:
I
(
V
) curves recorded at 2 K in the parallel (IPA) and antiparallel (IAP) magnetic configurations.
Figure 7.5 (a) H
2
Pc molecules adsorbed on cobalt islands with different out-of-plane magnetic orientations. (a) Topographic image of H
2
Pc molecules adsorbed onto two cobalt islands on the Cu(111) surface. Color code: measured d
I
/d
V
at −310 mV. The two island species can be distinguished by the magnetization parallel (in yellow) and antiparallel (in red) to the tip magnetization. (b) Typical d
I
/d
V
spectra taken on parallel and antiparallel oriented cobalt islands (marked by red and blue crosses in a) clearly reveal spin-polarized density of states below the Fermi edge. (c) Energy dependence of the optimistic TMR ratio calculated from the d
I
/d
V
spectra. The highest value is measured at approximately −350 meV and is used to distinguish between the magnetic orientations of the islands.
Figure 7.6 Raman spectrum of the PLD-deposited 7 nm thick rubrene film showing a broadband around 1360 cm
−1
characteristic for amorphous phase with superimposed weaker signatures corresponding to vibrational bands of the crystalline content.
Figure 7.7 Rubrene thin films deposited by MAPLE from solution in 1.1-DCE on Si substrate. (a) Stack-plotted Raman spectra recorded at three surface spots of the 120 nm thick film obtained from 0.5 wt% solution at laser fluence of 3.6 J cm
−2
(18 000 pulses) reveal presence of crystalline phase characterized by closely packed columnar crystals (inset). (b) Optical microscope view of the film sample produced from 0.35 wt% solution at 4.7 J cm
−2
(left) and SEM image (right) showing crystallites embedded in amorphous rubrene matrix.
Figure 7.8 Values of the carrier mobility reported for rubrene-based OS devices obtained by various fabrication techniques over the last two decades; data extracted from Table 7.1 refer to polycrystalline (squares) and single crystal (circles) materials, and these grown from solutions are highlighted (oval marks).
Figure 7.9 Schematic illustrations of the interactions between the metal d-band and the HOMO and LUMO of the organic molecule: (a) original molecular states, (b) formation of the broadened molecular states by the interaction with the broad continuum of the metal sp-bands, and (c) formation of the bonding and antibonding states by the interaction with the metal d-band states.
Figure 7.10 Magnetic coupling of FePc and CoPc to Co where the magnetization density is dominated by the iron and cobalt central atom at the molecular side in an out-of-plane geometry. Note the spin polarization present on carbon and nitrogen atoms of the phenyl rings, which is created through interaction with the spin-polarized Co-d states of the substrate.
Figure 7.11 (a) Schematic diagram of the architectures of the grown multilayers with LSMO crystal structure and chemical structure of the rubrene molecule. (b) Field-cooled (FC) magnetization as a function of temperature together with the first derivative of magnetization (c) for pure LSMO and the LSMO coated with rubrene as grown (sample A), surface treated (sample B), and one with an AlO
x
layer in between (sample C)).
Figure 7.12 Temperature dependence of magnetic properties of Fe(pyrazine)[Pt(CN)
4
] prepared under different crystal size.
Figure 7.13 (a) UV–Vis spectra showing the SCO behavior of the biomembrane. (b) LS state of the [Fe(ptz)
6
](BF
4
)
2
complex identified by
57
Fe Mössbauer spectroscopy.
Figure 7.14 Microcontact printing of the SCO complex [Fe(ptz)
6
](BF
4
)
2
.
Chapter 8: Application of Sol–Gel Method to Synthesize Organic–Inorganic Hybrid Coatings to Minimize Corrosion in Metallic Substrates
Figure 8.1 Interactions established between organic and inorganic components for class I, class II, and class III OIHs; here represents the inorganic network formed from inorganic precursors, and the organic components from organic precursors [33]. (Benvenutti, http://www.lume.ufrgs.br/handle/10183/72880. Used under CC BY NC SA https://creativecommons.org/licenses/by-nc-sa/2.5/.)
Figure 8.2 Generic reactions involved in the preparation of OIH materials through the sol–gel method. X here represents a
network-forming
element such as Si, Ti, Zr, Al, and so on. R
1
and R
2
are typically an alkyl group. (Adapted from Brinker and Scherer 1990 [20]. Reproduced with permission of Elsevier.)
Figure 8.3 Examples of different techniques of deposition. (a) Dip coating, (b) spin coating, (c) spraying, and (d) flow coating.
Figure 8.4 Schematic representation of the interactions between class II OIH and the metallic substrate where X represents a network-forming element such as Si, Ti, Zr, Al, B, and so on. R
1
is typically an alkyl group. (Figueira
et al
. 2014 [1]. Reproduced with permission of Springer.)
Figure 8.5 Example of Severe white rust on a HDGS surface due to contact with high alkaline solution.
Figure 8.6 Typical curve polarization plot for metal corrosion process.
Figure 8.7 Schematic Tafel plot representation with identification of the corrosion process parameters.
Figure 8.8 Potentiodynamic polarization curves obtained for HDGS coated with (a) one layer and (b) three layers of U(X) after being exposed in SCPS for 2 h. The curve for control samples was included for comparison purposes.
Figure 8.9 Representation of impedance (
Z
) function components (Nyquist diagram) in complex plane scales (a) and relation with impedance modulus, |
Z
|, and angle phase, θ, and corresponding representation using a Bode plot (b, c).
Figure 8.10 Impedance plane response of EEC.
Figure 8.11 Impedance plane response of electric equivalent circuits describing the response of a low conductive material, (a) with a single relaxation process and (b) dispersive charge transport relaxation response.
Figure 8.12 Representation of a complex plane spectrum obtained involving Warburg diffusion mechanism (a) and at limit conditions where charge transfer process occurs at metal substrate (b) and the proposed corresponding equivalent electric circuit (left).
Chapter 9: Gas-Organic and Gas-Inorganic Interfacial Effects in Gas/Adsorbent Interactions: The Case of CO2/CH4 Separation
Figure 9.1 Biogas production.
Figure 9.2 CO
2
separation technologies. PSA, VSA, TSA, and ESA stand for pressure swing adsorption, vacuum swing adsorption, temperature swing adsorption, and electric swing adsorption, respectively.
Scheme 9.1 Chemical structures of MEA, DEA, and MDEA.
Figure 9.3 Development timeline of the porous material families according to the pore size.
Figure 9.4 Schematic representation of the carbon structure evolution upon activation processes.
Figure 9.5 Schematic representation showing how MOFs can be obtained from metal-based moieties (green nodes) and organic linkers (orange lines). Solvent species are not shown.
Figure 9.6 The structures of IRMOF-1 (a) and Cu-BTC (b) metal–organic frameworks. Color code: White, H; gray, C; red, O from organic linkers; green, O from water; blue, Zn; and orange, Cu. Thin red lines represent the unit cell edges.
Scheme 9.2 The structures of the organic linkers derived from benzene-1,4-dicarboxylate (BDC) in the isoreticular IRMOF-
n
(
n
= 1–7) metal–organic frameworks.
Figure 9.7 Possible modifications for the (a) parent MOF structure: (b) chemical functionalization, (c) structure interpenetration, (d) open metal sites, (e) charged framework, and (f) breathing effects. (Adapted from Kong
et al
. 2014 [74].)
Scheme 9.3 The structures of the 2,6-NDC (left) and 4,4′-BPDC (right) organic linkers.
Figure 9.8 Functionalization of PMS via (a) co-condensation or via (b) “grafting” methodologies. R, R′, and R″ correspond to organic functionalities.
Scheme 9.4 Chemical structure of some amines used to impregnate porous silicas.
Scheme 9.5 Chemical structures of amine-silane precursors.
Figure 9.9 Schematic representation of the mechanisms of the reaction between primary amines with CO
2
molecules under (a) dry and (b) humid conditions. Figure adapted from Ref. [104].
Figure 9.10 Amine modification of the ethene-PMO: (i) bromination of the double bond and (ii) nuclear substitution of the bromine group by the NH
2
–R–NH
2
functional group. Green circles represent the inorganic motif of the structure, and salmon rectangles symbolize the organic bridge of the inorganic/organic network. The blue rectangles represent the organic functions introduced into the material.
Figure 9.11 Schematic representation of the grafting reaction of the alkyl amine functionalities on the free silanols of the phenylene-PMO. Color code according to Figure 9.10.
Figure 9.12 Functionalization of phenylene PMO with amine groups: (i) aromatic amination of the phenylene moieties of the Ph-PMO and (ii) grafting of APTMS groups to the free silanols of Ph-PMO and NH
2
-Ph-PMO. Color code as in Figure 9.10.
Chapter 10: Design and Characterization of MOFs (Metal–Organic Frameworks)
Figure 10.1 (a) A schematic representation of a MOF with the metal ions (M) acting as nodes and the organic ligands (L1, L2) acting as spacers to form a robust and porous crystalline structure. (b) The porous crystalline structure of IRMOF-1 (also known as
MOF-5
). The gray sphere shows the large accessible volume in the structure.
Figure 10.2 Examples of inorganic and organic components of most common MOFs. The two components represent the SBUs from which the framework is built.
Figure 10.3 Crystalline structures of common MOFs built with SBUs depicted in Figure 10.2.
Scheme 10.1 Design strategies applied to MOFs and characterization techniques to determine the properties in different application fields.
Figure 10.4 A pictorial representation of the most common synthetic methods (top), synthetic conditions (middle), and final products (bottom) in MOF synthesis.
Figure 10.5 Flowchart showing a HT approach to the MOFs synthesis.
Figure 10.6 Effects of the MOFs structural modifications on the gas adsorption properties. The ↑ and ↓ arrows indicate an increase or a decrease in the associated property, respectively.
Figure 10.7 (a) Dihydrogen interaction energy on siliceous and carbonaceous rings [76]. Data obtained at the MP2 (Møller–Plesset perturbation method to second order) level of calculation for the interaction of a hydrogen molecule with C
6
H
6
(circles), Si
6
O
6
H
12
(full squares), LiSi
5
AlO
6
H
12
(light gray squares), and NaSi
5
AlO
6
H
12
(gray squares). Basis sets used: Ahlrichs triple ζ valence basis set with polarization (TZVp) on the rings and Dunning's correlation consistent quadruple ζ valence basis sets with polarization augmented with diffuse function (aug-cc-pVQZ) on the H
2
molecule. (Data from Ref. [76].) (b) Dihydrogen adsorption isotherms recorded at 77 K on Ni
2
(dobdc) (gray circles) and Ni
2
(dobpdc) (black circles). (Data digitalized from Ref. [69].)
Figure 10.8 CO
2
excess adsorption isotherms on (a) M
2
(dobdc) with M = Mg (circles), Co (squares), Zn (diamonds), Ni (triangles); (b) Mg
2
(dobdc) (circles), Mg
2
(dobpdc) (black triangles), mmem-Mg
2
(dobpdc) (gray triangles), and IRMOF-74-III-Mg (stars). The vertical dashed line is placed at 0.4 mbar, that is, at the atmospheric CO
2
partial pressure.
Figure 10.9 Catalytic moieties differently included in MOFs.
Figure 10.10 (a) Structure of the NU-1000 node and linker (left), MOF structure (two views, center), and the dehydration of the NU-1000 node (right). Color code: Zr (blue); O (red); C (black); H (white); (b) decomposition reaction of DMNP; (c) decomposition reaction of GD.
Figure 10.11 A MIL-101(Cr)-coated monolith.
Figure 10.12 Schematic illustration of two types of Guest@MOF systems. (a) Light harvesting process is facilitated by guest molecules (red and yellow spheres) interaction with each other and framework linkers (L1 and L2). (b) The pathway for charge transfer is created through the binding of guest molecules (red spheres) with open metal sites (M) in the framework.
Figure 10.13 Schematic representation of the different use (left) and limitations (right) of MOFs for biomedical applications.
Figure 10.14 Loading of drugs into MOFs via non-covalent encapsulation (top), covalent attachment (middle), and surface functionalization (bottom).
Chapter 11: Nanocarbon–Ionic Liquid Hybrid Materials for Heterogeneous Catalysis
Figure 11.1 Schematic illustration of typical nanocarbons.
Figure 11.2 Typical cations and anions used in ionic liquids.
Figure 11.3 Images of bucky gel prepared by grinding of single-walled carbon nanotubes in an ionic liquid such as [Bmim][BF
4
].
Figure 11.4 (a) Multiwalled carbon nanotube (MWCNT) and ionic liquids hybrid before and after annealing process. (b) TEM image of pristine carbon nanotube (left) and hybrid with few layers ionic liquids coating (right). (c) Elemental mapping of nanocomposites.
Figure 11.5 A model on the ionic liquids immobilized on nanocarbon via physical methods consist of the strongly attached and loosely attached ionic liquids layers.
Figure 11.6 (a) Schematic procedures for synthesizing F-MWCNTs and (b) photos of pure [Bmim][PF
6
] and [Bmim][PF
6
] suspensions of pristine MWCNTs and F-MWCNTs, respectively. The samples were equilibrated for 2 weeks after preparation.
Figure 11.7 Ionic liquids bearing three and four nitrile groups derived carbons.
Figure 11.8 (a) Representation of the PILs-/PSs-based strategy. (b) Structures of the N-containing bases being investigated. (c) Thermal gravimetric analysis curves of typical PILs/PSs.
Figure 11.9 Scanning electron microscopy (SEM) (a) and TEM images at increasing magnifications (b–d) of a graphene composite made from fructose and [Bmim][FeCl
4
].
Figure 11.10 Synthesis of the carbon nanotube/ionic liquids core–sheath nanostructures: from a few layers ionic liquids to a heteroatom-rich surface.
Figure 11.11 The types of nanocarbon–ionic liquid hybrid catalysts.
Figure 11.12 Schematic illustration of the fabrication of the OPW dissolved carbon nanotube–ionic liquid nanocomposites.
Figure 11.13 Synthesis of cyclic carbonates catalyzed by nanocarbon–ionic liquid composites linked by chemical bond.
Figure 11.14 (a) and HRTEM (b,c) images, size distribution histogram of Pt nanoparticles (d), and XRD pattern (e) of the Pt/MWCNT composites obtained by a [Bmim][BF
4
]-assisted method with 2.0 wt% [Bmim][BF
4
] in EG/H
2
O (v/v = 2/1) at 115 °C. The loading is about 20 wt% in the composites.
Figure 11.15 TEM images and size distribution of nanoparticles of Pt/PtRu in carbon nanotube–ionic liquids hybrids. (a, e) PtRu/CNTs-IL; (b, f) PtRu/CNTs-IL; (c, g) Pt/CNT-IL; (d, h) Pt/CNTs.
Figure 11.16 The synthesis of Pd nanoparticles supported on nanocarbon–ionic liquid hybrids.
Chapter 12: Tough Hydrogels: Toughening Mechanisms and Their Utilization in Stretchable Electronics and in Regenerative Medicines
Figure 12.1 Schematic illustration of crack propagation in elastomers based on Lake–Thomas theory.
Figure 12.2 (a) Schematic representation of the process zone inside a hyperelastic material. and
h
represent infinitesimal volume element and height of the process zone, respectively. (b) Due to the formation of process zone, loading curve possesses hysteresis loop. Value of can be determined by calculating the area of this hysteresis curve.
Figure 12.3 Classification of tough hydrogels according to toughening strategies.
Figure 12.4 Schematic illustration of the structure of tetra-PEG tough hydrogels.
Figure 12.5 Schematic representation of sliding/slipping cross-linkers. Inset shows the basic structure of a polyrotaxane.
Figure 12.6 Schematic representation of the sequential polymerization of two polymers to synthesize DN hydrogels.
Figure 12.7 Schematic illustration of the structure and synthesis procedure of clay-based nanocomposite tough hydrogels.
Figure 12.8 Schematic representation of synthesis of microsphere-reinforced tough hydrogels. Unlike NC tough hydrogels, functionalities on microspheres act as both cross-linkers and initiators. In addition, the cross-linking bond between polymer chains and microspheres is covalent in nature.
Figure 12.9 Examples of chemical/physical linkages formed between hydrogels and surrounding tissues.
Figure 12.10 Schematic representations of clay/PNIPAAm hydrogel nanocomposite synthesis. (a) PNIPAAm and clay were uniformly dispersed in water. (b) The concentrations of KPS and TEMED were rich near the surface of the clay platelets. (c) Radicals were formed near the clay surface due to the high TEMED and KPS concentrations. (d) PNIPAAm brushes were formed on the clay surface. (e) Consequently, clay/PNIPAAm networks were formed.
Figure 12.11 A protocol to achieve strong bonding of tough hydrogels to diverse class of solids. The solid substrates, such as glass, ceramic, aluminum, and titanium, were exposed to oxygen plasma to introduce hydroxyl-activated surface oxides on their surfaces. Silane coupling agent was then grafted onto the hydroxyl-activated surface through siloxane covalent chemistry. Functional silane TMSPMA was then grafted onto the hydroxyl-activatedsurface through siloxane covalent chemistry. b. Alginate is grafted using EDC-Sulfo NHS chemistry onamino-silane functionalized substrates. c. Hyaluronan is grafted using the same EDC-Sulfo NHSchemistry on amino-silane functionalized substrates.
Figure 12.12 Schematic illustration of the design of stretchable hydrogel electronics and devices.
Figure 12.13 Schematic of a three-chambered soft robot.
Chapter 13: Ionic Liquids for the Synthesis and Design of Hybrid Biomaterials and Interfaces
Figure 13.1 Examples of common IL cations and anions.
Figure 13.2 Chemical structure of nontoxic anions.
Figure 13.3 Intermolecular (red) and intramolecular (blue) hydrogen bonds in cellulose (β-celluose).
Figure 13.4 Dissolution of cellulose in ILs via strong hydrogen bonding between individual −OH groups of the cellulose and different IL components.
Figure 13.5 Chemical structure of chitin.
Figure 13.6 Silk fibers in relaxed and extended form.
Figure 13.7 (a) Core–shell structure of a
Bombyx mori
silk fiber [114]. (b) Traditional degumming of silk fibers in textile industry. From left to right: technical setup,
B. mori
cocoons soaked in hot water, single fibers from each cocoon collected to coil them up onto a reel.
Figure 13.8 Chemical modifications of cellulose in homogeneous ionic liquid solution.
Figure 13.9 Preparation procedure of regenerated cellulose/MMT nanocomposite films using ionic liquid, BMIMCl.
Figure 13.10 FESEM image of TiO
2
/cellulose composite wire.
Chapter 14: Interface Engineering with Self-Assembled Monolayers in Biosensors
Figure 14.1 General configuration of a biosensor.
Figure 14.2 Types of transducer systems.
Figure 14.3 Formation of alkanethiol SAM on a gold surface.
Figure 14.4 Cyclic voltammetry (CV) has been performed of bare and AuNP-modified at different deposition times. (Malvano
et al
. [24], http://www.mdpi.com/2079-6374/6/3/33/htm. Used under CC-BY 4.0 https://creativecommons.org/licenses/by/4.0/.)
Figure 14.5 Schematic diagram of a self-assembled monolayer (SAMs) disulfide-capped polypeptides on a gold transducer and representative SPR spectra.
Figure 14.6 Schematic of optical waveguide spectroscopy (OWS) configuration and the waveguide–mode–detection scheme. The reflectivity (
R
) versus incident angle (θ) trace on the lower left shows waveguide modes for a nanoporous metal thin film.
Figure 14.7 Scheme for silanization with γ-APS.
Figure 14.8 Schematic of a basic SAW biosensor.
Chapter 15: Coordination Polymers for Medical Applications: Amorphous versus Crystalline Materials
Figure 15.1 (a) SEM images of Fe-BDC (BDC = benzene-1,4-dicarboxylate) NMOF particles with the formula Fe
3
(µ
3
-O)Cl(H
2
O)(BDC)
3
synthesized by microwave heating. (b) SEM images of nanoparticles Fe-BDC NMOF particles loaded with c,c,t-[PtCl
2
(NH
3
)
2
(OEt)(O
2
CCH
2
CH
2
CO
2
H)] anticancer prodrug. (c–e) SEM images of some nontoxic iron(III) carboxylate MOFs: MIL-100 (c), MIL-88A (d), and PEGylated MIL-88A nanoparticles (e).
Figure 15.2 (a, b) SEM images of Gd(BDC)
1.5
(H
2
O)
2
nanorods synthesized with different water/surfactant ratio: 5 : 1 (a) and 10 : 1 (b). (c) SEM image of Mn
3
(BTC)
2
(H
2
O)
6
spiral nanorods and TEM (inset) synthesized at room temperature. (d) SEM image of Mn
3
(BTC)
2
(H
2
O)
6
synthesized at 120 °C under microwave heating. TEM image for self-assembly of amorphous Zn-bisphosphonate NCPs (e) and size distribution measured by DLS (f).
Figure 15.3 Different metal–biomolecule frameworks of (a) [Ni
2.5
(OH)(L-Asp)
2
]·6.55H
2
O, (b) [Ni
2
(L-Asp)
2
(4,40-bipy)] resulting from linking Ni–Asp layers by 4,4-bipy co-ligands and (c) [Zn(Phe-tetrazole)] structure generated by using Phe functionalized with a tetrazole moiety.
Figure 15.4 Schematic showing the compositions of NCP/lipid coating/siRNAs and cisplatin release via reductive degradation of NCPs.
Figure 15.5 (a) Schematic illustration describing the encapsulation of drugs into metal–organic spheres created by the connection of metal ions through the multitopic organic ligand bix. (b) SEM and (c) TEM images of a representative colloidal solution of DOX/Zn(bix) spheres.
Chapter 16: High Pressure Hydrothermal Procedure: A Tool for Surface Modification of Superparamagnetic Nanostructured Materials for Medical Applications
Figure 16.1 (a) Simplified structure of hyperbranched poly(ethylene imine) (PEI) with molecular weight of 25 000 g mol
−1
. (b) Simplified structure of maltose-decorated hyperbranched PEI possessing a dense maltose shell (PEI-Mal A) and open maltose shell (PEI-Mal B). (c) Fifth-generation poly(propylene imine) (PPI) glycodendrimer with dense maltose shell (PPI-G5-Mal). T, terminal units; L, linear units; and D, dendritic structure. PPI-G5-Mal possessing only D units and 1,4-diaminobutane core unit.
Figure 16.2 FT-IR spectra of (a) commercial branched PEI, FeP18 (mass ratio 1 : 1, 1000 bar) and FeP45 (mass ratio 1 : 2), respectively. (b) PEI-Mal A and its hybrid FeP34 (mass ratio 1 : 6, 100 bar) and PEI-Mal B and its hybrids FeP35 and FeP36 (mass ratio 1 : 3, 100 bar).
Figure 16.3 FT-IR spectra of FeP40 and PPI-G4-Mal.
Figure 16.4 Temperature-dependent mass change (TG), mass loss rate (DTG), heat flow (DSC), and Gram–Schmidt curve of sample FeP18.
Figure 16.5 Overview about single IR spectra of sample FeP18 extracted at different temperatures.
Figure 16.6 Measured IR spectra at 114 and 218 °C compared with the database spectra of water, carbon dioxide, and ammonia.
Figure 16.7 Measured IR spectrum at 386 °C compared with the database spectrum of ammonia and the decomposition spectrum of a standard PEI bulk sample.
Figure 16.8 Measured IR spectra at 560 and 610 °C compared with the database spectra of carbon dioxide and carbon monoxide.
Figure 16.9 Temperature-dependent mass change (TG), mass loss rate (DTG), heat flow (DSC), and Gram–Schmidt curve of sample FeP36.
Figure 16.10 Overview about single IR spectra of sample FeP36 extracted at different temperatures.
Figure 16.11 Measured IR spectra at 105 and 266 °C compared with the database spectra of water and carbon dioxide.
Figure 16.12 Measured IR spectrum at 372 °C compared with the database spectra of carbon dioxide, ammonia, and the decomposition spectrum of a standard PEI bulk sample.
Figure 16.13 Measured IR spectra at 612 and 640 °C compared with the database spectrum and carbon dioxide.
Figure 16.14 Temperature-dependent TG and DSC curves for the double determination of sample FeP18.
Figure 16.15 TEM/HRTEM images of iron oxide–polymer nanostructures (a) TEM image of FeP18 (Fe:PEI = 1 : 1, 1000 bar), (b) HRTEM image of FeP18 (Fe:PEI = 1 : 1, 1000 bar), (c) TEM image of FeP36 (Fe: PEI-Mal B = 1 : 3, 100 bar), and (d) HRTEM image of FeP36.
Figure 16.16 ZFC–FC magnetization curves collected in 80 Oe measuring field on samples Fe-100 (a), FeP45 (b), FeP35 (c), and FeP34 (d). In insets are shown the corresponding field-dependent magnetization curves in the first quadrant, collected at 2 K.
