Table of Contents
Cover
Title Page
Copyright
List of Contributors
Chapter 1: Block Copolymer Templating as a Path to Porous Nanostructured Carbons with Highly Accessible Nitrogens for Enhanced (Electro)chemical Performance 1
1.1 Introduction
1.2 Electronic Properties of Graphene Edges
1.3 Edge Functionalization of Graphene
1.4 Block Copolymer Templating as a Path to High Surface Area N-Doped Carbons with Accessible Nitrogen-Containing Graphitic Edges
1.5 Evidence of Enhanced Electrochemical Performance of Nitrogen-Rich Copolymer-Templated Mesoporous Carbons
1.6 CTNCs as CO2 Sorbents
1.7 Conclusions
Acknowledgments
References
Chapter 2: Functional Carbon Materials from Ionic Liquid Precursors 1
2.1 Introduction
2.2 Ionic Liquids as Carbon Precursors
2.3 N-Doped Carbon Materials
2.4 From Ionic Liquids to Carbon Materials – Structural Development during Carbonization
2.5 N-Doped Carbon Materials from Ionic Liquid Precursors
2.6 Processing, Shaping, and Functionalization
2.7 Deep Eutectic Solvents – Supramolecular ILs for Carbon Materials
2.8 Applications of IL Derived Carbons
2.9 Conclusion
References
Chapter 3: Functionalization of Graphene Oxide by Two-Step Alkylation1
3.1 Introduction
3.2 Results and Discussion
3.3 Conclusion
Acknowledgments
Supporting Information
References
Chapter 4: Toward Rationally Designed Graphene-Based Materials and Devices1
4.1 Introduction
4.2 Graphene Synthesis
4.3 Structure–Property Relationships
4.4 Graphene Separation
4.5 Graphene-Based Catalysis
4.6 Graphene Functionalization and Templating
4.7 Conclusion
Acknowledgments
References
Chapter 5: Supramolecular Synthesis of Graphenic Mesogenic Materials1
5.1 Introduction
5.2 Liquid Crystal Precursors and Phases
5.3 Methods for Directing Assembly
5.4 Graphenic Mesogenic Materials and their Applications
5.5 Comparison of Thermotropic and Lyotropic Assembly Routes
5.6 Outlook
Acknowledgments
References
Chapter 6: Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes1
6.1 Introduction
6.2 Experimental Section
6.3 Results and Discussion
6.4 Raman Spectroscopy
6.5 Conclusions
Acknowledgments
References
Chapter 7: Chemical Synthesis of Carbon Materials with Intriguing Nanostructure and Morphology1
7.1 Introduction
7.2 Zero-Dimensional Carbon Materials: Carbon Quantum Dots and Carbon Spheres
7.3 One-Dimensional (1D) Carbon Materials
7.4 Two-Dimensional (2D) Carbon Materials: Membranes and Films
7.5 Three-Dimensional (3D) Carbon Materials: Monoliths
7.6 Summary and Outlook
Acknowledgments
References
Chapter 8: Novel Radiation-Induced Properties of Graphene and Related Materials1
8.1 Introduction
8.2 Radiation-Induced Reduction of Graphene Oxide
8.3 Nanopatterning
8.4 Blue Emission from Graphene-Based Materials
8.5 Photothermal Effects in Laser-Induced Chemical Transformations
8.6 Graphene as an Infrared Photodetector
8.7 Reduced Graphene Oxide as an Ultraviolet Detector
8.8 Laser-Induced Unzipping of Carbon Nanotubes to Yield Graphene Nanoribbons
8.9 Generation of Graphene and Other Inorganic Graphene Analogs by Laser-Induced Exfoliation in Dimethylformamide
8.10 Conclusion
References
Chapter 9: Heterofullerenes: Doped Buckyballs
9.1 Introduction
9.2 Heterofullerenes (Cn m n m
9.3 Synthesis and Functionalization of Azafullerenes: An Overview
9.4 Recent Developments: Pentaadducts C59 N(R)5 , Synthetic Efforts Toward C58 N2 , Azafullerene Peapods, Endohedral Azametallofullerenes, and Application of Azafullerenes in Organic Solar Cells
9.5 Conclusions
Acknowledgments
References
Chapter 10: Graphene–Inorganic Composites as Electrode Materials for Lithium-Ion Batteries
10.1 Introduction
10.2 Graphene/0D Inorganic Composites for LIBs
10.3 Graphene/1D Inorganic Composites for LIBs
10.4 Graphene/2D Inorganic Composites for LIBs
10.5 Summary and Future Outlook
References
Index
End User License Agreement
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Guide
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Table of Contents
Begin Reading
List of Illustrations
Chapter 1: Block Copolymer Templating as a Path to Porous Nanostructured Carbons with Highly Accessible Nitrogens for Enhanced (Electro)chemical Performance 1
Figure 1.1 Common N-functionalities in graphitic systems.
Scheme 1.1 Accepted mechanisms of PAN stabilization (a) and carbonization (b) [24].
Figure 1.2 Nanometer-scale self-assembly and conversion of PAN-b -PBA to a nanoporous N-rich carbon material. The green shaded regions point to the two different types interfaces between the semicrystalline PAN and sacrificial block.
Figure 1.3 (a) Schematic, (b) AFM, and (c) grazing incidence small angle X-ray scattering (GISAXS) of a zone cast thin film of PBA-b -PAN and the (d) schematic, (e) comprising stacked nanographenes, and (f) grazing incidence wide angle X-ray scattering (GIWAXS) of the resultant lamellae CTNC film.
Figure 1.4 (a) Small angle X-ray scattering profiles of AN99 -b -BA70 annealed at 200 °C (dashed) and its corresponding CTNC pyrolyzed at 700 °C (solid). (b) XPS high resolution N 1s spectra of mesoporous carbon prepared from AN99 -b -BA70 .
Figure 1.5 Summary plot of specific capacitance and specific surface area values for carbon materials commonly used in supercapacitors.
Figure 1.6 Possible pseudo-Faradaic reaction of the pyridinic group in acidic medium [144].
Figure 1.7 (a) Cyclic voltammetry of CTNCs from AN99 -b -BA70 at a scan rate of 2 mV s−1 using different pyrolysis temperatures (700 and 1000 °C) and electrolyte (H2 SO4 and KOH). (b) Specific capacitance plots for CTNCs from AN99 -b -BA70 pyrolyzed at 700 °C in H2 SO4 electrolyte as a function of pyridinic N-P/C atomic ratio %.
Figure 1.8 Cyclic voltammetry curves of oxygen reduction reaction experiments using nanoporous carbon from a AN99 -b -BA70 precursor at scan rates (a) 10 mV s−1 and (b) 100 mV s−1 in N2 saturated and O2 saturated 0.1 M KOH aqueous solution.
Figure 1.9 (a) CO2 adsorption isotherms of nanoporous carbon prepared from AN99 -b -BA70 pyrolyzed at 700 °C. Solid lines through the data points are fits to the Langmuir–Freundlich equation [160]. (b) Calculated isosteric heat of CO2 adsorption as a function of coverage.
Chapter 2: Functional Carbon Materials from Ionic Liquid Precursors 1
Figure 2.1 Molecular structures of different ILs used as carbon precursors.
Figure 2.2 TGA measured on different ILs. (A) a – BMIM-Tf2 N; b – BCNIM-Tf2 N; c – BCNIM-beti; and d – BCNIM-Cl. (B) a – BMIM-Tf2 N; b – BMIM-tcm; c – EMIM-tcm; and d – DMIM-tcm. (C) a – 3MBP-dca and b – EMIM-dca.
Figure 2.3 Different bonding environments of nitrogen in carbon.
Figure 2.4 HRTEM images of the N-doped carbon synthesized at 1000 °C.
Figure 2.5 HRTEM images of the carbon product from VEIM-dca with 12 wt% FeCl2 ·4H2 O pyrolyzed at 1000 °C before (a) and after (b) removal of iron via an HCl etching process.
Figure 2.6 TEM/SEM-images of (a) porous alumina membrane, (b) SBA-15, (c) silica monolith, and (d) Ludox templated N-doped carbon using 3MBP-dca or EMIM-dca as IL precursor.
Figure 2.7 SEM micrographs of (a) DES derived resin containing MWCNT, (b) carbonized composite material derived from DES-based system, and (c) composite derived from aqueous system without DES.
Figure 2.8 (A) (a) HRTEM of coated Li4 Ti5 O12 . (b) SEM image of coated Li4 Ti5 O12 particles and the EDX mapping images of Ti, C, and N elements. (B) (a) The discharge/charge capacities of pristine and coated Li4 Ti5 O12 at different current rates. (b) Specific capacities of pristine Li4 Ti5 O12 and differently coated samples at different current rates.
Chapter 3: Functionalization of Graphene Oxide by Two-Step Alkylation1
Figure 3.1 Proposed reactions during the treatment of GO with n -BuLi and then with 2-ethylhexyl bromide resulting in the alkyl-functionalized-GO material (i -octyl-Bu-GO).
Figure 3.2 FTIR spectra of GO and i -octyl-Bu-GO. Strong stretching vibration of C−H at 2960, 2926, 2864 cm−1 in i -octyl-Bu-GO indicates functional alkyl chain groups are chemically attached to the GO sheets.
Figure 3.3 Raman spectra of GO and i -octyl-Bu-GO. The ratio of the intensities (I D /I G = 0.87) for i -octyl-Bu-GO is markedly increased compared with that (I D /I G = 0.75) of GO, indicating the break of CC and the formation of much sp3 carbon in i -octyl-Bu-GO by the nucleophilic addition of n -BuLi to the plane of GO.
Figure 3.4 TGA curves of GO and i -octyl-Bu-GO obtained with a heating rate of 5 °C min−1 under purified nitrogen gas flow. Compared with GO, the slower weight loss of i -octyl-Bu-GO below 240 °C indicates that the main oxygen-containing functional groups of GO have been converted to thermal stability functional groups after generic reaction.
Figure 3.5 Concentration dependence of UV absorption of i -octyl-Bu-GO in ODCB (concentrations are 1.99, 3.96, 5.91, 7.84, 9.76, 11.65, 13.53, 15.38, 17.22, 19.05 mg l−1 from a to j, respectively). Shown in the inset are a plot of optical density at maximal absorption position (295 nm) for the GO moiety versus concentration and optical image of GO and i -octyl-Bu-GO dispersed in ODCB (0.4 mg ml−1 ), respectively.
Figure 3.6 (a) TEM images of GO and (b,c) TEM images of i -octyl-Bu-GO. Functionalized sample i -octyl-Bu-GO is still in monolayer dispersion but the surface becomes coarser with many defects after functionalization.
Figure 3.7 (a) AFM image of GO sheets on a mica surface. (b) AFM image of i -octyl-Bu-GO sheets on a mica surface. Single sheets of i -octyl-Bu-GO with an average thickness of about 0.8 nm are present, with different lateral dimensions between 20 and 200 nm.
Chapter 4: Toward Rationally Designed Graphene-Based Materials and Devices1
Figure 4.1 Chemical structure of GO with hydroxides (−OH) and epoxides (−O−) on the surface and carboxylic acids (−OOH), ketones (O) and lactol rings at the edges.
Figure 4.2 Atomic resolution TEM of RGO showing contaminated regions, topological defects, ad-atoms, substitutions, and holes.
Figure 4.3 (a) Isopycnic sorting of an SEG dispersion in an iodixanol density gradient. (b) Atomic force micrograph (AFM) of fraction 4, which is the thinnest, least-dense SEG fraction. (c) AFM of fraction 16, which is a thicker, more-dense SEG fraction. (d) Mean flake thickness histograms plotted by relative frequency for fractions 4, 16, and 28.
Figure 4.4 AFM of Hummers-method-based GO separated on the basis of sedimentation coefficient, from the least dense to the most dense: (a) fraction 4, (b) fraction 10, (c) fraction 15, (d) fraction 20, (e) fraction 25, and (f) fraction 30, with 500 nm scale bars. (g) Spectrally resolved optical absorbance measurements showing the differential visible light absorption of each fraction resulting from differential GO surface chemistry.
Figure 4.5 Scanning electron micrograph of (a) SEG-P25 and (b) SRGO-P25 composite photocatalysts. (c) Acetaldehyde photo-oxidation rate constants and (d) CO2 photo-reduction efficiencies for SEG-P25 and SRGO-P25 composite photocatalysts.
Figure 4.6 Noncovalently bound organic monolayers on epitaxially grown graphene. Room temperature scanning tunneling micrograph of (a) the bare graphene surface, (b) PTCDI-C8 on graphene, and (c) PTCDA on graphene with 3 nm scale bars. Schematic model and unit cell of the (d) PTCDI-C8 monolayer, and (e) PTCDA monolayer.
Figure 4.7 Schematic diagram of a highly porous COF assembled in solution from PBBA and HHTP on a substrate-supported graphene surface.
Chapter 5: Supramolecular Synthesis of Graphenic Mesogenic Materials1
Figure 5.1 Optical textures in liquid crystal phases used as precursors to carbon materials: (a) free surface (gas–liquid interface) of naphthalene homopolymer melt phase [19] under the reflectance mode with crossed-polars and half-wave retarder plate and (b) calamitic (rod-like) nematic phase seen in chromonic liquid crystals used to synthesize vertically aligned graphene layer arrays [2]. Transmission mode, crossed polars.
Figure 5.2 Disk-like or plate-like precursor molecules and their liquid crystal phases. (a) Hexa-alkoxy or -alkyl benzoates of triphenylene engineered to form thermotropic liquid crystal phases [21]. (b) Hexabenzocoronene, a large, planar polyaromatic compound that does not form liquid crystal phases but rather high-melting solid crystalline phases. In pure form, such compounds either melt directly into isotropic liquid phases or decompose. (c) Carbonaceous mesophase, the polyaromatic mixture that exhibits thermotropic liquid crystal phases due to melting point depression associated with its many components [22]. Carbonaceous mesophase derived from thermal treatment of lower molecular weight hydrocarbon feedstocks is a practical precursor for a range of commercially important carbon materials made through liquid crystal synthesis. (d, e) Planar core–periphery amphiphiles that form chromonic liquid crystal phases (l). (f–h) Additional molecular cores that form chromic liquid crystals if sulfonated to impart water solubility. (i–k) Thermotropic discotic liquid crystal phases that include the columnar (i), nematic (j), and isotropic (k) phases. (l) The chromonic lyotropic nematic liquid crystal phase formed by self-repulsion of rod-like supramolecular stacks in aqueous solution. The (l) image adapted from molecular simulations reported in the work of Chami and Wilson [23], (d–h). Note that the π-stacked columns in chromonics are not always a single molecule in width, but can be aggregates.
Figure 5.3 Liquid crystal surface anchoring and confinement. (a) Sketch of various discotic surface anchoring states: “planar” or edge-on, “homeotropic” or face-on. (b) Various order modes for discotic liquid crystals confined in cylindrical geometry [44]. (c) Anchoring states including the tilted state. Also shown is the interfacial excluded volume associated with the edge-on or planar anchoring state.
Figure 5.4 Assembly mechanism for mesogenic graphene structures formed from chromonic liquid crystals. Top sketch shows water-soluble disks with hydrophobic cores and hydrophilic peripheries undergoing π-stacking in aqueous phase to form supramolecular rods. Above a threshold concentration (N/I transition) the rods align into a nematic liquid crystal phase (optical image, crossed polars). Meyer bar coating of the rods followed by drying produces a uniaxially ordered organic film that can be directly converted to graphenic carbon by thermal treatment. The results are vertically aligned graphene layer arrays whose layer orientations can be observed by high-resolution TEM following substrate thinning.
Figure 5.5 A selection of graphenic mesogenic materials. (a) Mesocarbon microbeads (MCMBs). (b, c) A variety of nanofiber types that have been demonstrated by confining mesophase (naphthalene homopolymer) in aluminum oxide nanochannels. (d) Carbon nanotubes form rod-like liquid crystal phases, either in liquid crystal host solvents or alone [50]. (e) The sketch of the VAGLA structure made by chromonic liquid crystals assembly on substrates.
Figure 5.6 Potential applications for vertically aligned graphene layer arrays (VAGLAs) fabricated from chromonic liquid crystals. (a, b) Transparent conducting polarizing thin films, whose thickness can be tuned by adjusting the concentration of precursor in solution. (c, d) Hidden polarization-active micropatterns produced by local shear flow using an artist's brush. (e–g) Superhydrophilic surfaces formed by functionalization of the active upper surface. Panels f and g show contact angles relative to conventional carbon films subjected to the same treatment [65]. (h, i) High-rate alkali-ion battery electrodes that exploit the open interlayer spaces and short diffusion paths offered by the VAGLA structure. (j) Catalyst supports, in which active nanoparticles are tethered or bound to graphene edge sites.
Chapter 6: Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes1
Scheme 6.1 Reactions of SWNT (1 ) and SWNT–CONH(CH2 )17 CH3 (2 ) with chromium hexacarbonyl and (η6 -benzene)chromium tricarbonyl.
Scheme 6.2 Schematic illustration of the main distinctions between exohedral and endohedral bonding of the rehybridized SWNT carbon atoms involved in overlap with the metal d-orbitals in η6 -SWNT complexes.
Figure 6.1 POAV1 pyramidalization angles [74, 75], hybrid orbital eigenfunctions (ψπ ) [72], and hybridizations [74, 75]. Note that θP bears no relationship to θ, which is used in specification of polar coordinates.
Figure 6.2 TGA measurements, together with residual metal oxide (MeO) of (a) purified SWNT and its complexes: SWNT (black), (η6 -SWNT)Cr(CO)3 (blue), (η6 -SWNT)Cr(C6 H6 ) (red); and (b) octadecylamine-functionalized SWNT and its complexes: SWNT–CONH(CH2 )17 CH3 (black), (η6 -SWNT-CONH(CH2 )17 CH3 )Cr(CO)3 (blue), [η6 -SWNT-CONH(CH2 )17 CH3 ]Cr(benzene) (red).
Scheme 6.3 Relationship of rehybridization and pyramidalization, where the rehybridized orbital is h π and the pyramidalization angle is θP (which bears no relationship to θ, which is used in specification of polar coordinates in the text).
Scheme 6.4 Schematic representation of some modes of complexation of carbon nanotubes with chromium metal. Clar structural representation (7 ) of a selected area of a carbon nanotube, chromium complexes of the Clar structure (8 ), full exohedral complexation (9 ) where chromium metal is complexed only above the plane, and mixed exohedral and endohedral complexations (10 ). It is important to note that structure 9 provides a likely packing motif for chromium cluster formation and the SWNT surface is well disposed to template this reaction (see text).
Figure 6.3 TEM images of (a) pristine SWNT, 1 , (c) (η6 -SWNT)Cr(CO)3 complex, 3a , (e) after decomplexation of 3a with mesitylene, (b) starting organic soluble SWNT–CONH(CH2 )17 CH3 , 2 , (d) (η6 -SWNT-CONH(CH2 )17 CH3 )Cr(CO)3 complex, 4a , and (f) after decomplexation of 4a with mesitylene.
Figure 6.5 HRTEM images of (a–d) Cr-functionalized SWNTs: (η6 -SWNT)Cr(C6 H6 ) (5a ), and (e) EDS measurement of (η6 -SWNT)Cr(C6 H6 ) (5a ), showing the presence of Cr.
Figure 6.4 HRTEM images of (a) purified SWNTs, and (b–d) Cr-functionalized SWNTs: (e) (η6 -SWNT)Cr(CO)3 (3a ). (f) EDS measurement of (η6 -SWNT)Cr(CO)3 (3a ), showing the presence of Cr.
Figure 6.6 ATR-IR spectra of chromium hexacarbonyl, (η6 -benzene)chromium tricarbonyl, pristine SWNTs, octadecylamine-functionalized SWNT, and their chromium complexes.
Figure 6.7 XPS survey spectra of (a) SWNT, 1 , and (b) SWNT–CONH(CH2 )17 CH3 , 2 , and their Cr-complexes: (c) (η6 -SWNT)Cr(CO)3 , 3a ; (d) [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(CO)3 , 4a ; (e) (η6 -SWNT)Cr(C6 H6 ), 5a ; and (f) [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(C6 H6 ), 6a .
Figure 6.8 Raman spectra of SWNT, (η6 -SWNT)Cr(CO)3 and (η6 -SWNT)Cr(C6 H6 ), (a–c, 532 nm excitation and d–f, 780 nm excitation); SWNT–CONH(CH2 )17 CH3 , [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(CO)3 , and [(η6 -SWNT-CONH(CH2 )17 CH3 )Cr(C6 H6 )] (g–i, 532 nm and j–l, 780 nm). All spectra are normalized to the 2660 cm−1 peak intensity.
Figure 6.9 Absorbance spectra of the starting material SWNT–CONH(CH2 )17 CH3 , 2 (black), and its reaction product with chromium hexacarbonyl, [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(CO)3 , 4a (red), measured on dispersions in carbon tetrachloride at a concentration of 0.25 mg ml−1 (the spectra are not normalized). Inset shows a schematic representation of the density of states (DOS) of semiconducting, doped semiconducting, and metallic SWNTs with corresponding interband (S11 , S22 , and M11 ) and free carriers (S1fc and M0 ) excitations.
Figure 6.10 Vis–NIR–MIR spectroscopy showing absorbance spectra of SWNTs functionalized with octadecylamine, SWNT–CONH(CH2 )17 CH3 , 2 (black), and its chromium products: [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(C6 H6 ), 6a (a,b) (blue), and [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(CO)3 , 4a (c,d) (red) dispersed in CCl4 . Note that the energy scale is linear in (a) and (c) and logarithmic in (b) and (d).
Figure 6.11 Suppression of the peak intensities of the S11 (black squares) and S22 (blue circles) interband electronic transitions as a function of Cr:C atomic ratio for [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(CO)3 (Cr: C = 1 : 5) and [(η6 -SWNT-CONH(CH2 )17 CH3 )]Cr(C6 H6 ) (Cr: C = 1 : 2) chromium products. The value of the peak suppression is obtained by normalization of S11 and S22 peak intensities of the products to the corresponding peak intensities of the starting SWNT–CONH(CH2 )17 CH3 material.
Scheme 6.5 Schematic model of the metal atom trajectory, showing the initially formed (η6 -SWNT)M complex with subsequent metal atom migration to form the (η6 -SWNT)2 M bis-hexahapto-SWNT inter-CNT junction.
Figure 6.12 Conductivity of SWNT films as a function of the duration of metal deposition.
Chapter 7: Chemical Synthesis of Carbon Materials with Intriguing Nanostructure and Morphology1
Figure 7.1 (a, b) SEM images of RF polymer particles at different magnifications, (c) TEM image, and (d) DLS (Dynamic Light Scattering) plot of the RF resins spheres prepared by the extended Stöber method. (Inset: Photograph illustrating the dispersity of the RF resin spheres in ethanol.)
Figure 7.2 (A) SEM images of the monodisperse polymer nanospheres prepared at different initial reaction temperatures: (a) 15 °C, (c) 24 °C, (e) 28 °C, and their accordingly carbonized analogs CBFS (b), (d), and (f). (B) The curves showing the relationship between the initial reaction temperature (IRT) and the sizes of polybenzoxazine-based polymers nanosphere (a) and carbon nanosphere (b).
Figure 7.3 HRSEM images of the ordered mesoporous carbon nanospheres prepared by a low-concentration hydrothermal method at 130 °C: carbon nanospheres with a diameter of (a) 140 nm; (b) 90 nm; (c) 50 nm; and (d) 20 nm.
Figure 7.4 (A) SEM images of MF microspheres (a) as-synthesized, (b) high monodispersity, and (c) surface condition of carbon spheres prepared after pyrolysis of MF spheres at 900 °C. (B) (a) SEM image of 200-nm carbon spheres prepared at 0.5 M, 160 °C, 3.5 h, (b) TEM image of 1500-nm carbon spheres prepared at 1 M 180 °C, 10 h, and (c) magnified TEM image of an individual carbon sphere.
Figure 7.5 STEM images of hollow carbon spheres (a, c) Z -contrast and (b, d) bright field.
Figure 7.6 (A) (a) Schematic illustration of the fabrication of NGHCs. (b) Diffusion of lithium ions and electrons during the discharge (insertion) and charge (extraction) processes of the NGHCs electrode. (B) (a) TEM and (b) HRTEM images of NGHCs (pyrolyzed at 1000 °C). The inset of (b) is the SAED patterns.
Figure 7.7 (a) Schematic illustration of the procedure for the confined nanospace pyrolysis of hollow carbon nanospheres; TEM images of the product obtained from each step: (b) PS, (c) PS@PF, (d) PS@PF@SiO2 , and (e) HCS, insets are the photographs of the stable aqueous suspensions of these products.
Figure 7.8 TEM images of (a) the polymer spheres, (b) the resultant hollow graphitic spheres (CS-Fe) after acid leaching; STEM images of (c) CS-Fe after acid leaching and grinding.
Figure 7.9 Illustration of the synthesis procedure. (a) Carbon capsule; (b) carbon capsule loaded with the inorganic precursor; and (c) inorganic nanoparticles encapsulated within the mesoporous carbon shell. (1) Filling of the carbon capsule with the inorganic precursor and (2) conversion of the inorganic precursor into inorganic nanoparticles. Bar scale = 100 nm.
Figure 7.10 Scanning electron microscopic images of arrays of mesoporous carbon nanofibers after being calcined at 600 °C for 3 h: (a) top and (b) side views of mesoporous carbon nanofiber arrays within the pores of AAO membranes; (c) top and (d) side views of nanofiber arrays prepared on a silicon wafer by a supercritical CO2 drying process following the dissolving of AAO membrane.
Figure 7.11 (a, b) Optical images of the flexible CNF membrane, the inset in (a) shows the optical image of the CNF solution used for casting the membrane. (c) Low- and high-magnification (the inset) SEM images showing surface morphology of the CNF-50 membrane.
Figure 7.12 Electron microscopic images of the carbon film. (a) Z -contrast image of the large-scale homogeneous carbon film in a 4 × 3 mm area. The scale bar is 1 mm. (b) Z -contrast image showing details of the highly ordered carbon structure. The scale bar is 300 nm. (c) HRSEM image of the surface of the carbon film with uniform hexagonal-pore array. The pore size is 33.7 ± 2.5 nm and the wall thickness is 9.0 ± 1.1 nm. The scale bar is 100 nm. (d) SEM image of the film cross section, which exhibits all parallel straight channels perpendicular to the film surface. The scale bar is 100 nm.
Figure 7.13 (a) 30, 22, 12, and 4 nm-thick TGFs on quartz (2.5 × 2.5 cm2 ) with “M,” “P,” “I,” and “P” letters inside, erased from the film before heat treatment; (b) illustration of the mechanism of the intermolecular condensation of nanographene (PAHs) into graphitic networks; and (c) illustration of the solar cell; the four layers from bottom to top are Ag, a blend of P3 HT and PCBM, TGF, and quartz, respectively.
Figure 7.14 SEM of carbon aerogels derived from polyurea aerogels made of Desmodur RE triisocyanate. Densities (inset) are those of the parent polyurea aerogels. Scale bar: 5 µm. Densities of the actual C samples (from left to right): (a) not measured (sample broke to pieces); 0.29 ± 0.06 and 0.40 ± 0.02 g cm−3 and (b) 0.62 ± 0.08, 0.72 ± 0.03, and 0.78 ± 0.01 g cm−3 .
Figure 7.15 (a) Photograph of as-made polymer monolith and its carbonized product. (b) N2 -sorption isotherms of the obtained carbon monolithic pyrolyzed at different temperatures (P /P 0 is the relative pressure). (c) SEM image of sample RFL-500 (the inset shows an overview of the macroscopic structure). (d) TEM image of sample RFL-500.
Figure 7.16 The synthesis procedure for the GO-RF aerogel and graphene aerogel.
Figure 7.17 Digital photos of the aqueous suspension of graphene oxide (a), the graphene hydrogel (b) in a vial prepared by heating the mixture of graphene oxide and l-ascorbic acid without stirring, the supercritical CO2 -dried (left) and freeze-dried (right) graphene aerogel (c), and a 7.1 mg graphene aerogel pillar with a diameter of 0.62 cm and a height of 0.83 cm supporting a 100 g counterpoise, more than 14 000 times its own weight (d).
Figure 7.18 Scanning electron microscopic (SEM) images (a, b), photograph (c), and TEM image (d) of silica and carbon monoliths.
Figure 7.19 Transparent monolithic silica gels containing different amounts of [Bmim][NTf2 ] (x = 0.3 and 2.0 for (a, b), respectively). After heat treatment under N2 , the clear monolith (a) turned black (c). (d) Structure of [Bmim][NTf2 ].
Figure 7.20 Photograph of the synthesized polymer (a) and carbon monolith (b); TEM images (c–e): images viewed in the [100], [110], and [111] direction; the insets are the corresponding fast Fourier transform (FFT) diffractograms and HR-SEM images (f, g) of the carbon monolith HCM-DAH-1.
Chapter 8: Novel Radiation-Induced Properties of Graphene and Related Materials1
Figure 8.1 Schematic diagram showing irradiation-induced reduction of graphene oxide.
Figure 8.2 Atomic force microscopy image of GO sheets. Inset shows the height profile along the white line.
Figure 8.3 FESEM images of (a) untreated exfoliated graphene oxide, (b) after the irradiation by sunlight for 10 h, (c) by ultraviolet light for 2 h, and (d) by excimer laser for 40 min.
Figure 8.4 FTIR spectra of (a) untreated exfoliated graphene oxide, (b) after the irradiation by sunlight for 10 h, (c) by ultraviolet light for 2 h, and (d) by excimer laser for 40 min.
Figure 8.5 Photographs of aqueous solutions of graphene oxide irradiated by (a) excimer laser and (b) sunlight.
Figure 8.6 Schematic shows two routes for the fabrication of graphene from aromatic self-assembled monolayers (SAMs). (a) Formation of a SAM on Au substrate, (b) electron-induced cross-linking into a supramolecular carbon nanosheet followed by either possible route–route (i): (c) transformation into graphene via vacuum annealing and (d) subsequent transfer to a new (SiO2 ) substrate, and route (ii): (e) transfer to a new substrate and (f) annealing.
Figure 8.7 Schematic diagram illustrating masked laser patterning.
Figure 8.8 FTIR spectra of GO (a) before and (b) after laser reduction (LRGO). Insets show photographs of GO before and after reduction. (c) Current–voltage characteristics of 1, GO; 2, LRGO; and 3, LRGO-Pt.
Figure 8.9 (a) Optical microscopic image of the pattern achieved after excimer laser reduction of graphene oxide and (b) the large-area FESEM image of the pattern. FESEM images of patterns produced with GO + metal salt mixtures subjected to laser irradiation. Large-area image of a pattern produced by laser irradiation of a mixture of GO with (c) HAuCl4 and (d) H2 PtCl6 . FESEM images showing (e) Au and (f) Pt nanoparticles on the graphene surface.
Figure 8.10 Variation in sample resistance per square against the electron irradiation dose (the dashed black lines is a guideline for the eyes). The inset shows an illustration of the device configuration under irradiation with a beam of electrons.
Figure 8.11 (a) Photoluminescence spectra of exfoliated graphene oxide (GO) and reduced graphene oxide obtained by radiation with sunlight (SRGO), ultraviolet light (URGO), and excimer laser (LRGO). (b) CIE diagram.
Figure 8.12 White light emission from ZnO–LRGO nanocomposite.
Figure 8.13 Photoluminescence (PL) spectra (excitation at 325 nm) of progressively reduced GO thin films. The total time of exposure to hydrazine is noted in the legend mentioned in the figure.
Figure 8.14 Schematic showing laser-induced photochemical transformations.
Figure 8.15 FTIR spectra of (a) hydrogenated graphene and (b) chlorinated graphene irradiated for 45 min with an excimer laser.
Figure 8.16 Changes in temperature of the solution with laser irradiation time for (a) aqueous dispersion of graphene oxide (GO) with varying pulse energy and repetition rate, (b) GO dispersions in different solvents keeping the average energy and repetition rate of the laser source constant, (c) aqueous dispersion of GO with different laser wavelengths, and (d) aqueous dispersion of different graphitic materials with constant average energy and repetition rate of the laser source. For all the cases, 3 mg of sample was dispersed in 3 ml of the solvent and was then irradiated with laser source for 45 min. In all the experiments, the temperature rise of the corresponding solvents due to laser irradiation have been taken account of and shown in the corresponding figure.
Figure 8.17 Temperature changes of graphite oxide solutions during laser irradiation with the 1064, 532, and 355 nm of the Nd/YAG laser (5 W, 30 Hz). Photographs show the changes in the colors of the solutions with laser irradiation. Dotted curves show the temperature changes due to the same volume of water with the same irradiating condition (5 W, 30 Hz).
Figure 8.18 Photothermal effect exhibited by (a) various hydrogenated graphenes and (b) chlorinated graphene.
Figure 8.19 Photocurrent generated at a back-gate bias of ≈−15 V with the incident power. Inset shows the schematic of the measurement. Scale bar 5 µm.
Figure 8.20 (a) Photocurrent as a function of time with different IR intensities at 2 V for reduced graphene oxide (RGO). Inset shows the photo response of the device at 80 mW cm−2 to show the reproducibility of data with time at 2 V for RGO. (b) Photocurrent as a function of time with different IR intensities at 2 V for graphene nanoribbons (GNRs). The photo response of the device for GNR at 80 mW cm−2 is shown as inset.
Figure 8.21 Photocurrent as a function of time with human body IR at 2 V for reduced graphene oxide.
Figure 8.22 Representative diagram for photodetector mechanism.
Figure 8.23 (a) Typical I–V characteristics of the dark (squares) and under UV illumination (circles) of the device at 360 nm with 0.3 mW cm−2 . Top left inset shows the reproducibility of the data with time as UV source was turned on and off. Bottom right inset shows the schematic diagram of the device structure and (b) represents the photo-response before saturation.
Figure 8.24 TEM and FESEM images for GNRs obtained by laser irradiation of MWNTs: (a) CVD-MWNT sample irradiated at 250 mJ and (b) arc-MWNT sample irradiated at 350 mJ. Corresponding FESEM image are shown as insets.
Figure 8.25 Photographs of (i) dispersions of (a) graphite powder and (b) bulk BN in DMF and (ii) of the supernatant liquid after laser irradiation.
Figure 8.26 (a, b) FESEM images and (c, d) TEM images of laser-exfoliated graphene sheets.
Figure 8.27 (a) AFM image of laser-exfoliated graphene. Height profiles of graphene sheets showing (b) single-, (c) bi-, and (d) few-layer graphenes.
Figure 8.28 (a) FESEM and (b) TEM images of laser-exfoliated BN. Inset in Figure 8.3b shows an electron diffraction pattern of the BN sheets.
Figure 8.29 (a) AFM image of laser-exfoliated BN sheets. Height profiles of (b) single-, (c) bi-, and (d) five-layer BN.
Chapter 9: Heterofullerenes: Doped Buckyballs
Figure 9.1 The aza[60]fullerene radical (1 ) and its dimer (2 ).
Figure 9.2 FT-ICR mass spectra demonstrating the synthesis of C59 B− from pristine C60 .
Scheme 9.1 (a) Synthesis of 2H -pyran ring-containing fullerene cage 4 [66]. (b) Synthesis of fullerendione 5 and orifice-closed compound 6 [67].
Figure 9.3 Oxofulleroids C59 O3 , C60 O4 and suggested structure of in situ– dioxafullerene C58 O2 [44].
Scheme 9.2 Wudl's synthesis of (C59 N)2 [29].
Scheme 9.3 Radical-type functionalization of C59 N [74, 77–79].
Scheme 9.4 Nucleophilic functionalization of C59 N+ via electrophilic aromatic substitution (a) [82], Mannich-type addition of enolizable nucleophiles (b) [83], or direct addition of an alcohol as nucleophile (c) [84].
Scheme 9.5 (a) Synthesis and spectroscopically assigned structure of C59 NAr(Cl)4 [94]. (b) Synthesis and (c) X-ray structure of C59 N(CF3 )5 .
Scheme 9.6 (a) Synthetic pathway leading to pentaaryladduct 28 . (b) One of several isolated mono- and dihydroazafullerene intermediates (29 ). (c) X-ray structure of 28 .
Scheme 9.7 Synthesis of mixed pentaadduct C59 N(OOt 4 Br (31 ) [76].
Scheme 9.8 Tether-based approach for the synthesis of C58 N2 starting from monoazafullerene 33 [111].
Scheme 9.9 (a) Tweezer-based approach for the synthesis of C58 N2 starting from C60 and bisazide 34 . (b) MALDI-TOF mass spectrum clearly showing C58 N2 (m /z = 724) as the dominant fullerene species (Gmehling, unpublished results). *One of several possible bisketolactam isomers is shown [112].
Scheme 9.10 (a) Multistep synthesis of ketoimide 42 . (b) MALDI-TOF mass spectrum resulting from nonsoluble intermediate 41 , clearly showing a peak for protonated diazafullerene C58 N2 H+ . *This compound could also be present as the tautomeric hemiaminal.
Figure 9.4 Azafullerene(43 )/SWCNT peapods as evidenced by HR-TEM micrograph.
Figure 9.5 (a) Single-crystal X-ray structure of Tb2 @C79 N, co-crystallized with nickel octaethylporphyrin. (b) Calculated spin density for Y2 @C79 N.
Figure 9.6 Azafullerene-based bulk heterojunction solar cells and their key performance parameters. (a) Gan and Ding's azafullerene bisadduct. (b) Azafullerene pentaadduct studied by Wessendorf and Hirsch. (c) Azafullerene monoadduct studied by Viterisi and von Delius [139–141]. Results for reference devices (PCBM) shown in parentheses.
Chapter 10: Graphene–Inorganic Composites as Electrode Materials for Lithium-Ion Batteries
Figure 10.1 Schematic illustration of a rechargeable lithium ion battery cell composed of cathode, anode, and electrolyte.
Figure 10.2 Schematic diagram of graphene-based electrode materials composited with (a) 0D, (b) 1D, and (c) 2D electrochemically active inorganic substances.
Figure 10.3 (a) Transmission electron microscopy (TEM) image of a SnO2 –SiC/G particle and the SAED pattern of SiC in the inset. (b) Magnified TEM image of the SnO2 –SiC/G particle. (c) High-resolution TEM image of individual SnO2 nanoparticles supported on the SiC surface. (d) The corresponding SAED pattern of SnO2 nanoparticles. (e) High-resolution TEM image of the edge of the SnO2 –SiC/G particle. (f) Schematic illustration of the preparation process of the SnO2 –SiC/G nanocomposite.
Figure 10.4 (a) Scanning electron microscopic (SEM) image of the prepared porous RGO film. (b) Scanning transmission electron microscopic (STEM) and elemental mapping of RGO/Co3 O4 composites. (c) Cycling performances of Co3 O4 , physical mixture of Co3 O4 and RGO (p -Co3 O4 /RGO), RGO film, and Co3 O4 /RGO film electrodes at a current density of 50 mA g−1 .
Figure 10.5 Schematic illustrating aerosol-assisted capillary assembly of crumpled-graphene-wrapped Si nanoparticles.
Figure 10.6 (a) Representative pattern of GO immobilizing S. The hydroxyl enhances the binding of S to the C−C bond due to the ripples induced by epoxy or hydroxyl groups. Yellow, red, and white balls denote S, O, and H atoms, respectively, while the others are C atoms. Note that the C atoms bonding to S or O are highlighted as blue balls. (b) Cycling performance at the current rate of 0.1 C (167.5 mA g−1 ) after initial activation processes at 0.02 C for 2 cycles.
Figure 10.7 Scanning electron microscopic (SEM) (a) and TEM (b, c) images of the as-synthesized nanocables. The lower part of (b) is an enlarged image of the area marked by the box in the upper part with a schematic diagram of the morphology of an individual nanocable inserted. The insets in (c) show the HRTEM image and corresponding SAED pattern. (d) Scanning transmission electron microscopic (STEM) and element mapping images of an individual nanocable.
Figure 10.8 (a) Schematic illustration of the fabrication (upper panel) and adapting (lower panel) of SiNW@G@RGO. (b) Cross-section SEM image of SiNW@G@RGO with an enlarged view in the inset. (c) Comparison of capacity retention of different electrodes.
Figure 10.9 (a) SEM images of the graphene–SnS2 composite. (b) Rate performance of different samples at 100, 200, 400, 800, 1600, 3200, 6400, and 100 mA g−1 from left to right. (Luo 2011 [146]. Reproduced with permission of Royal Society of Chemistry.) (c) TEM image of the RGO–MoS2 composite material with the Mo : C molar ratio of 1 : 2.25. (d) Rate capability of graphene–MoS2 samples at different current densities: (1) RGO/MoS2 (1 : 1); (2) RGO/MoS2 (2 : 1); and (3) RGO/MoS2 (4 : 1).
Figure 10.10 (a) Procedure for the formation of graphene-confined Sn nanosheets. (b) TEM images of the 2D/2D graphene/Sn nanocomposite. The inset of (b) shows selected area electron diffraction (SAED) pattern of the region marked in (b). (c) Comparative cycling performance of different samples.
List of Tables
Chapter 2: Functional Carbon Materials from Ionic Liquid Precursors 1
Table 2.1 List of nitrogen contents and BET surface areas of different IL derived carbons
Chapter 3: Functionalization of Graphene Oxide by Two-Step Alkylation1
Table 3.1 Comparison of the dependence of sheet resistance and film (∼100 nm thickness) conductivity of i -octyl-Bu-GO for different reducing methods
Chapter 4: Toward Rationally Designed Graphene-Based Materials and Devices1
Table 4.1 Summary of process scalability and materials characteristics of graphene produced from the most widely used synthetic methods
Chapter 6: Synthesis and Characterization of Hexahapto-Chromium Complexes of Single-Walled Carbon Nanotubes1
Table 6.1 Chromium content in SWNT–chromium complexes from TGA
Chemical Synthesis and Applications of Graphene and Carbon Materials
Edited by Markus Antonietti and Klaus Müllen
The Editors
Prof. Markus Antonietti
MPI of Colloids and Interfaces
Colloid Chemistry
Research Campus Golm
Colloid Chemistry
14424 Potsdam
Germany
Prof. Klaus Müllen
MPI für Polymerforschung
Ackermannweg 10
55128 Mainz
Germany
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