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Author: Weekit Sirisaksoontorn Publisher: ISBN: Category : Graphite intercalation compounds Languages : en Pages : 147
Book Description
Novel donor-type graphite intercalation compounds (GICs) containing tetra-n-alkylammonium (TAA) cations have been synthesized by using both ion-exchange and electrochemical methods. Structural and compositional data of the resulting TAA-GICs are investigated by using powder X-ray diffraction (PXRD), one-dimensional electron density calculations, thermogravimetric and elemental analyses, and capillary zone electrophoresis (CZE). A new GIC with composition of [(C4H9)4N]C44 is prepared by intercalation of tetra-n-butylammonium cation, (C4H9)4N, via ion exchange from a [Na(en)1.0]C15 GIC (en = ethylenediamine). The synthesis reaction proceeds at 60°C for 90 min in a N, N-dimethylformamide (DMF) solvent. A dull-black stage-1 [(C4H9)4N]C44 provides the gallery height of di = 0.802 nm, indicating a presence of flattened cation conformation. CZE data reveal that the Na(en) cationic complex is quantitatively displaced by (C4H9)4N+ cations. A homologous series of TAA-GICs; i.e. TAA = symmetric (C[subscript n]H[subscript 2n+1])4N+ (n = 3-8) and asymmetric (CH3)3(C12H25)N+, (CH3)3(C1H3-- )N+ and (CH3)2(C1H3-- )2N+, are prepared using the similar ion-exchange procedure, albeit with shorter reaction time (10 min), in dimethylsulfoxide (DMSO). The obtained TAA-GICs contain either monolayer or bilayer arrangement of flattened TAA intercalates with significant co-intercalation of DMSO molecules in a bilayer arrangement. PXRD data suggest that the monolayer is also observed with small TAA intercalates such as (C3H-- )4N+ and (C4H9)4N+ with di ~ 0.80 nm. On the other hand, larger symmetric TAA cations, (C[subscript n]H[subscript 2n+1])4N+ (n = 5-8), and asymmetric TAA cations all form only the bilayer arrangement with d[subscript i] ~ 1.10 nm. Thermogravimetric analyses combined with mass spectrometry and elemental analyses show a presence of ~1-2 DMSO co-intercalates per bilayer cation. The generated electron density map is sufficient to confirm the existence of bilayer structures, including DMSO co-intercalates. These GICs have very low charge density on graphene sheets for stage-1 GICs, namely C63p− for [(C7H15)4N]C63p−1.4DMSO, as confirmed by Raman peak shifts. In addition, TAA-GICs are also synthesized using the electrochemical reduction on a graphite electrode in TAABr/DMSO-based electrolytes. Similar to GIC products obtained from a chemical ion-exchange method, large TAA cations, (C[subscript n]H[subscript 2n+1])4N+ (n = 5-8), form the bilayer arrangement with 0.7-1.2 DMSO co-intercalates per TAA cation and di ~ 0.11 nm. A mixed phase product, including a stable (C4H9)4N+ monolayer arrangement (di = 0.815 nm), is observed in (C4H9)4N+ intercalation with a little amount of DMSO. No stable and isolable GIC products are obtained in case of TAA cations smaller than (C4H9)4N+ even though cyclic voltammograms show the characteristic features of reversible intercalation/de-intercalation for these cations. Therefore, a surface passivation model is proposed to describe the relative stabilities of GICs containing large TAA intercalates. The effect of surface passivation is further studied on the preparation of (C2H5)4N-GIC. Large TAA cation such as (C6H13)4N+, (C--H15)4N+ or (C8H1-- )4N+, is used to passivate the graphite surface of [Na(en)1.0]C15, followed by ion exchange with (C2H5)4N+ to obtain a (C2H5)4N-GIC product. PXRD data suggest the formation of a stage-1 compound with di ~ 0.81 nm, indicating monolayer arrangement of intercalate. The GIC composition is found to be [(C2H5)4N]C5--.0.5DMSO. Additionally, the hydrophobic nature of passivated GIC surfaces enhances the chemical stabilities in aqueous media and other protic solvents.
Author: Weekit Sirisaksoontorn Publisher: ISBN: Category : Graphite intercalation compounds Languages : en Pages : 147
Book Description
Novel donor-type graphite intercalation compounds (GICs) containing tetra-n-alkylammonium (TAA) cations have been synthesized by using both ion-exchange and electrochemical methods. Structural and compositional data of the resulting TAA-GICs are investigated by using powder X-ray diffraction (PXRD), one-dimensional electron density calculations, thermogravimetric and elemental analyses, and capillary zone electrophoresis (CZE). A new GIC with composition of [(C4H9)4N]C44 is prepared by intercalation of tetra-n-butylammonium cation, (C4H9)4N, via ion exchange from a [Na(en)1.0]C15 GIC (en = ethylenediamine). The synthesis reaction proceeds at 60°C for 90 min in a N, N-dimethylformamide (DMF) solvent. A dull-black stage-1 [(C4H9)4N]C44 provides the gallery height of di = 0.802 nm, indicating a presence of flattened cation conformation. CZE data reveal that the Na(en) cationic complex is quantitatively displaced by (C4H9)4N+ cations. A homologous series of TAA-GICs; i.e. TAA = symmetric (C[subscript n]H[subscript 2n+1])4N+ (n = 3-8) and asymmetric (CH3)3(C12H25)N+, (CH3)3(C1H3-- )N+ and (CH3)2(C1H3-- )2N+, are prepared using the similar ion-exchange procedure, albeit with shorter reaction time (10 min), in dimethylsulfoxide (DMSO). The obtained TAA-GICs contain either monolayer or bilayer arrangement of flattened TAA intercalates with significant co-intercalation of DMSO molecules in a bilayer arrangement. PXRD data suggest that the monolayer is also observed with small TAA intercalates such as (C3H-- )4N+ and (C4H9)4N+ with di ~ 0.80 nm. On the other hand, larger symmetric TAA cations, (C[subscript n]H[subscript 2n+1])4N+ (n = 5-8), and asymmetric TAA cations all form only the bilayer arrangement with d[subscript i] ~ 1.10 nm. Thermogravimetric analyses combined with mass spectrometry and elemental analyses show a presence of ~1-2 DMSO co-intercalates per bilayer cation. The generated electron density map is sufficient to confirm the existence of bilayer structures, including DMSO co-intercalates. These GICs have very low charge density on graphene sheets for stage-1 GICs, namely C63p− for [(C7H15)4N]C63p−1.4DMSO, as confirmed by Raman peak shifts. In addition, TAA-GICs are also synthesized using the electrochemical reduction on a graphite electrode in TAABr/DMSO-based electrolytes. Similar to GIC products obtained from a chemical ion-exchange method, large TAA cations, (C[subscript n]H[subscript 2n+1])4N+ (n = 5-8), form the bilayer arrangement with 0.7-1.2 DMSO co-intercalates per TAA cation and di ~ 0.11 nm. A mixed phase product, including a stable (C4H9)4N+ monolayer arrangement (di = 0.815 nm), is observed in (C4H9)4N+ intercalation with a little amount of DMSO. No stable and isolable GIC products are obtained in case of TAA cations smaller than (C4H9)4N+ even though cyclic voltammograms show the characteristic features of reversible intercalation/de-intercalation for these cations. Therefore, a surface passivation model is proposed to describe the relative stabilities of GICs containing large TAA intercalates. The effect of surface passivation is further studied on the preparation of (C2H5)4N-GIC. Large TAA cation such as (C6H13)4N+, (C--H15)4N+ or (C8H1-- )4N+, is used to passivate the graphite surface of [Na(en)1.0]C15, followed by ion exchange with (C2H5)4N+ to obtain a (C2H5)4N-GIC product. PXRD data suggest the formation of a stage-1 compound with di ~ 0.81 nm, indicating monolayer arrangement of intercalate. The GIC composition is found to be [(C2H5)4N]C5--.0.5DMSO. Additionally, the hydrophobic nature of passivated GIC surfaces enhances the chemical stabilities in aqueous media and other protic solvents.
Author: Tosapol Maluangont Publisher: ISBN: Category : Alkali metals Languages : en Pages : 165
Book Description
Novel ternary graphite intercalation compounds (GICs) of alkali metal cations and a wide variety of amines have been synthesized by one-pot chemical syntheses. Alkali metals studied includes Li, Na and K. The families of amines employed are nalkylamines, branched alkylamines, and different structural isomers of diamines and polyamines. Intragallery structures of the amine co-intercalates residing between the graphene sheets are proposed based on powder X-ray diffraction (PXRD), supplemented by compositional analyses, thermal analyses, and structure optimization when appropriate. A homologous series of M-n-alkylamine-GICs (M = Na, Li) is reported for the first time, with the n-alkylamines of 3-14 carbon atoms (nC3-nC14). The following new GICs with indicated stages and intercalate arrangements are obtained: stage 1, d[subscript i] ~ 0.70 nm, monolayer (nC3, nC4); stage 1, d[subscript i]~ 1.10 nm, bilayer (nC6, nC8); and stage 2, d[subscript i] ~ 1.10 nm, bilayer (nC12, nC14). Here d[subscript i] is the gallery height. Two features new to donor-type GICs found are (i) an intercalate bilayer arrangement with guest alkyl chains parallel to encasing graphene layers, and (ii) the transition from an intercalate bilayer to monolayer arrangement upon evacuation for nC6. GICs containing branched alkylamines co-intercalates are prepared and their intragallery structures compared to those of selected n-alkylamines. A notable difference is observed for amines with 4 carbon atoms. While the linear n-butylamine forms parallel monolayers (d[subscript i] ~ 0.70 nm), the branched analogs (iso-butylamine and sec-butylamine) instead form bilayers with d[subscript i] ~ 1.30 nm. This result contrasts with the general observation that more sterically-hindered intercalates tend to intercalate at lower concentrations. This structural difference is not observed, however, between npropylamine and iso-propylamine (d[subscript i] ~ 0.70 and 0.76 nm respectively). A rare example of a ternary GIC exhibiting cation-directed orientation of the diamine co-intercalate (1,2-diaminopropane, 12DAP) is reported. Depending on the cation M, this diamine can exhibit either perpendicular (M = Li, d[subscript i] ~ 0.81 nm), parallel (M = K, d[subscript i] ~ 0.70 nm) or a tilted orientation (M = Na, d[subscript i] ~ 0.75 nm). Interestingly, the gallery expansions increase as the cationic radii decrease. The structural effect of the diamines is systematically investigated, employing diamines with different alkyl chain lengths, different positions of an -NH2 group, and different -CH3 substituent patterns. The first example of a monolayer perpendicularto- parallel transition in a GIC is reported for Li- ethylenediamine (EN)-GIC, with the respective change in d[subscript i] from 0.85 to 0.68 nm. The sodium analog, Na-EN-GIC, is also prepared and described. We also report quaternary compounds of mixed cations (Li, Na)-12DAP-GIC and mixed amines Na-(EN,12DAP)-GIC. Ternary graphite intercalation compounds (GICs) of alkali metals and polyamines are prepared. Structural modifications similar to the diamines indicated above are also observed for polyamine intercalates. The polyamines studied include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, N, N, N', N', N'- pentamethyldiethylenetriamine, and tris(2-aminoethyl)amine. Most of the new GICs have amine intercalates in parallel orientation (d[subscript i] ~ 0.76-0.86 nm for monolayers, and 1.13 nm for bilayers), though the GIC stage numbers depend on the size of the polyamine. In contrast, the star-shaped polyamine tris(2-aminoethyl)amine shows a perpendicular monolayer orientation with d[subscript i] ~ 1.06 nm.
Author: Toshiaki Enoki Publisher: Oxford University Press ISBN: 9780195351842 Category : Science Languages : en Pages : 556
Book Description
Graphite intercalation compounds are a new class of electronic materials that are classified as graphite-based host guest systems. They have specific structural features based on the alternating stacking of graphite and guest intercalate sheets. The electronic structures show two-dimensional metallic properties with a large variety of features including superconductivity. They are also interesting from the point of two-dimensional magnetic systems. This book presents the synthesis, crystal structures, phase transitions, lattice dynamics, electronic structures, electron transport properties, magnetic properties, surface phenomena, and applications of graphite intercalation compounds. The applications covered include batteries, highly conductive graphite fibers, exfoliated graphite and intercalated fullerenes and nanotubes.
Author: Hartmut Zabel Publisher: Springer Science & Business Media ISBN: 3642752705 Category : Science Languages : en Pages : 365
Book Description
The progress of materials science depends on the development of novel materials and the development of novel experimental techniques. The research on graphite intercalation compounds combines both aspects: new compounds with strikingly new and anisotropic properties have been synthesized and analyzed during the past couple of years by means of state-of-the-art experimental methods. At the same time, the preparation of the compounds already known has improved con siderably, giving increased reliability and reproducibility of the experimental results. The high quality experimental data now available have stimulated theo retical work. Moreover, the theoretical work has had a great impact on further experimental studies, with the effect of a much improved understanding of this class of materials. This volume is dedicated to a thorough description of all relevant experimen tal and theoretical aspects of the structural and dynamical properties of graphite intercalation compounds. Because of the large number of topics, a second vol ume, which is now in preparation, will follow and will treat the electronic, transport, magnetic, and optical properties. The second volume will also contain a chapter on applications of graphite intercalation compounds. There have been a number of reviews written on selected aspects of these compounds in various journals and conference proceedings during the last couple of years, but this is the first comprehensive review since the thorough overview provided by M.S. Dresselhaus and G. Dresselhaus appeared ten years ago.
Author: Hartmut Zabel Publisher: Springer Science & Business Media ISBN: 3642844790 Category : Science Languages : en Pages : 442
Book Description
The research on graphite intercalation compounds often acts as a forerunner for research in other sciences. For instance, the concept of staging, which is fundamental to graphite intercalation compounds, is also relevant to surface science in connection with adsorbates on metal surfaces and to high-temperature superconducting oxide layer materials. Phonon-folding and mode-splitting effects are not only basic to graphite intercalation compounds but also to polytypical systems such as supercon ductors, superlattices, and metal and semiconductor superlattices. Charge transfer effects playa tremendously important role in many areas, and they can be most easily and fundamentally studied with intercalated graphite. This list could be augmented with many more examples. The important message, however, is that graphite inter calation compounds represent a class of materials that not only can be used for testing a variety of condensed-matter concepts, but also stimulates new ideas and approaches. This volume is the second of a two-volume set. The first volume addressed the structural and dynamical aspects of graphite intercalation compounds, together with the chemistry and intercalation of new compounds. This second volume provides an up-to-date status report from expert researchers on the transport, magnetic, elec tronic and optical properties ofthis unique class of materials. The band-structure cal culations of the various donor and acceptor compounds are discussed in depth, and detailed reviews are provided ofthe experimental verification ofthe electronic struc ture in terms of their photoemission spectra and optical properties.
Author: Richard C. Alkire Publisher: John Wiley & Sons ISBN: 3527697519 Category : Science Languages : en Pages : 472
Book Description
The book sets the standard on carbon materials for electrode design. For the first time, the leading experts in this field summarize the preparation techniques and specific characteristics together with established and potential applications of the different types of carbon-based electrodes. An introductory chapter on the properties of carbon together with chapters on the electrochemical characteristics and properties of the different modifications of carbon such as carbon nanotubes, graphene, carbon fiber, diamond or highly ordered pyrolytic graphite provide the reader with the basics on this fascinating and ubiquitous electrode material. Cutting-edge technologies such as carbon electrodes in efficient supercapacitors, Li-ion batteries and fuel cells, or electrodes prepared by screen-printing are discussed, giving a complete but concise overview about the topic. The clearly structured book helps newcomers to grasp easily the principles of carbon-based electrodes, while researchers in fundamental and applied electrochemistry will find new ideas for further research on related key technologies.
Author: Hartmut Zabel Publisher: Springer ISBN: 9783540539216 Category : Science Languages : en Pages : 433
Book Description
The research on graphite intercalation compounds often acts as a forerunner for research in other sciences. For instance, the concept of staging, which is fundamental to graphite intercalation compounds, is also relevant to surface science in connection with adsorbates on metal surfaces and to high-temperature superconducting oxide layer materials. Phonon-folding and mode-splitting effects are not only basic to graphite intercalation compounds but also to polytypical systems such as supercon ductors, superlattices, and metal and semiconductor superlattices. Charge transfer effects playa tremendously important role in many areas, and they can be most easily and fundamentally studied with intercalated graphite. This list could be augmented with many more examples. The important message, however, is that graphite inter calation compounds represent a class of materials that not only can be used for testing a variety of condensed-matter concepts, but also stimulates new ideas and approaches. This volume is the second of a two-volume set. The first volume addressed the structural and dynamical aspects of graphite intercalation compounds, together with the chemistry and intercalation of new compounds. This second volume provides an up-to-date status report from expert researchers on the transport, magnetic, elec tronic and optical properties ofthis unique class of materials. The band-structure cal culations of the various donor and acceptor compounds are discussed in depth, and detailed reviews are provided ofthe experimental verification ofthe electronic struc ture in terms of their photoemission spectra and optical properties.
Author: Watcharee Katinonkul Publisher: ISBN: Category : Graphite fluorides Languages : en Pages : 304
Book Description
New chemical synthesis strategies have been investigated for the preparation of acceptor-type graphite intercalation compounds (GIC's) with fluoroanions in order to obtain new materials and to develop a better understanding of the synthetic approaches and properties of the products. New GIC's containing borate chelate anion such as bis(oxalato)borate, CxB[OC(O)C(O)O]2[delta]F, are prepared by the chemical oxidation of graphite with fluorine gas in the presence of a solution containing the intercalate anion in anhydrous hydrofluoric acid. Due to the chemical method employed (F2/AHF as the oxidizing agent), fluoride co-intercalates are present in the galleries. The GIC's compositions are determined using a newly-developed digestion method with an ion-selective electrode and potentiometer. The composition parameters x and [sigma] are obtained using both elemental and thermogravimetric analyses (TGA). Elemental analyses of B and F for a stage 1 GIC indicate x [approximately equal to] 41 and [delta] [approximately equal to] 4. Powder XRD data and the structural refinement of these GIC's show that the intercalate anions "stand up" in the galleries, with the longer anion dimension oriented perpendicular to the graphene sheets, leading to the relatively large gallery height of di [approximately equal to] 1.42 nm. The same chemical synthesis strategy is also used for chemical preparations of other two borate chelate GIC's; bis(perfluoropinacolato)borate, CxB[OC(CF3)2C(CF3)2O]2[sigma]F, and bis(hexafluorohydroxyisobutyrato)borate, CxB[OC(CF3)2C(O)O]2[sigma]F. Stage 1 GIC's of these anions are obtained with the gallery height, di, of 1.43-1.45 nm. The fluoride co-intercalate contents in these GIC samples are also determined. The composition parameters x and [sigma] are obtained using elemental analyses for stage 1 CxB[OC(CF3)2C(CF3)2O]2[sigma]F and for stage 1 CxB[OC(CF3)2C(O)O]2[sigma]F. TGA cannot be used to confirm these compositions due to the incomplete degradation of intercalates. Most likely, anions and their degradation products are trapped in the bulk of the large flaky graphite particles. The detailed compositions of GIC's containing bis(trifluoromethanesulfonyl) imide, CxN(SO2CF3)2[sigma]F, and perfluorooctanesulfonate, CxC8F17SO3[sigma]F and fluoride co-intercalates are determined for the first time. These GIC's are prepared in aqueous HF, using K2MnF6 as the oxidizing agent. The fluoride co-intercalate content is approximately equimolar to anion content in both GIC's. For CxN(SO2CF3)2[sigma]F, the fluoride content increases steadily with reaction time while the anion content is relatively constant. In contrast, CxC8F17SO3[sigma]F shows little change in the fluoride content over time.
Author: Hari Singh Nalwa Publisher: Academic Press ISBN: 0125137605 Category : Nanostructure materials Languages : en Pages : 809
Book Description
"Nanostructured materials is one of the hottest and fastest growing areas in today's materials science field, along with the related field of solid state physics. Nanostructured materials and their based technologies have opened up exciting new possibilites for future applications in a number of areas including aerospace, automotive, x-ray technology, batteries, sensors, color imaging, printing, computer chips, medical implants, pharmacy, and cosmetics. The ability to change properties on the atomic level promises a revolution in many realms of science and technology. Thus, this book details the high level of activity and significant findings are available for those involved in research and development in the field. It also covers industrial findings and corporate support. This five-volume set summarizes fundamentals of nano-science in a comprehensive way. The contributors enlisted by the editor are at elite institutions worldwide. Key Features * Provides comprehensive coverage of the dominant technology of the 21st century * Written by 127 authors from 16 countries, making this truly international * First and only reference to cover all aspects of nanostructured materials and nanotechnology" -- OCLC.
Author: Hartmut Zabel Publisher: Springer My Copy UK ISBN: 9783642752711 Category : Languages : en Pages : 378
Book Description
This book covers the basic physics and chemistry of graphite intercalation compounds. Emphasis is laid on the layered or quasi-two-dimensional structure of these compounds, which provides an exciting arena for testing physical concepts in lower dimensions. The chapters in this volume, all of which have been written by internationally recognized experts in the field, cover the following topics: the structure and phase transitions of intercalate atoms and molecules in graphite, the physics of staging formation and staging transitions, the lattice dynamics of these compounds as determined by inelastic neutron scattering and optical methods, the diffusivity of the guest species, mesoscopic properties such as domain structures and stacking arrangements, and the synthesis of new compounds. The reviews provide a comprehensive overview of the current status of the field of two- dimensional physics.
Author: Weekit Sirisaksoontorn
Author: Weekit Sirisaksoontorn
Author: Tosapol Maluangont
Author: Toshiaki Enoki
Author: Hartmut Zabel
Author: Hartmut Zabel
Author: Richard C. Alkire
Author: Hartmut Zabel
Author: Watcharee Katinonkul
Author: Hari Singh Nalwa
Author: Hartmut Zabel