DE102011118819A1 - Constructing superconducting carbon nano-tubes at room temperature by interior doping of their cavities with rod-shaped neutral or charged electrons, mesomeric structure and dipolar molecular structure easily adjustable at their ends - Google Patents

Abstract

The method of constructing superconducting carbon nano-tubes (CNTs) at room temperature by interior doping of their cavities with rod-shaped neutral or charged electrons, mesomeric structure and dipolar molecular structure easily adjustable at their ends, is claimed, where a position of mesomeric molecular rods takes place along unsaturated molecular chains arrayed in the CNTs not by a chemical bond in a horizontal orientation to planar molecular strands, but via direct, vertical or tilted contact with an inner surface of the CNTs having a polarizable atom of the used dipole molecules. The method of constructing superconducting carbon nano-tubes (CNTs) at room temperature by interior doping of their cavities with rod-shaped neutral or charged electrons, mesomeric structure and dipolar molecular structure easily adjustable at their ends, is claimed, where a position of mesomeric molecular rods takes place along unsaturated molecular chains arrayed in the CNTs not by a chemical bond in a horizontal orientation to planar molecular strands, but via direct, vertical or tilted contact with an inner surface of the CNTs having a polarizable atom of the used dipole molecules that are not coordinated as single molecules to generate an optimal contact angle, as a radiation of star-shaped molecular structures, as ligand with acceptors to form metal atoms or as ligand with the acceptors to form molecular asterisk nuclear structures and as charged or neutral molecules that are radially aligned with the acceptors bridged by itself or linked to a given geometry. A diameter of the molecular structure is compatible with the cross-sectional area of the considered nanotube having an internal cavity that is filled with concentrated solution via diffusion by capillary action, to which the asterisks are configured to reach the maximum possible surface contacts of their radiation peaks with physical methods such as ionizing and others known methods. A solvent is removed by conventional methods and still remains between the CNTs, and the adhered asterisks are successively eluted by gentle washing with the solvents of different strength. Short, long or ultra-long, electrically uniform or defect-free single and multi-walled metallic CNTs have diameters. The ligands are chemically bonded to the molecular asterisk nuclear structure having the geometry such as neopentyl, and/or tetramethylmethane core, and are positively ionized by salt formation. Donor-acceptor substituted pi -systems are designed as dipolar molecular structures of conjugated oligomers, where the conjugated oligomers are terminated at their one end by an electron donor and other end by an electron acceptor and covalently bind to the acceptor and the molecular asterisk nuclear structure. Dyes such as diethyl-cyanine/iodide and structural analogues compounds are used as dipolar molecular structures, and are covalently bonded to the molecular asterisk nuclear structure. Resistant, rod-like color molecular structures are used as neutral color molecules. Dye classes are covalently attached at its one end by the strong electron donor and at its other end by the strong electron acceptor. A formation of an ideal color system is only possible for ions whose ionization occurs during bridging of the acceptors with the molecular asterisk core to form salts.

Description

At room temperature, superconducting linear organic conduction chains open up fundamentally new perspectives and possibilities in science and technology, such as:
Lossless energy transfer, more efficient electric motors, exceptionally strong electromagnets, very low heat radiation, switching elements in computers, ie more compact design, faster signal transmission, loss-free magnetic tracks (Meissner-Ochsenfeldeffekt) and more ...

The superconductivity in metals is based on the interaction of the conduction electrons with the crystal lattice. When an electron moves through the metal, it attracts the positively charged metal ions to their solid lattice sites, moving toward each other in its wake. The resulting region of positive excess charge is able to attract a second electron and thereby indirectly couple to the first: both electrons form a Cooper pair. As if they were connected by a spring, they always move at the same speed, but in the opposite direction through the grid - in other words, they swing against each other. The reason for this is that the compressed lattice atoms, which generate a region of positive excess charge and thus cause the electrons to move toward one another, are pushed back to their equilibrium position by restoring forces a little later. However, they shoot beyond the target, creating an area of reduced positive charge density that repels the electrons. As they move toward each other, they swing back and forth - and with them the electrons of the Cooper couple.

In analogy to the superconductivity of metals, but considering the isotope effect (it is all the more difficult to generate a vibration, the larger the mass of the oscillating particle is) WA Little 1964, a theory of high-temperature superconductivity on (Physical Review, Volume 134, Number 6A) , Since, according to the BCS model, the critical temperature of the superconductivity was limited by the relation T = (1 / M) ^1/2 by the mass of the vibrating atoms, a polarizable medium with small atomic masses was sought. Since the atomic masses were much too large, only electrons came into question. The Cooper pair formation should not be made by phonon coupling, but via the electron system. Conceivable would be org. Superconductors in which Cooper pairs come about through the polarization of side molecules (mesomeric push-pull molecules) on a carbon chain and not via a deformation of the crystal lattice. If a conduction electron travels along the carbon chain, the chain forms the backbone of the molecule as the "rail" for the passage of the electrons, repelling the easily displaceable valence electrons of the side molecules (Coulomb repulsion), so that they escape to the "remote end" of the molecules and leave a positive charge surplus at the near end. As with the lattice polarization of the metallic superconductors, the charge shift on the substituents of the electron movement on the wiring harness lags behind in time. The polarization of the substituents is still partially preserved when the next electron passes the substituent. Due to the positive polarization in the region of the conduction channel, the subsequent electron is "sucked into" the channel and coupled by the vibration of the electron cloud in the image of BCS theory with the preceding electron to a kind of Cooper pair. When two electrons are coupled in this way, they oscillate in the same way as the partners of a Cooper pair in metallic superconductors. Since the mass of an electron is smaller by a factor of about 100,000 than that of a typical lattice building block in a metal, the propensity for Cooper pair formation would increase by the square root of 100,000, or about a factor of 300. The chain could z. B. an org. Polymer with a π-bonding system (eg the unstable polyacetylene), but also a chain strand of metal atoms. The substituents of the chain, or the ligands of the metal atoms should contain fluctuating dipoles. As org. Molecules that could fulfill this mediator role suggested Little Hydrocarbons (especially org. Dyes, such as non-persistent diethyl cyanine / iodide) with easily mobile electrons.

The electrical resistance of a macroscopic wire depends on its cross-section and length. This is no longer the case in the case of a nanoscale conductor. The resistance of such a nanowire is independent of its length. The charge transport takes place via cable channels. Prerequisite is the absolute freedom from defects of the considered one-dimensional wire. In real nanowires it comes u. a. on interactions of electrons with the atomic framework. The electrons travel long distances without interaction with the carbon skeleton as they travel through the nanotube (ballistic transport). CNTs can therefore conduct electricity better than metals. The electrons experience no resistance on their free paths (no effect with phonons or lattice defects). Only at the end of their free path do they step into effect with the material. In metallic CNTs, the mean free path is about 1 μm at low field and 10-100 nm at high field.

The structure of any promising chain-like org. Leiters is determined by two requirements:
On the one hand, the chain molecules, as Little postulated, must have a planar structure with maximum π-capping and be non-disruptive (without intramolecular and extramolecular steric hindrance, deformation, torsion and decreasing capping of the π orbitals by substituents), so that the conduction electrons can move easily from one molecule to another. Between the chains, charge carriers must bounce, flow or tunnel. Second, it does not take much energy to partially fill or empty a valence band. The non-persistent polyacetylene favored by Little can be considered in some respects as a kind of low-dimensional homologue of CNTs. It consists of a chain of alternating single and double bonds, so that a molecular wire with a fully conjugated π system is present. Very large annulenes are approaching the electronic structure of polyacetylene. CNTs are considered to be parallel strung polyacetylene molecules rolled up to a tube. Their behavior corresponds to a quasi-one-dimensional molecular wire. However, it also shows that the electronic properties are closely related to those of two-dimensional graphene. Their small diameter causes the occurrence of quantum effects.

Molecules with the structural and electronic presuppositions postulated by Little have been successfully synthesized to this day despite many different approaches, not even partial ones.

task

There are so far no known methods in which in the cavities, the requirements of length and diameter of appropriately sized, metallic carbon nanotubes (CNTs) stored in the highest possible concentration for internal doping fluctuating dipole molecules, while the dipole molecules aligned radially, as di-, tri-, Tetra-, penta-, hexa-, hepta-, octa-, nona-pode or in other suitable geometry are used as polyhedra, the pods with a readily polarizable atom directly the inside curved surface of the CNTs with those given by the geometry of the pod kernels Touch angles. The object of the present invention is therefore to make available, by inserting suitable dipole molecules into the cavities of the CNTs, a CNT-dipole molecule system which, with an optimal arrangement (number of surface contacts, favorable contact angles) of the incorporated dipole molecules, into the correspondingly dimensioned, electrically conductive CNTs. as superconductor meets the criteria of Little's theory.

materials

Carbon nanotubes (CNTS)

Used are short, long or ultra-long, electrically uniform, substantially defect-free or defect-free single-walled and multi-walled metallic CNTS with the respective necessary diameters for filling with fluctuating dipole molecules.

Fluctuating dipole molecules

To ensure that the dipole molecules do not lie flat on the inner surface of the CNTs, but contact the inner surface with only one atom at sufficiently favorable angles, the dipoles, with the optimum possible contact angles, become beams of stellate molecular structures in suitable orientation, either as ligands with their acceptors Metal atoms coordinated or chemically bonded to molecular star core structures, as a charged or neutral molecules star-shaped aligned at their acceptors with themselves bridged or fixed to a predetermined in their geometry, suitable molecular star structure with their acceptors.

Dipole molecules for the construction of star-shaped molecular structures

1) Ligands in metal complexes

Metal complexes with central atoms known from the literature such as Fe, Cu, Ni, Zn, etc., and other metal atoms suitable for the respective complex formation, which are known from dipole ligands known in the literature such as -SCN, -NCS, -NO, -NO ₂ , -CO, -CO ₂ , -CN, -NC, -OCN, -NCO, -NO ⁺ and other ligands suitable in their electronic structure from the repertoire of complex chemistry to trigonal, tetrahedral, square-planar, trigonal-pyramidal, square-pyramidal, hexagonal-pyramidal, trigonal Prismatic and other coordination polyhedra of suitable geometry for the maximum possible contacting of the ligands with the inside of the network structure of the CNTs are coordinated.

2) ligands bridged with molecular star core structures

1), which are chemically bound to star-shaped molecular nuclei of suitable geometry (neopentyl, tetraethylmethane or their derivatives, etc.) and, depending on the structure, additionally by salt formation (eg addition of methyl iodide) can be ionized.

3) donor-acceptor-substituted π systems (D-π-A / push-pull systems)

Suitable conjugated oligomers are used in their geometry, which are terminated at their one end by an electron donor, at the other end by an electron acceptor and covalently bind at the acceptor to molecular star core structures, as cited under 2) and below under molecular star core structures. The push-pull effect of this class of compounds depends on the strength of the donor and the acceptor, but also on the conjugated π system, in which a zwitterionic resonance structure is involved: [D-π-A ↔ D ⁺ -π-A ^- ]
For the energy content of the dipolar boundary structure not only the charge separation, but also the change of the π-system is decisive. In the case of an oligoene chain, this change is less significant than in repeat units of aromatic ring systems whose zwitterionic resonance structure has a p-quinoid character.

4) dyes

The dyes proposed by W.A. Little (diethyl cyanine / iodide and structurally related compounds, resonance hybrids of two borderline structures) are not used as single molecules, but covalently bonded to molecular star core structures as indicated under 2) and 3). The dyes proposed by Little prove to be non-persistent, as is the polyene chain. The proposed dyes should therefore be used only on a trial basis.

Steric reasons require the use of rod-like dye molecule structures. Usable are stable, capable of mesomerism π-electron systems of linear molecular structures from the inventory of different classes of dyes, which at one end via a sufficiently strong electron donor, at its other end via a sufficiently strong electron acceptor, where the dye molecule is covalently bound to the molecular star nucleus, feature. If, in the context of mesomerism, the two end groups mutually merge, the intensity of a mesomerism reaches its maximum with complete valence compensation. If the electron exchange between donor and acceptor is not associated with any fundamental energy tone, then neutral dye molecules can be used. In most cases, the formation of an ideal color system is possible only with ions. The ionization takes place on bridging the acceptors with the molecular star nuclei with salt formation. In symmetric molecules, the ionized structural motif acts as an acceptor. As donors or donor components, structural motifs with electrons readily displaceable on their heteroatoms (N, S, O, P, etc.), such as pyridine, 4-H pyran, 4-H thiopyran, 1,2,3-dithiazole, become necessary according to donors to be modified, as shown on the rod molecules ( J. Am. Chem. Soc., Vol 118, no. 28, 1996, page 6767 ) or other donor-suitable molecular structures that directly contact the CNT network with their molecular beams terminating heteroatoms.

Molecule stellar core structures

Fullerenes are used, which are linked along their coordinate axes with at least six dipole molecules. Neopentyl, Tetraethylmethankerne or their derivatives, etc., quaternary amines, tertiary sulfur compounds, Tetraphenylboratderivate, other Borderivate or other suitable for the construction of molecular stars in geometry and structure analog molecular nuclei.

Structure of the superconductor

For the construction of superconducting CNTs, the star-shaped molecular structures, whose diameters are compatible with the cross-section of the nanotube under consideration, are incorporated into the inner cavity of the tube as a concentrated solution by capillary diffusion, whereupon the stars are used to achieve maximum possible surface contact of their beam tips using physical methods such as Sonization and other methods known in the art, the solvent removed by conventional methods and the still remaining on and between the CNTs, adhering stars are gradually eluted by gentle washing with solvents of different strengths successively. In contrast to the theory of WA Little, the positioning of the substituents along the unsaturated molecular chains aligned in the CNTs does not occur by a chemical bond in a horizontal orientation to the planar molecular strands, but by direct, vertical or tilted contacting of the nearly planar inner surface of the strung in the CNTs Chain molecules through a polarizable atom of the used mesomeric dipole molecules (rays).

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited non-patent literature

• WA Little, 1964, a theory of high temperature superconductivity (Physical Review, Volume 134, Number 6A) [0003]
• J. Am. Chem. Soc., Vol 118, no. 28, 1996, page 6767 [0014]

Claims (8)

Method for building at room temperature superconducting carbon nanotubes (CNTs) by internal doping of their cavities with rod-like neutral or charged, with at their ends easily displaceable electrons, mesomeric, dipolar molecular structures, the positioning of the mesomeric molecular rods along the lined up in the CNTs unsaturated molecular chains not by a chemical bonding in a horizontal orientation to the planar molecular strands, but by direct, vertical or tilted contacting of the CNT inner surface with a polarizable atom of the dipole molecules used is effected in that these not as individual molecules, but to produce the best possible contact angle, as rays (Poden) star-shaped molecular structures coordinated in a suitable orientation either as ligands with the acceptors to metal atoms or chemically bonded as ligands with the acceptors to molecular star structures, as a charged or neut Rale molecules are star - shaped aligned with the acceptors or linked to their acceptors by a molecular star structure predefined in their geometry. The star - shaped molecular structures whose diameter is compatible with the cross section of the considered nanotube are embedded in the inner cavity of the Tube as a concentrated solution by diffusion by capillary effect, after which the stars to achieve maximum possible surface contacts their beam tips using physical methods such as sonication and other methods known to those skilled compresses, then the solvent removed by conventional methods and the remaining on and between the CNTs, adhering stars are eluted successively by gentle washing with solvents of various strengths. The method of claim 1, wherein short, long or ultra-long, electrically uniform, largely defect-free or defect-free single and multi-walled metallic CNTs are used with the respective necessary diameters. The process according to claim 1, wherein dipole ligands known from the literature are used to form the metal complexes, such as -SCN, -NCS, -NO, -NO ₂ , -CO, -CO ₂ , -CN, -NC, -OCN, -NCO, -NO ⁺ and Other suitable in their electronic structure ligands from the repertoire of complex chemistry can be used. The method of claim 1, and 3, wherein the ligands are chemically bonded to molecular star core structures of suitable geometry such as neopentyl, Tetraethylmethankerne or their derivatives and then, depending on the structure, can be additionally ionized by salt formation positive. The method of claim 1, wherein as dipolar molecular structures donor-acceptor-substituted π-systems (D-π-A / push-pull systems), in their geometry suitable conjugated oligomers, which at one end by an electron donor, at the other Terminated by an electron acceptor and covalently bind to the acceptor to molecular star core structures are used. The method of claim 1, wherein as dipolar molecular structures dyes such as diethyl cyanine / iodide and structurally related compounds are not covalently bound as single molecules, but to molecular star core structures used. The method of claim 1, and 6, wherein stable, rod-like dye molecule structures with π-electron systems capable of mesomerism linear molecular structures from the collection of different classes of dyes, at one end via a sufficiently strong electron donor, at its other end via a sufficiently strong electron acceptor on the dye molecule is covalently bound to the molecular star nucleus, are used as neutral dye molecules, but in most cases the formation of an ideal color system is possible only for ions whose ionization takes place during bridging the acceptors with the molecular star nuclei under salt formation and symmetric molecules in the Bridging ionized structural motif acts as an acceptor, as donors or donor components structural motifs with at their heteroatoms (N, S, O, P, etc.) easily displaced electrons, such as pyridine, 4-H pyran, 4-H thiopyran, 1,2, 3-dithiazole, the Erfor according to donors to be modified, as indicated on the rod molecules (J. At the. Chem. Soc., Vol 118, no. 28, 1996, page 6767) or other donor-suitable molecular structures that directly contact the CNT network with their molecular beams terminating heteroatoms. The method of claim 1, wherein as molecular star core structures fullerenes linked along their coordinate axes with at least six dipole molecules, neopentyl, Tetraethylmethankerne or their derivatives, etc., quaternary amines, tertiary sulfur compounds, Tetraphenylboratderivate, other Borderivate and others for the construction of molecular stars in geometry and Structure suitable analog molecular nuclei are used.