CA2124191A1 - Novel salts of fullerenes - Google Patents
Novel salts of fullerenesInfo
- Publication number
- CA2124191A1 CA2124191A1 CA002124191A CA2124191A CA2124191A1 CA 2124191 A1 CA2124191 A1 CA 2124191A1 CA 002124191 A CA002124191 A CA 002124191A CA 2124191 A CA2124191 A CA 2124191A CA 2124191 A1 CA2124191 A1 CA 2124191A1
- Authority
- CA
- Canada
- Prior art keywords
- fullerene
- group
- anion
- composition
- potential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/152—Fullerenes
- C01B32/156—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The present invention relates to new compositions of matter having the formula AnCx, wherein A is a monovalent cation and Cx is a fullerene anion, preferably wherein x is equal to 60 and 70. The present invention also relates to a process for preparing the composition by applying an electrical potential to a non-aqueous solution of a fullerene and a salt containing a monovalent cation. The present invention also relates to a method for electrochemically generating fulleride salts as a solution in other hydrocarbons. The present invention also relates to a method for electrochemically preparing solid fulleride salts. The compositions may be used as electrode material in reversible electrochemical cells, superconductors, spin labels, magnetic thermometers, organic, and polymer precursors.
Description
' W0 93/11067 ~ 1 3 1 Pcr/uss2~10 NOVEL SALTS OF FULLERENES
FIELn OF THE INVENTIQN
The present ~nvention relates to novel salts of fullerenes also known as fulleride salts, their preparation and use.
BACKGRQUND OF_~ I~VENTION
Diamond and graphite are two well known allotropic forl~s of carbon. Another form, the fullerenes, have been prepared by graphite volatilizat~on (See W. Kratschmer et al, Nature, 347, p. 354 (1990)).
Pot~ssium and other metal complexes of fullerenes have been observed ln the gas phase by mass spectrometry (See D. M. Cox et al, J. Chem.
~PhYs. 88(3~, 1588 ~19B8)).
Fullerenes are hollow molecules composed only of carbon ato~s and constltute a new allotropic form of car~on. Typically, f~ renes ~ach have carbon atoms arranged as 12 pentagons, but d~f~er1ng numbers of hex~gons having the formula C2n where n is equal to or greater than 16 (hereinafter UfullerenesN). The pentagons are requlred in order to allow the ourYature and eventual closure of the c~osed surface upon ~tself. The most abundant species of fullerenes ident1f~ed to date ~s the C60 molecule or Buchminsterfullerene (here-~nafter ~C60~). C~o oons~sts of 12 pentagons and 20 hexagons.
Ho~ever9 other species, includ1ng C70 have also been ~dentified.
~MMARY OF ~HE INVENTION
The portion of this invention that relates to C60 fulleride salts was f~rst dlsclosed by appllcants at a seminar in Boston, Massa~husetts on November 29, 1990, and subsequently published in Mat.
Re$. Soc. SvmP. Proc., Vol. 206, p. 659 tl991). This invention provides new composit~ons of matter having the formula AnCX~ wherein C~ is a fullerene anion wherein x is preferably selected from the group consisting Of C60 and C70 and wherein A is a monovalent cation.
WOg3/11067 ~J~ 3 PCr/US~2/10120 Preferred monovalent cations, in accordance with the present inven-tion, include ammonium cations, alkyl ammonium cations such as quater-nary ammunium cations, alkali metal cations, phosphonium and arsonium cations, especially organophosphonium and organoarsonium ions, partic-ularly phenylphosphonium and phenylarsonium cations. The preferred fullerene used ~n the practice of the present invent~on is Cho.
In one embodiment of the present invention, the ~ulleride salt compounds of the present ~nvention are prepared by passing a~
electr1c current through (electrolyzing) a non-aqueous solution of fullerenes ~n the presence of a soluble salt containing a cat~on, A, of the AnCX compound to be formed. The electric potential is applied for ~ t~me sufficient to generate fullerene anions in the solut~on.
In another embod~ment of the present invention, the fulleride salt compounds are prepared ~n the solid state. The ccmpounds of the present ~nvention exhibit reversible electrochem~cal reduction; and, consequently, are partlcularly useful as electrode components in electrochem~cal cells sueh as secondary batteries.
The fullerene anions, C60-Y and C70-Y, wherein y is a charge of from 1 to 3, spec~fically 1, 2, and 3 ~n the compound of the present invant~on contain unpaired electrons and thus have paramag-netic properties. In the case of, for example, c60-l and C6o-2~ these propert~es are con~irmed by electron spin resonance spectroscapy ESR~) ~or the tetralkyl ammonium fulleride salt containing ~he c60-l monoan~on. The magnitude of the magnet~c suscept~b~llty of the compound of the present invention var~es with the temperature accord-lng to the Curie-We~ss law, wh~ch ls known to one hav~ng ordinary sklll ~n the art. Since a one-to-one magnet~c susceptibillty tempera-ture correspondence ex~sts, these compounds may be used as magnetic thermometers. ~:
Sim~larly, fuller~de salts containing c60-l monoan~ons may be used as semiconductors (See P. M. Allemand et al., J. Am. Chem.
Soc~, 113,2780 (1991)) wh~le those containing C60-3 ~nd alkali-metals may be used as superconductors ~See A. F. Hebard et al., Nature 350,600 (199i)).
WO 93/11067 PCr/US92/10120 , ';' ~' '',1 ... ,.~ i -. .1 Alkali salts Of C60 also can serve as starting materials for the preparation of other materials. The reaction of the lithium salt of C60, for example, with alkyl halides yield alkyl derivatives of fullerenes (See J. W. Bausch et al., J. Am. Chem. Soc., 113,320 (1991)) that may-be useful as polymer blends, composites and building bl ~cks .
Further, the AnCX fulleride salts are stable in the absence of a~r and other react~ve molecules. Their free radical charac~er may make them suitable as spin labels. Spin labels are usually organic ~olecules that contain an unpaired electron ~for example, a nitrox~yl rad~cal) and are used to render diamagnetic molecules to which they are attached susceptible to analys~s by magnetic spin re!sonance techniques. ~he AnCX spln labels m~xed, for example with polymers, 0ay allow valuable information concerning polymer dynamics and struc-tures t~ be obtained.
qESCRIPT~ON OF THE PREFERRED EMBDDIMENTS
The present invention encompasses novel compositions of matter ha~ing the formula AnCX~ wherein Cx is a fbllerene anion, whcre~n Cx ls preferably selected from the group consisting of C60 and C70, where1n A is a monovalent cation and wherein n is an integer from 1 to 3 ~nclusive, specifically 1, 2~ and 3. The cation, A, may be selected from a w~de range of cations. The fullerene anion is further selected from the group consist~ng of monovalent, divalent and trt-valent an~ons. Its valence, however, depends on the formula of the monovalent cation, An. Thus, for example where the monovalent catlon, An~ has the formuls (A~ , Cx wlll be a monovalent anion; where An has the formula (A~1)2, Cx w~ll be a divalent anion; for (A+1)3, Cx w~ll be a triYalent anion. Particularly preferred cations for A
~nclude ammonium and alkyl ammon~um cations, organophosphon~um or organoarsonium cations, espec~ally tetraorganophosphonium and tetra-organoarsan~um ions, such as tetraphenylphosphonium and tetraphenyl-arson~um cat~ns, alkali metal cations, and the like. Among the alkali metal cations, L~, Na and K are especially preferred. The WO 93/110~i7 PCl~US9~/10120 -i~ L r:
preferred fullerene used in the practice of the present invention is c6o~
) The starting materials for $he practice of the present invention can be obtained from con~Tercial sources. In addition, ~he fullerenes may be prepared by graphite volatilizatlon ~see W.
Kr~tschmer, et al, Nature, 347, p. 354 ~1990)).
When the compounds of the present inYention are made by electrolyziny a non-aqueous solution containing fullerenes and a soluble salt of a cat~on, A, such as one of the aforementioned ca~-ions, the etectrochem~cal reduotion of fullerenes ~s conducted prefer-ably ~n a low or h~gh polar~ty solvent as required tQ diss~lve the reactants, but wh~ch will be inert to the reaction~ 'INon-aqueous'' as used here~n means solvent systems wherein waterl if present, ~s electrochemically and chem~cally ~nert. Thus, by way of example, tolu~ne, d~chloromethane in the case where the cation, A, îs ~rganic and a h~gh polar~y solvent such as dimethyl sulfoxide when the cation A ~s ~norgan~c. Slngle, b~nary or mult~component mixtures of tetrahy-drofuran, ethylene chlorlde, toluene, xylenes, d~methyl sul:fox~de, d~chloromethane, benzene are part~cularly suitable for dissolving the fullerenes. Add~t~onally, the salt conta~nlng the cat~on, A, of de~red compound, A~CX, must have some solubility in the organic solvent system used. Typically, therefore, salts containing organo groups sueh as7 but not restr~cted to7 R4~Cl, R4AsCl, R4PCl, P(4NPF6, and R4NBF4 are part~cu~arly su~table. In the forego~ng s~lts, R is sel~!cted from the group cons~sting of hydro~en and an organ~c moiety.
lhe organ1c moiety should be chosen in order to render the salt soluble in the solvent system. It is within the skill of one of ordinary sk~ll ln the art to make a selection of the appropriate solvent system. R may, for example, be selected from alkyl groups having from 1 to 16 carbon atoms and phenyl groups. Other useful sa~ts include alkali metal salts haYing anions containing sufficient organic moiet~es to render the salt soluble in the solvent system.
Representat~ve examples include Na8Ph4, K8Ph4 where (~Ph" as used herein means phenyl or substituted phenyl group). When ~norganic salts containing the cation A are used, the solvent system is more wo s3/lto67 .~ s~ ~ 9 1 PCT/uS92/10120 polar. Inorganic salts such as NaBF4, KCl and KBr should be used with m~xtures of tetrahydrofuran, dimethyl sulfoxide, dimethyl formam;de, toluene and the l~ke. The relative ratio o~ components of the solv~nt mixtures should be such as to insure some degree of solubility of both start~ng materials; i.e., fullerenes (which are soluble in relatively non-polar solvents) and inorganic salts (more soluble in polar sol-vents like dimethyl sulfoxide). It is within the skill of a person with average skill in the art to select the optimum mixture of sol-vents suitable for a given inorganic salt containing a desired A
cation. The resultant AnCX fulleride salts need not be soluble in the solvent mixtures used and 1t is preferred that they are not ~f ~sola-tion o~ the sol~d salt is desirable.
A commercially available PAR (Princeton Appl~ed Research) System equlpped with Pt wire auxiliary electrode, standard calomel reference e~ectrode (SCE) and a Pt gauze working electrode may be ~sed to reduce, for example, up to gram quantit~es of the particular fullerene. Other commerclal units ~ay be used to prepare larger qu~nt1t~es of fulleride salts. A potentiostat regulates the potential necess~ry to produce the desired reduction state (salt of anion) of the fullerene in the particular solvent system. The molar rat;o of salt to fullerene used in the solvent system will be generàlly greater than 3:1 and, preferably, wlll be in the range of about 10 to 20. The potent~al ~ay be appl~ed using any known source o~ direct current after ~mmersing the work~ng and reference electrodes into the solvent system. The aux~liary ele~trode may be isolated from the working electrode compartment dur~ng appl~cation of the electric potential, th~ ~ixture may be stirred, but such is not necessary. Typically, the react~on takes place at room temperature and pressure under a blanket of inert gas. Alternatively, an inert gas (for example, N2, Ar) may be bubbled through the solvent mixture. For example, for the produc-tion of C60-l monoanion from C60 a potential of -0.45 V versus SCE in the DMSO solvent system uslng KBr as supporting electrolyte resulted ~n product10n of only the fullerene salts containing C60 monoanion.
Since the potential necessary to produce the anions of desired valence is solvent dependent its value can be determined via cyclic voltam-metry (CV) or d~fferential pulse polarography (DPP). Care must be w ~ 93/11067 ~ 3 I PcT/uss2/l taken in choosîng solvent system, electrolyte, temperature, eleotrode type, etc. to obta~n reversible well separated waves in CV at slow scan speeds. These conditions are necessary for selective production r of the particular fullerene salt and to ensure that once produced they àre not decomposed during the bulk electrolysis. For typical examples of well separated waves in CV and DPP data on C60 and C7~ fullerenes, see S. M. Gorun et. al, Mat. Res. Soc~_~ymD~_Proc. 206, 659 ~1931).
The process of the present inven~ion may be used t~ selec-tively generate the salt of the fullerene anions in solutions of the fullerenes and other hydrocarbons by applying a current to the solu-tion, wherein the current is of sufficiently low voltage to selective-ly reduce the particular fullerene to the correspondent salt off ~he fullerene anion without reducing the other hydrocar60ns. The fuller-ene anions have the formula Cx-Y, wherein Cx iS a fullerene, prefera-bly a fullerene selected from the group cons~sting af C60 and C70 and where~?n y is an integer of from 1 to 3, spec~fically 1, 2 and 3. ~he range of electric potent~als will vary wi?lth the solvent system, but can readily be selected by one havin~ ordinary skttl in the art. ~he electric potentiial is ~rom about zero to about -0.7 V, when the fullerene anion is selected from the group consisting of c60-l (when : the fullerene ~?s C60) and c70-1 when the fullerene is C70; ~t is from about -0.80 Y to about -1.1 V when the fullerene anion is setec~ed ~ro~ the group consist~ng of C6o-2 (when the fullerene is C60) and C70-2 (when the ~ullerene ~s C60) and C70-2 (when the fullerene is G70~; and it is from about -1.3 V to about -1.7 ~ when the fullerene an~on t?s selected from the group consisting of C~o~~ (when the fu~ler-ene ~s C60) and C70-3 ~when the ~ullerene is C7~3. For example, c60-l~ which is prepared from C60 at a potentiial of -0.70 V in 1:2 d~?chloromethane/toluene milxtures, may be selectively prepared as the sa~t of the c60-l an~on ~rom mixtures of C60 w~th other hydrocarbons havin~ hlgher potentials (that is, having a chemical inertness with~n ~he range of potenti?als at which the c60-l anion is produced) by apply~ng the foregoi?ng chemiical potentlals to the solution. The salt of the fullerene anion may be present iin the solution or precipitated therefrom. The actual voltage may vary, depending on the solvent in which the reduct~on is conducted. However, the potential should be . ~i .~ 1 1 3 1 chosen within the range of the electrochemical potential necessary to generate the particular salt of the fullerene anion and within the ranQe of chem~cal inertness for the other hydrocarbons. (For techni-cal deta~ls see, for example, P. T~ Kissinger and Wm. H. Heineman, Editors, ~aborat~ry Techniques in Electrochem;strY, Marcel Decker, Inc., N.Y. (1984~; and A. Bard and L. Faulkner, lectrochemical MethQds, Wiley and Sons, N.Y. (1980)).
During the electrolysis, the progress of the reaction is ~onitored by measuring the amount o~ current that passes through the solut10n. Alternatively, s~nce the fullerene anions are paramagnetic wh~le the start~ng fullerenes are diamagnetic, quantitative ESR
spectroscopy can be used for the same purpose. Similar results are expected for c70-1 monoanion. (See, for example M. A. Greaney et al., . PhYs, Chem. 9~,7142 (1991) for the ESR signatures of the c60-l and c70-1 and D. Dubo1s et al., J. Am. Chem. Soc. 113,4364 (199lJ for C6o~2). For ~60, applicants found that the most convenient method to detect c60-l is the monitoring of the near infrared spectrum of the solut~on. ~ strong absorption band centered at approximately 1065 nm ~s present ~n c60-l~ but mlssing in C60. This band, which is attr1b-uted to the HOMO-LUMO (highest occupied molecular orbital-lowest unoccup1ed molecular orbital) electronic transition of C~o-1 disap-pears upon ox~dat~on of c60-l to C60 and can be regenerated upon furth~r reductlon. Its position and intensity is practically indepen-dènt of the A cation, being observed for both organic (e.g., Bu4N) and 1n~rganic (e.g., K) salts of c60~ n a variety of solvents. As used hereln, ~Bu~ means ~butyl~.
~ The AnCX product ~ay be isolated by precipitat~on; for example, using a non-solvent or precipitatlng agent, such as toluene or ether or by reducing the volume of the solvent used v~a vacuum distillatlon or low temperature freez~ng. Using th~s technique, only the fullerene salt precipitates. For example, ~f KCl is used as a source of potassium cat~on, only KC60, not KCl is precipitated. Only traces of chloride ~ons are detectable in the KC60 solid precipitate ~a scanning electron microscopy energy dispersive spectra technique.
WO93/11067 ' ~ PCr/US9:2110120 The following examples are intended to demonstrate the invention and not limit ~t in any way.
EXAMPLES
In all of the following examples, the solvents were dried and ~egassed according to standard methods. A blanket of inert gas prevented the contact of the reaot~on mixture with the atmosphere.
All reactions are carried out at ambient temperature and prl~ssure unless stated otherwise. Mixtures of C60fC70 were obtained by solvent ex~racting the soot produced via the carbon arc synthesis method, as statet ~n D. M. Cox et al., J.l4m. Çhem Soc. 113, 294Q ~19~13. P~re C60 was produced by chromatography from ~ixtures ~f C60 and C70 full erenes, as descri bed in the 1 iterature. See, for exampl e, ~. M.
Cox et al~, ?. Am. Chem. Soc. 113, 2g40 (1991).
Exam,~
A methylene chloride/toluene solution (2~1 v/v~ containin~
0 025 ~ C60 and 0.5 9 (BU4N3~l(pF6)-l was ele~trolyzed at.-0.70 Y YS.
SCE for a time suffioient to reduce C60. Electronic spectroscopy and ESR spectra ~ndiczted the formation of the alkyl ammonium C~o ful~er-~de salt, (BU4N~lc6o~ yclic Yoltommetry and DPP conFirmed ~he presence Of ~60-~-E~Z
The procedure speoified in Example 1 was employed using Cand produced the alkyla~monium c70-1 fulleride salt (BU4N)+lC70^l~ as shown by electrochem~cal and ESR analys~s~
~ample 3 .
A tetrahydrofuran solution containing 0~002 9 60 and 0.30 9 NaBF4 was electrolyzed at -0.7 V vs. SCE for a time sufficient to reduce the C60. ~he properties of the resulting inorganic ful~eride salt Na~lC60-l are similar to those of its BU4N+c6o-l counterpart in WO93/11067 i i r~ ~ 1 9 1 PCl/US92/10120 Example 1 (as determined by electronic and magnetic resonance spec-troscopy).
Example 4 A polar solvent system consisting of a dimethyl sulfoxlde DMS0/toluene solution (6/1 v/v) containing a suspension of 0.1 9 C60 and 0.25 KCl was electrolyzed at -0.45 V vs. SCE for a time sufficient to produce c60-l- The solution ~urned red at the end of the reduc-tion. Add~t~on of toluene (about 5:1 toluene/DMS0) and refrigeration overnlght at -20~C allowed for the removal of most of DMS0 and some toluene as a frozen soltd. Addltion of freshly distilled diethyl ether to the remaining solution resulted in the precipitation of KC60 as a black powder, which was isolated via filtration or decanting the liqu1d~ Electronic and ESR spectra of DMS0 solutions of the solid confirmed the presence of C60-1 in the inorganic K~C60-1 f~lleride salt. Onlytracesofchloride ~ons were detected via scann~ng elec-tron ~lcroscopy energy dispers~Ye speetroscopy, which also confirmed the presence of the K~60 salt.
Ex~mp~
the procedure of Fxample 4 was repeated using KBr instead of KCl to produc~ K~lC60-1 fulleride salt.
. x~mPle 6 -This example illustrates the use of C60 as a solid state electrode component. A toluene solution of C60 was deposited on a glassy carbon electrode. Upon solvent evaporat;on, the electrode was coated with sol~d C60. The coated electrode was immersed in an aceton~tr~le solution containing 0.4 9 BU4NPF6 as the supportina electrolyte. C60 and ~ts anions are not soluble in acetonitrile.
Cycl~c voltametrlc scans revealed the reversible formation of c60-l~
C60-~ C60-3 anions in the solid film. The additions of electrons to C6Q was reversible; the CV scans are similar to those obtained previ-ously by using a solution of C60. A control CV analysis of a -WO 93/11067 P(~/US92tlO120 ' ~ ~lJ~
suspens~on Of C60 in acetonitrile solution conta~ning the same sup-port~ng electrolyte revealed practioally nQ fullerene-an~on ~ormation~
~,.
FIELn OF THE INVENTIQN
The present ~nvention relates to novel salts of fullerenes also known as fulleride salts, their preparation and use.
BACKGRQUND OF_~ I~VENTION
Diamond and graphite are two well known allotropic forl~s of carbon. Another form, the fullerenes, have been prepared by graphite volatilizat~on (See W. Kratschmer et al, Nature, 347, p. 354 (1990)).
Pot~ssium and other metal complexes of fullerenes have been observed ln the gas phase by mass spectrometry (See D. M. Cox et al, J. Chem.
~PhYs. 88(3~, 1588 ~19B8)).
Fullerenes are hollow molecules composed only of carbon ato~s and constltute a new allotropic form of car~on. Typically, f~ renes ~ach have carbon atoms arranged as 12 pentagons, but d~f~er1ng numbers of hex~gons having the formula C2n where n is equal to or greater than 16 (hereinafter UfullerenesN). The pentagons are requlred in order to allow the ourYature and eventual closure of the c~osed surface upon ~tself. The most abundant species of fullerenes ident1f~ed to date ~s the C60 molecule or Buchminsterfullerene (here-~nafter ~C60~). C~o oons~sts of 12 pentagons and 20 hexagons.
Ho~ever9 other species, includ1ng C70 have also been ~dentified.
~MMARY OF ~HE INVENTION
The portion of this invention that relates to C60 fulleride salts was f~rst dlsclosed by appllcants at a seminar in Boston, Massa~husetts on November 29, 1990, and subsequently published in Mat.
Re$. Soc. SvmP. Proc., Vol. 206, p. 659 tl991). This invention provides new composit~ons of matter having the formula AnCX~ wherein C~ is a fullerene anion wherein x is preferably selected from the group consisting Of C60 and C70 and wherein A is a monovalent cation.
WOg3/11067 ~J~ 3 PCr/US~2/10120 Preferred monovalent cations, in accordance with the present inven-tion, include ammonium cations, alkyl ammonium cations such as quater-nary ammunium cations, alkali metal cations, phosphonium and arsonium cations, especially organophosphonium and organoarsonium ions, partic-ularly phenylphosphonium and phenylarsonium cations. The preferred fullerene used ~n the practice of the present invent~on is Cho.
In one embodiment of the present invention, the ~ulleride salt compounds of the present ~nvention are prepared by passing a~
electr1c current through (electrolyzing) a non-aqueous solution of fullerenes ~n the presence of a soluble salt containing a cat~on, A, of the AnCX compound to be formed. The electric potential is applied for ~ t~me sufficient to generate fullerene anions in the solut~on.
In another embod~ment of the present invention, the fulleride salt compounds are prepared ~n the solid state. The ccmpounds of the present ~nvention exhibit reversible electrochem~cal reduction; and, consequently, are partlcularly useful as electrode components in electrochem~cal cells sueh as secondary batteries.
The fullerene anions, C60-Y and C70-Y, wherein y is a charge of from 1 to 3, spec~fically 1, 2, and 3 ~n the compound of the present invant~on contain unpaired electrons and thus have paramag-netic properties. In the case of, for example, c60-l and C6o-2~ these propert~es are con~irmed by electron spin resonance spectroscapy ESR~) ~or the tetralkyl ammonium fulleride salt containing ~he c60-l monoan~on. The magnitude of the magnet~c suscept~b~llty of the compound of the present invention var~es with the temperature accord-lng to the Curie-We~ss law, wh~ch ls known to one hav~ng ordinary sklll ~n the art. Since a one-to-one magnet~c susceptibillty tempera-ture correspondence ex~sts, these compounds may be used as magnetic thermometers. ~:
Sim~larly, fuller~de salts containing c60-l monoan~ons may be used as semiconductors (See P. M. Allemand et al., J. Am. Chem.
Soc~, 113,2780 (1991)) wh~le those containing C60-3 ~nd alkali-metals may be used as superconductors ~See A. F. Hebard et al., Nature 350,600 (199i)).
WO 93/11067 PCr/US92/10120 , ';' ~' '',1 ... ,.~ i -. .1 Alkali salts Of C60 also can serve as starting materials for the preparation of other materials. The reaction of the lithium salt of C60, for example, with alkyl halides yield alkyl derivatives of fullerenes (See J. W. Bausch et al., J. Am. Chem. Soc., 113,320 (1991)) that may-be useful as polymer blends, composites and building bl ~cks .
Further, the AnCX fulleride salts are stable in the absence of a~r and other react~ve molecules. Their free radical charac~er may make them suitable as spin labels. Spin labels are usually organic ~olecules that contain an unpaired electron ~for example, a nitrox~yl rad~cal) and are used to render diamagnetic molecules to which they are attached susceptible to analys~s by magnetic spin re!sonance techniques. ~he AnCX spln labels m~xed, for example with polymers, 0ay allow valuable information concerning polymer dynamics and struc-tures t~ be obtained.
qESCRIPT~ON OF THE PREFERRED EMBDDIMENTS
The present invention encompasses novel compositions of matter ha~ing the formula AnCX~ wherein Cx is a fbllerene anion, whcre~n Cx ls preferably selected from the group consisting of C60 and C70, where1n A is a monovalent cation and wherein n is an integer from 1 to 3 ~nclusive, specifically 1, 2~ and 3. The cation, A, may be selected from a w~de range of cations. The fullerene anion is further selected from the group consist~ng of monovalent, divalent and trt-valent an~ons. Its valence, however, depends on the formula of the monovalent cation, An. Thus, for example where the monovalent catlon, An~ has the formuls (A~ , Cx wlll be a monovalent anion; where An has the formula (A~1)2, Cx w~ll be a divalent anion; for (A+1)3, Cx w~ll be a triYalent anion. Particularly preferred cations for A
~nclude ammonium and alkyl ammon~um cations, organophosphon~um or organoarsonium cations, espec~ally tetraorganophosphonium and tetra-organoarsan~um ions, such as tetraphenylphosphonium and tetraphenyl-arson~um cat~ns, alkali metal cations, and the like. Among the alkali metal cations, L~, Na and K are especially preferred. The WO 93/110~i7 PCl~US9~/10120 -i~ L r:
preferred fullerene used in the practice of the present invention is c6o~
) The starting materials for $he practice of the present invention can be obtained from con~Tercial sources. In addition, ~he fullerenes may be prepared by graphite volatilizatlon ~see W.
Kr~tschmer, et al, Nature, 347, p. 354 ~1990)).
When the compounds of the present inYention are made by electrolyziny a non-aqueous solution containing fullerenes and a soluble salt of a cat~on, A, such as one of the aforementioned ca~-ions, the etectrochem~cal reduotion of fullerenes ~s conducted prefer-ably ~n a low or h~gh polar~ty solvent as required tQ diss~lve the reactants, but wh~ch will be inert to the reaction~ 'INon-aqueous'' as used here~n means solvent systems wherein waterl if present, ~s electrochemically and chem~cally ~nert. Thus, by way of example, tolu~ne, d~chloromethane in the case where the cation, A, îs ~rganic and a h~gh polar~y solvent such as dimethyl sulfoxide when the cation A ~s ~norgan~c. Slngle, b~nary or mult~component mixtures of tetrahy-drofuran, ethylene chlorlde, toluene, xylenes, d~methyl sul:fox~de, d~chloromethane, benzene are part~cularly suitable for dissolving the fullerenes. Add~t~onally, the salt conta~nlng the cat~on, A, of de~red compound, A~CX, must have some solubility in the organic solvent system used. Typically, therefore, salts containing organo groups sueh as7 but not restr~cted to7 R4~Cl, R4AsCl, R4PCl, P(4NPF6, and R4NBF4 are part~cu~arly su~table. In the forego~ng s~lts, R is sel~!cted from the group cons~sting of hydro~en and an organ~c moiety.
lhe organ1c moiety should be chosen in order to render the salt soluble in the solvent system. It is within the skill of one of ordinary sk~ll ln the art to make a selection of the appropriate solvent system. R may, for example, be selected from alkyl groups having from 1 to 16 carbon atoms and phenyl groups. Other useful sa~ts include alkali metal salts haYing anions containing sufficient organic moiet~es to render the salt soluble in the solvent system.
Representat~ve examples include Na8Ph4, K8Ph4 where (~Ph" as used herein means phenyl or substituted phenyl group). When ~norganic salts containing the cation A are used, the solvent system is more wo s3/lto67 .~ s~ ~ 9 1 PCT/uS92/10120 polar. Inorganic salts such as NaBF4, KCl and KBr should be used with m~xtures of tetrahydrofuran, dimethyl sulfoxide, dimethyl formam;de, toluene and the l~ke. The relative ratio o~ components of the solv~nt mixtures should be such as to insure some degree of solubility of both start~ng materials; i.e., fullerenes (which are soluble in relatively non-polar solvents) and inorganic salts (more soluble in polar sol-vents like dimethyl sulfoxide). It is within the skill of a person with average skill in the art to select the optimum mixture of sol-vents suitable for a given inorganic salt containing a desired A
cation. The resultant AnCX fulleride salts need not be soluble in the solvent mixtures used and 1t is preferred that they are not ~f ~sola-tion o~ the sol~d salt is desirable.
A commercially available PAR (Princeton Appl~ed Research) System equlpped with Pt wire auxiliary electrode, standard calomel reference e~ectrode (SCE) and a Pt gauze working electrode may be ~sed to reduce, for example, up to gram quantit~es of the particular fullerene. Other commerclal units ~ay be used to prepare larger qu~nt1t~es of fulleride salts. A potentiostat regulates the potential necess~ry to produce the desired reduction state (salt of anion) of the fullerene in the particular solvent system. The molar rat;o of salt to fullerene used in the solvent system will be generàlly greater than 3:1 and, preferably, wlll be in the range of about 10 to 20. The potent~al ~ay be appl~ed using any known source o~ direct current after ~mmersing the work~ng and reference electrodes into the solvent system. The aux~liary ele~trode may be isolated from the working electrode compartment dur~ng appl~cation of the electric potential, th~ ~ixture may be stirred, but such is not necessary. Typically, the react~on takes place at room temperature and pressure under a blanket of inert gas. Alternatively, an inert gas (for example, N2, Ar) may be bubbled through the solvent mixture. For example, for the produc-tion of C60-l monoanion from C60 a potential of -0.45 V versus SCE in the DMSO solvent system uslng KBr as supporting electrolyte resulted ~n product10n of only the fullerene salts containing C60 monoanion.
Since the potential necessary to produce the anions of desired valence is solvent dependent its value can be determined via cyclic voltam-metry (CV) or d~fferential pulse polarography (DPP). Care must be w ~ 93/11067 ~ 3 I PcT/uss2/l taken in choosîng solvent system, electrolyte, temperature, eleotrode type, etc. to obta~n reversible well separated waves in CV at slow scan speeds. These conditions are necessary for selective production r of the particular fullerene salt and to ensure that once produced they àre not decomposed during the bulk electrolysis. For typical examples of well separated waves in CV and DPP data on C60 and C7~ fullerenes, see S. M. Gorun et. al, Mat. Res. Soc~_~ymD~_Proc. 206, 659 ~1931).
The process of the present inven~ion may be used t~ selec-tively generate the salt of the fullerene anions in solutions of the fullerenes and other hydrocarbons by applying a current to the solu-tion, wherein the current is of sufficiently low voltage to selective-ly reduce the particular fullerene to the correspondent salt off ~he fullerene anion without reducing the other hydrocar60ns. The fuller-ene anions have the formula Cx-Y, wherein Cx iS a fullerene, prefera-bly a fullerene selected from the group cons~sting af C60 and C70 and where~?n y is an integer of from 1 to 3, spec~fically 1, 2 and 3. ~he range of electric potent~als will vary wi?lth the solvent system, but can readily be selected by one havin~ ordinary skttl in the art. ~he electric potentiial is ~rom about zero to about -0.7 V, when the fullerene anion is selected from the group consisting of c60-l (when : the fullerene ~?s C60) and c70-1 when the fullerene is C70; ~t is from about -0.80 Y to about -1.1 V when the fullerene anion is setec~ed ~ro~ the group consist~ng of C6o-2 (when the fullerene is C60) and C70-2 (when the ~ullerene ~s C60) and C70-2 (when the fullerene is G70~; and it is from about -1.3 V to about -1.7 ~ when the fullerene an~on t?s selected from the group consisting of C~o~~ (when the fu~ler-ene ~s C60) and C70-3 ~when the ~ullerene is C7~3. For example, c60-l~ which is prepared from C60 at a potentiial of -0.70 V in 1:2 d~?chloromethane/toluene milxtures, may be selectively prepared as the sa~t of the c60-l an~on ~rom mixtures of C60 w~th other hydrocarbons havin~ hlgher potentials (that is, having a chemical inertness with~n ~he range of potenti?als at which the c60-l anion is produced) by apply~ng the foregoi?ng chemiical potentlals to the solution. The salt of the fullerene anion may be present iin the solution or precipitated therefrom. The actual voltage may vary, depending on the solvent in which the reduct~on is conducted. However, the potential should be . ~i .~ 1 1 3 1 chosen within the range of the electrochemical potential necessary to generate the particular salt of the fullerene anion and within the ranQe of chem~cal inertness for the other hydrocarbons. (For techni-cal deta~ls see, for example, P. T~ Kissinger and Wm. H. Heineman, Editors, ~aborat~ry Techniques in Electrochem;strY, Marcel Decker, Inc., N.Y. (1984~; and A. Bard and L. Faulkner, lectrochemical MethQds, Wiley and Sons, N.Y. (1980)).
During the electrolysis, the progress of the reaction is ~onitored by measuring the amount o~ current that passes through the solut10n. Alternatively, s~nce the fullerene anions are paramagnetic wh~le the start~ng fullerenes are diamagnetic, quantitative ESR
spectroscopy can be used for the same purpose. Similar results are expected for c70-1 monoanion. (See, for example M. A. Greaney et al., . PhYs, Chem. 9~,7142 (1991) for the ESR signatures of the c60-l and c70-1 and D. Dubo1s et al., J. Am. Chem. Soc. 113,4364 (199lJ for C6o~2). For ~60, applicants found that the most convenient method to detect c60-l is the monitoring of the near infrared spectrum of the solut~on. ~ strong absorption band centered at approximately 1065 nm ~s present ~n c60-l~ but mlssing in C60. This band, which is attr1b-uted to the HOMO-LUMO (highest occupied molecular orbital-lowest unoccup1ed molecular orbital) electronic transition of C~o-1 disap-pears upon ox~dat~on of c60-l to C60 and can be regenerated upon furth~r reductlon. Its position and intensity is practically indepen-dènt of the A cation, being observed for both organic (e.g., Bu4N) and 1n~rganic (e.g., K) salts of c60~ n a variety of solvents. As used hereln, ~Bu~ means ~butyl~.
~ The AnCX product ~ay be isolated by precipitat~on; for example, using a non-solvent or precipitatlng agent, such as toluene or ether or by reducing the volume of the solvent used v~a vacuum distillatlon or low temperature freez~ng. Using th~s technique, only the fullerene salt precipitates. For example, ~f KCl is used as a source of potassium cat~on, only KC60, not KCl is precipitated. Only traces of chloride ~ons are detectable in the KC60 solid precipitate ~a scanning electron microscopy energy dispersive spectra technique.
WO93/11067 ' ~ PCr/US9:2110120 The following examples are intended to demonstrate the invention and not limit ~t in any way.
EXAMPLES
In all of the following examples, the solvents were dried and ~egassed according to standard methods. A blanket of inert gas prevented the contact of the reaot~on mixture with the atmosphere.
All reactions are carried out at ambient temperature and prl~ssure unless stated otherwise. Mixtures of C60fC70 were obtained by solvent ex~racting the soot produced via the carbon arc synthesis method, as statet ~n D. M. Cox et al., J.l4m. Çhem Soc. 113, 294Q ~19~13. P~re C60 was produced by chromatography from ~ixtures ~f C60 and C70 full erenes, as descri bed in the 1 iterature. See, for exampl e, ~. M.
Cox et al~, ?. Am. Chem. Soc. 113, 2g40 (1991).
Exam,~
A methylene chloride/toluene solution (2~1 v/v~ containin~
0 025 ~ C60 and 0.5 9 (BU4N3~l(pF6)-l was ele~trolyzed at.-0.70 Y YS.
SCE for a time suffioient to reduce C60. Electronic spectroscopy and ESR spectra ~ndiczted the formation of the alkyl ammonium C~o ful~er-~de salt, (BU4N~lc6o~ yclic Yoltommetry and DPP conFirmed ~he presence Of ~60-~-E~Z
The procedure speoified in Example 1 was employed using Cand produced the alkyla~monium c70-1 fulleride salt (BU4N)+lC70^l~ as shown by electrochem~cal and ESR analys~s~
~ample 3 .
A tetrahydrofuran solution containing 0~002 9 60 and 0.30 9 NaBF4 was electrolyzed at -0.7 V vs. SCE for a time sufficient to reduce the C60. ~he properties of the resulting inorganic ful~eride salt Na~lC60-l are similar to those of its BU4N+c6o-l counterpart in WO93/11067 i i r~ ~ 1 9 1 PCl/US92/10120 Example 1 (as determined by electronic and magnetic resonance spec-troscopy).
Example 4 A polar solvent system consisting of a dimethyl sulfoxlde DMS0/toluene solution (6/1 v/v) containing a suspension of 0.1 9 C60 and 0.25 KCl was electrolyzed at -0.45 V vs. SCE for a time sufficient to produce c60-l- The solution ~urned red at the end of the reduc-tion. Add~t~on of toluene (about 5:1 toluene/DMS0) and refrigeration overnlght at -20~C allowed for the removal of most of DMS0 and some toluene as a frozen soltd. Addltion of freshly distilled diethyl ether to the remaining solution resulted in the precipitation of KC60 as a black powder, which was isolated via filtration or decanting the liqu1d~ Electronic and ESR spectra of DMS0 solutions of the solid confirmed the presence of C60-1 in the inorganic K~C60-1 f~lleride salt. Onlytracesofchloride ~ons were detected via scann~ng elec-tron ~lcroscopy energy dispers~Ye speetroscopy, which also confirmed the presence of the K~60 salt.
Ex~mp~
the procedure of Fxample 4 was repeated using KBr instead of KCl to produc~ K~lC60-1 fulleride salt.
. x~mPle 6 -This example illustrates the use of C60 as a solid state electrode component. A toluene solution of C60 was deposited on a glassy carbon electrode. Upon solvent evaporat;on, the electrode was coated with sol~d C60. The coated electrode was immersed in an aceton~tr~le solution containing 0.4 9 BU4NPF6 as the supportina electrolyte. C60 and ~ts anions are not soluble in acetonitrile.
Cycl~c voltametrlc scans revealed the reversible formation of c60-l~
C60-~ C60-3 anions in the solid film. The additions of electrons to C6Q was reversible; the CV scans are similar to those obtained previ-ously by using a solution of C60. A control CV analysis of a -WO 93/11067 P(~/US92tlO120 ' ~ ~lJ~
suspens~on Of C60 in acetonitrile solution conta~ning the same sup-port~ng electrolyte revealed practioally nQ fullerene-an~on ~ormation~
~,.
Claims (10)
1. A composition of matter having the formula AnCx wherein A is a monovalent cation, wherein Cx is a fullerene anion, selected from the group consisting of C60 and C70, and wherein n is an integer from 1 to 3.
2. The composition of claim 1 wherein the monovalent cation is selected from the group consisting of ammonium, alkyl ammonium, alkali metal cations, organophosphonium and organoarsonium cations
3. The composition of claim 1 wherein the fullerene anion is selected from the group consisting of monovalent, divalent and trivalent anions.
4. A method for preparing a fulleride salt composition comprising:
applying an electrical potential to a non-aqueous solution of a fullerene selected from the group consisting of C60 and C70 and a salt containing a monovalent cation, A, selected from the group con-sisting of ammonium, alkyl ammonium, alkali metal cations, organo-phosphonium and organoarsonium cations, for a time sufficient to prepare a composition having the formula AnCx wherein A is a mono-valent cation, and wherein n is an integer from 1 to 3, and wherein Cx a fullerene anion selected from the group consisting of C60 and C70.
applying an electrical potential to a non-aqueous solution of a fullerene selected from the group consisting of C60 and C70 and a salt containing a monovalent cation, A, selected from the group con-sisting of ammonium, alkyl ammonium, alkali metal cations, organo-phosphonium and organoarsonium cations, for a time sufficient to prepare a composition having the formula AnCx wherein A is a mono-valent cation, and wherein n is an integer from 1 to 3, and wherein Cx a fullerene anion selected from the group consisting of C60 and C70.
5. The method of claim 4 wherein the non-aqueous solution is an organic solvent system.
6. The composition of claim 1 wherein An is selected from the group consisting of Na, K, Bu4N and Ph4P, wherein Bu is butyl and wherein Ph is selected from the group consisting of phenyl and phenyl-substituted groups.
7. A method for selectively generating a soluble salt of fullerenes from a solution of fullerenes and hydrocarbons comprising;
applying an electrical potential to said solution wherein the electri-cal potential is in a range equal to the potential sufficient to reduce the fullerene to the corresponding fullerene anions and wherein the electric potential is within the range of the chemical inertness of the hydrocarbons, for a time sufficient to generate said fullerene anions.
applying an electrical potential to said solution wherein the electri-cal potential is in a range equal to the potential sufficient to reduce the fullerene to the corresponding fullerene anions and wherein the electric potential is within the range of the chemical inertness of the hydrocarbons, for a time sufficient to generate said fullerene anions.
8. The method of claim 6 wherein the electrical potential is from about zero to about -0.7 V, and wherein the fullerene anion is selected from the group consisting of C60-1 when the fullerene is C60 and C70-1 when the fullerene is C70.
9. The method of claim 7 wherein the electrical potential is from about -0.80 V to about -1.1 V, wherein the fullerene anion is selected from the group consisting of C60-2 when the fullerene is C60 and C70-2 when the fullerene is C70.
10. The method of claim 7 wherein the electrochemical potential is from about -1.3 V to about -1.7 Y, and wherein the fullerene anion is selected from the group consisting of C60-3 when the fullerene is C60 and C70-3 when the fullerene is C70.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79839091A | 1991-11-26 | 1991-11-26 | |
| US798,390 | 1991-11-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2124191A1 true CA2124191A1 (en) | 1993-06-10 |
Family
ID=25173281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002124191A Abandoned CA2124191A1 (en) | 1991-11-26 | 1992-11-23 | Novel salts of fullerenes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0614444A4 (en) |
| JP (1) | JPH07501782A (en) |
| AU (1) | AU3223093A (en) |
| CA (1) | CA2124191A1 (en) |
| WO (1) | WO1993011067A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE148079T1 (en) * | 1992-09-16 | 1997-02-15 | Hoechst Ag | METHOD FOR SEPARATING FULLERENES |
| US5811460A (en) | 1994-01-24 | 1998-09-22 | The Regents Of The University Of California | Water soluble fullerenes with antiviral activity |
| EP1199281B1 (en) * | 2000-10-20 | 2005-12-28 | Pirelli & C. S.p.A. | Process for producing a metal fulleride |
| EP2322475A1 (en) | 2009-11-17 | 2011-05-18 | Siemens Aktiengesellschaft | Method of synthesis of a fulleride of metal nano-cluster and material comprising a fulleride of metal nano-cluster |
| CN109053468B (en) * | 2018-07-03 | 2020-12-15 | 苏州大学 | Fullerene ammonium tripropionate derivative, preparation method and application thereof |
-
1992
- 1992-11-23 EP EP93900639A patent/EP0614444A4/en not_active Withdrawn
- 1992-11-23 WO PCT/US1992/010120 patent/WO1993011067A1/en not_active Application Discontinuation
- 1992-11-23 JP JP5510208A patent/JPH07501782A/en active Pending
- 1992-11-23 AU AU32230/93A patent/AU3223093A/en not_active Abandoned
- 1992-11-23 CA CA002124191A patent/CA2124191A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP0614444A1 (en) | 1994-09-14 |
| JPH07501782A (en) | 1995-02-23 |
| AU3223093A (en) | 1993-06-28 |
| EP0614444A4 (en) | 1995-03-15 |
| WO1993011067A1 (en) | 1993-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Damien et al. | Direct deposition of MoSe 2 nanocrystals onto conducting substrates: towards ultra-efficient electrocatalysts for hydrogen evolution | |
| US10260154B2 (en) | Method for the synthesis of layered luminescent transition metal dichalcogenide quantum dots | |
| Fedurco et al. | Electrochemical Synthesis of a Redox‐Active Polymer Based on Buckminsterfullerene Epoxide | |
| Touhara et al. | Discharge reaction mechanism in graphite fluoride-lithium batteries | |
| US20130177820A1 (en) | Silicon-containing compositions, methods of their preparation, and methods of electrolytically depositing silicon on a current carrier for use in lithium ion battery applications | |
| DE10108893A1 (en) | Production of metals and their alloys and compound semiconductors comprises galvanically depositing metals, alloys or compound semiconductors from an ionic liquid or suitable molten salt in an electrolysis device | |
| Behl | Anodic oxidation of lithium bromide in tetrahydrofuran solutions | |
| KR101750279B1 (en) | Electrochemical conversion system of carbon dioxide | |
| CA3125105A1 (en) | Systems and methods for the production of tunable conductive molybdenum disulfide thin films | |
| Hussey et al. | An electrochemical study of the Fe (iii)/Fe (ii) electrode reaction in the aluminum chloride+ N-(n-butyl) pyridinium chloride molten salt system | |
| DE102017223892A1 (en) | Process for the preparation of a functionalized semiconductor or conductor material and its use | |
| CA2124191A1 (en) | Novel salts of fullerenes | |
| Nakayasu et al. | Rapid, one-step fabrication of MoS2 electrocatalysts by hydrothermal electrodeposition | |
| Foss et al. | Transition Metal Chelate‐Fulleride Compounds: Electrocrystallization of Semiconducting [Ru (bpy) 3](C 60) 2 | |
| Shokhen et al. | Electrochemical intercalation of sodium in vertically aligned molybdenum disulfide for hydrogen evolution reaction | |
| Datsenko et al. | Electrochemical Reduction of Pentafluorophenylxenonium,‐diazonium,‐iodonium,‐bromonium, and‐phosphonium Salts | |
| Wang et al. | Electrochemical deposition of magnesium from analogous ionic liquid based on dimethylformamide | |
| Manoharan et al. | Hydrogen Evolution on Sr x NbO3− δ (0.7≤ x≤ 0.95) in Acid | |
| Arakawa et al. | Decomposition of propylene carbonate in a lithium/metal phthalocyanine cell | |
| John et al. | Hydrogen generation from glucose depolarized water electrolysis | |
| Miller et al. | Electrochemical crystallization of tetraphenylphosphonium and tetraphenylarsonium fullerides | |
| WO2022173046A1 (en) | Method for producing carbon material | |
| JP5109118B2 (en) | A depolymerization method of a conductive polymer and a repolymerization method thereof. | |
| JPS61147891A (en) | Electrode activated by heteropolyacid and its production | |
| Takada et al. | The electrochemical formation of graphite Intercalation compound in γ-butyrolactone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19960525 |