CA1332643C - Electronic conductive polymers doped by heteropolyanions, their preparation process and their use in chemical and electrochemical catalysis - Google Patents
Electronic conductive polymers doped by heteropolyanions, their preparation process and their use in chemical and electrochemical catalysisInfo
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- CA1332643C CA1332643C CA000586460A CA586460A CA1332643C CA 1332643 C CA1332643 C CA 1332643C CA 000586460 A CA000586460 A CA 000586460A CA 586460 A CA586460 A CA 586460A CA 1332643 C CA1332643 C CA 1332643C
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- heteropolyacid
- anions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
- C08G2261/312—Non-condensed aromatic systems, e.g. benzene
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
DESCRIPTIVE ABSTRACT
The invention relates to an electronic conductive polymer doped by the anions of a hetero-polyacid of formula:
Hn(XMyVy,Oz) in which n, y, y' and z are such that 2?n?6, 6?y?18, 0?y'?12, 24?z?70 and 6?y+y'?18, X being an element such as P or Si and M is Mo or W.
These polymers can be prepared by chemical or electrochemical oxidation from a solution containing the heteropolyacid and the monomer able to form an electronic conductive polymer by oxidation, e.g.
pyrrole, thiophene, aniline, paraphenylene diamine, acetylene, benzene and their substituted derivatives.
The doped electronic conductive polymer makes it possible to reduce the protons of a solution as is shown by curve (1) of the attached Fig. 2.
(Fig. 2)
The invention relates to an electronic conductive polymer doped by the anions of a hetero-polyacid of formula:
Hn(XMyVy,Oz) in which n, y, y' and z are such that 2?n?6, 6?y?18, 0?y'?12, 24?z?70 and 6?y+y'?18, X being an element such as P or Si and M is Mo or W.
These polymers can be prepared by chemical or electrochemical oxidation from a solution containing the heteropolyacid and the monomer able to form an electronic conductive polymer by oxidation, e.g.
pyrrole, thiophene, aniline, paraphenylene diamine, acetylene, benzene and their substituted derivatives.
The doped electronic conductive polymer makes it possible to reduce the protons of a solution as is shown by curve (1) of the attached Fig. 2.
(Fig. 2)
Description
.
, 1 3 ~643 ELECTRONIC ~ONDUCTIVE POLYMERS DOPED BY
HETEROPOLYANIONS, THEIR PREPARATION
PROCESS AND THEIR USE IN CHEMICAL
AND ELECTROCHEMICAL CATALYSIS
DESCRIPTION
The present invention relates to electronic con-ductive polymers doped by heteropolyanions, their preparation process and their use in chemical and electrochemical catalysis~
More specifically, it relates to the immobili-zation of heteropolyanions within electronic conductive polymers such as polypyrrole, polythiophene, polyaniline, poly-p-phenylene and more generally all conjugate polymers.
The heteropolyanions are used in the form of their acid derivatives, i.e. heteropolyacids in which the anions of each acid retain their structural identity within the complex radical or the molecule form~d.
Among these heteropolyacids, acids of formula Hn(XM12040) are known, in which X isa heteroatom and M is molybdenum or tungsten. These heteropolyacids and the heteropolyanions are known to catalyze a considerable number of reactions mostly carried out in the homogeneous phase. In addition, the use of these heteropolyacids for catalysis leads to considerable difficulties, particularly in connection with the recovery of the catalyst. It is therefore of great interest to be able to immobilize these catalysts in a solid phase in order to facilitate the performance of the reaction.
A known procedure for carrying out this immobillzation consists of immobilizing the hetero-polyacid in polyvinyl-4-pyrrldine, as is described by .~
B 9547.3 MDT ~
~, ~ , . .
. . . -~ . . :
, 1 3 ~643 ELECTRONIC ~ONDUCTIVE POLYMERS DOPED BY
HETEROPOLYANIONS, THEIR PREPARATION
PROCESS AND THEIR USE IN CHEMICAL
AND ELECTROCHEMICAL CATALYSIS
DESCRIPTION
The present invention relates to electronic con-ductive polymers doped by heteropolyanions, their preparation process and their use in chemical and electrochemical catalysis~
More specifically, it relates to the immobili-zation of heteropolyanions within electronic conductive polymers such as polypyrrole, polythiophene, polyaniline, poly-p-phenylene and more generally all conjugate polymers.
The heteropolyanions are used in the form of their acid derivatives, i.e. heteropolyacids in which the anions of each acid retain their structural identity within the complex radical or the molecule form~d.
Among these heteropolyacids, acids of formula Hn(XM12040) are known, in which X isa heteroatom and M is molybdenum or tungsten. These heteropolyacids and the heteropolyanions are known to catalyze a considerable number of reactions mostly carried out in the homogeneous phase. In addition, the use of these heteropolyacids for catalysis leads to considerable difficulties, particularly in connection with the recovery of the catalyst. It is therefore of great interest to be able to immobilize these catalysts in a solid phase in order to facilitate the performance of the reaction.
A known procedure for carrying out this immobillzation consists of immobilizing the hetero-polyacid in polyvinyl-4-pyrrldine, as is described by .~
B 9547.3 MDT ~
~, ~ , . .
. . . -~ . . :
- 2 - 13~3264 3 K. Nomiya et al in Polyhedron, vol.5, no.4, pp.1031-1033, 1986.
Another immobilization method described in French patent FR-A-2 573 779 consists of depositing these heteropolyacids and the corresponding anions on a conductive surface, e.g. on a graphite or vitreous carbon electrode, with a view to activating the electrode and using it in an electrolytic cell for hydrogen production. The latter method does not make it possible to include the heteropolyacid in the mass of the electrode and thus limits the effect obtained as a result of the addition of the heteropolyanion.
However, the first method does permit this y immobilization in the mass of a support, but the poly-vinyl pyrridine support is not electricity conducting, which constitutes a disa~vantage for the catalysis of redox reactions, where it is important to be able to pass the electrons and protons within the support up to the reaction site.
The present invention specifically relates to the immobilization of heteropolyacids or their anions in the mass of a solid conductive phase, which makes it possible to obtain a greater catalytic effect than in the case of the aforementioned materials.
The material of the present invention is an electronic conductive polymer having a polymer matrix doped by anions, said anions incorporating those of at least one heteropolyacid of formula:
Hn~XMyVy~Oz) in which n is a number between 2 and 6, X is an element chosen from the group constituted by H, Cu, Be, Zn, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and rare earths, B 9547.3 MDT
' ' ' ~ '~
:
. ~ .
-.
, .
. . , . ~ . :
Another immobilization method described in French patent FR-A-2 573 779 consists of depositing these heteropolyacids and the corresponding anions on a conductive surface, e.g. on a graphite or vitreous carbon electrode, with a view to activating the electrode and using it in an electrolytic cell for hydrogen production. The latter method does not make it possible to include the heteropolyacid in the mass of the electrode and thus limits the effect obtained as a result of the addition of the heteropolyanion.
However, the first method does permit this y immobilization in the mass of a support, but the poly-vinyl pyrridine support is not electricity conducting, which constitutes a disa~vantage for the catalysis of redox reactions, where it is important to be able to pass the electrons and protons within the support up to the reaction site.
The present invention specifically relates to the immobilization of heteropolyacids or their anions in the mass of a solid conductive phase, which makes it possible to obtain a greater catalytic effect than in the case of the aforementioned materials.
The material of the present invention is an electronic conductive polymer having a polymer matrix doped by anions, said anions incorporating those of at least one heteropolyacid of formula:
Hn~XMyVy~Oz) in which n is a number between 2 and 6, X is an element chosen from the group constituted by H, Cu, Be, Zn, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and rare earths, B 9547.3 MDT
' ' ' ~ '~
:
. ~ .
-.
, .
. . , . ~ . :
3 133~643 M is Mo or W, y is a number between 6 and 18, y' is a number between 0 and 12, with y+y' ranging between 6 and 18, and Z is a number from 24 to 70.
The heteropolyacids in which M is molybdenum or tungsten and y' is equal to 0 are known compounds and which are in particular described by G.A.Tsigdinos in "Heteropolycompounds of Molybdenum and Tungsten", Topics in Current Chemistry, 76, Springer-Verlag, Berlin, New York, Heidelberg, 1978.
In these heteropolyacids, the molybdenum or tungsten can be partly replaced by vanadium and in this case y' is a number from 0 to 12. The most widely used heteropolyacids are those in which y'=0 and y=12.
Examples of such polyacids are silicotungstic acid H4(SiW12040), phosphotungstic acid H3(PW12040), phosphomolybdic acid (H3(PMol2040), silicomolybdic acid H4(5iMol2040), borotungstic acid, germanotungstic acid, phosphomolybdic acid and germanomolybdic acid.
It is also possible to use other heteropolyacids, e.g. those in which y=18 and y'=0, such as phospho-tungstic acid H6(P2~18062) and phosphomolybdic acid H6(P2Mol8062).
In the heteropolyacids used in the invention, X
can represent one of the elements of groups I to VII of the periodic classification of elements in the following oxidation states:
Periodic Group Elements I Cu2+, H
II Be+2, Zn+2 III B+3, A~3, 6a+3 IV Si+4, Ge+4, Sn+4, Ti+4, Zr+4, Th+4, Hf+4, Ce+3, Ce+4 and the other rare earths.
V N+5, P+3, P+5, As+3, As+5, V+4, Y+5, Sb+3, Sb+5~, Bi+3 !
B 9547.3 MDT
.. . .. . .
. . , . ~
; ., ~ .
., *~
The heteropolyacids in which M is molybdenum or tungsten and y' is equal to 0 are known compounds and which are in particular described by G.A.Tsigdinos in "Heteropolycompounds of Molybdenum and Tungsten", Topics in Current Chemistry, 76, Springer-Verlag, Berlin, New York, Heidelberg, 1978.
In these heteropolyacids, the molybdenum or tungsten can be partly replaced by vanadium and in this case y' is a number from 0 to 12. The most widely used heteropolyacids are those in which y'=0 and y=12.
Examples of such polyacids are silicotungstic acid H4(SiW12040), phosphotungstic acid H3(PW12040), phosphomolybdic acid (H3(PMol2040), silicomolybdic acid H4(5iMol2040), borotungstic acid, germanotungstic acid, phosphomolybdic acid and germanomolybdic acid.
It is also possible to use other heteropolyacids, e.g. those in which y=18 and y'=0, such as phospho-tungstic acid H6(P2~18062) and phosphomolybdic acid H6(P2Mol8062).
In the heteropolyacids used in the invention, X
can represent one of the elements of groups I to VII of the periodic classification of elements in the following oxidation states:
Periodic Group Elements I Cu2+, H
II Be+2, Zn+2 III B+3, A~3, 6a+3 IV Si+4, Ge+4, Sn+4, Ti+4, Zr+4, Th+4, Hf+4, Ce+3, Ce+4 and the other rare earths.
V N+5, P+3, P+5, As+3, As+5, V+4, Y+5, Sb+3, Sb+5~, Bi+3 !
B 9547.3 MDT
.. . .. . .
. . , . ~
; ., ~ .
., *~
4 1 3;~2~43 VI Cr+3, S~4, Te~4, Te+6 VII Mn+2, Mn+4, 1~7 YIII Fe~3, Co+2, Co+3, Ni+2, Ni+4, Rh~3, Pt+4.
S ~ The existence of these oxidation states is not certain).
Generally in the invention, use is made of hetero-polyacids in which X represents P or Si.
The electronic conductive polymers usable according to the invention are conjugate polymers.
Such polymers can e.g. be obtained from pyrrole, thiophene, aniline, paraphenylenediamine, acetylene, benzene and their substituted derivatives. It is also possible to use within the invention nitrogenous electronic conductive polymers described in French patent FR-A-2 588 007 pub~hedon03-~-l987andnitrogenous electronic conductive polymers containing sulphur described in french patent FR-A-2 591 605 published on 19-06-1987.
The use within the invention of a solid phase constituted by an electronic conductive polymer makes it possible to obtain a fixation of the anion of the heteropolyacid in the mass of the polymer and in this way to obtain a better catalytic effect than in the case of the deposition on a conductive surface or the immobilization in a non-conductive polymer> such as polyvinyl-4- pyridine.
Therefore, the electronic conductive polymers according to the invention and which are doped by anions of heteropolyacids can have numerous different appli-catlons. Thus, they can be used as an activated electrode for electrochemical reduction and particularly as a chemical or electrochemical catalyst, particularly in the following fields:
B 9547.3 MDT
.
.. ~ .
... - :, ., ~ ~ - - ;
S ~ The existence of these oxidation states is not certain).
Generally in the invention, use is made of hetero-polyacids in which X represents P or Si.
The electronic conductive polymers usable according to the invention are conjugate polymers.
Such polymers can e.g. be obtained from pyrrole, thiophene, aniline, paraphenylenediamine, acetylene, benzene and their substituted derivatives. It is also possible to use within the invention nitrogenous electronic conductive polymers described in French patent FR-A-2 588 007 pub~hedon03-~-l987andnitrogenous electronic conductive polymers containing sulphur described in french patent FR-A-2 591 605 published on 19-06-1987.
The use within the invention of a solid phase constituted by an electronic conductive polymer makes it possible to obtain a fixation of the anion of the heteropolyacid in the mass of the polymer and in this way to obtain a better catalytic effect than in the case of the deposition on a conductive surface or the immobilization in a non-conductive polymer> such as polyvinyl-4- pyridine.
Therefore, the electronic conductive polymers according to the invention and which are doped by anions of heteropolyacids can have numerous different appli-catlons. Thus, they can be used as an activated electrode for electrochemical reduction and particularly as a chemical or electrochemical catalyst, particularly in the following fields:
B 9547.3 MDT
.
.. ~ .
... - :, ., ~ ~ - - ;
Electrolysis of water in an acid medium.
Oxidation of alcohols in an acid medium.
Oxidation of cyclohexanol in cyclohexanone and adipic acid.
Oxidation of diols in diacids.
Oxidation of methacrolein in methacrylic acid.
Synthesis of methyl formate by the electro-catalytic oxidation of methanol Anode and cathode for fuel cells in ~n acid medium.
Oxidation o~ carbon monoxide and reduction of nitrogen oxide.
Catalysts for the purification of exhaust gases of internal combustion engines.
Hydrodesulphurization of hydrocarbons.
Oxidation of benzene in phenol.
Preparation of saturated carbonyl compounds.
Dehydration of alcohols in olefins.
Hydration of propene.
~onversion of methanol into hydrocarbon.
Activation and photochemical functionalization of alkanes.
Friedel-Crafts catalyst.
~atalyst for the polymerization of benzyl alcohols.
Photoelectrochemical photosensiti7er for the photooxidation of organic substrates, including alcohols, ethers, amides, etc. and more generally photo-electrochemical dehydrogenation.
Dehydrogenating oxidation of isobutyric acid.
Epoxidation of olefins.
Proton conductors for electrolyzer membranes or fuel cells.
The electronic conductive polymers according to the invention doped by anions of heteropolyacids can be prepared by a process comprising:
8 9547.3 MDTI
..i~,, ~. .. .. -~ ... .. . .
. ~ .
. " . , 1) ~irstly preparing a solution containing on the one hand a monomer able to form the polymer matrix by oxidation and on the other a heteropolyacid of formula:
Hn(XMyVy~Oz) in which n is a number between 2 and 6, X is an element chosen from within the group constituted by H, Cu, Be, Zn, B, A~, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, fe, Co, Ni, Rh, Pt and rare earths, M is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70 and 2) forming a polymer doped by the anions of the heteropolyacid from said solution by chemical or electrochemical oxidation.
When it is wished to carry out the oxidation of the monomer electrochemically, it is possible to use an aqueous or organic solution and to make use of the heteropolyacid as the electrolyte. The oxidation of the monomer is carried out by applying a potential difference between two electrodes immersed in the solution. This makes it possible to directly form on one of the electrodes an electronic conductive polymer deposit doped by the anions of the heteropolyacid.
This electrochemical oxidation can be carried out under the condition normally used for the preparation of electronic conductive polymers by the electrochemical oxidation of the corresponding monomers, e.g. using the conditions described in FR-A-2 545 494 and FR-A-2 588 007.
The electrodes used for the deposition of the electronic conductive polymer doped by the anions of the heteropolyacid can be made from platinum, nickel, Monel (nickel - copper alloy), carbon or a material coated with carbon, e.g. stainless steel coated with B 95~7.3 MDT
. . . . ~ ~: ::
- 1 3`~2643 a graphite-containing paint.
The current densities used for carrying out the electrochemical oxidation are more particularly dependent on the monomer to be oxidized and can vary between 0.01 and 200 mAtcm .
This electrochemical oxidation makes it possible to obtain doped electronic conductive polymers in which the anion quantity is relatively high and is e.g.
between 0.01 and 0.3 anion per monomer unit of the polymer.
Thus, at the end of the operation, an electrode is obtained on which is deposited the electronic con-ductive polymer doped by the anions of the heteropoly-acid and said electrode can be used as such for chemical or electrochemical catalysis.
However, in certain cases, it is preferable to subject it to a complementary activation treatment by chemical or electrochemical reduction, particularly when it is intended for the production of hydrogen by the electrolysis of water. This activation treatment can consist of applying a cathode potential of -0.2 to -5 volts for 0.1 to 500 min.
It is also possible to prepare the electronic con-ductive polymers according to the invention doped by anions of the heteropolyacid by carrying out the oxidation of the monomer chemically.
In this case, it is possible to use a conventional oxidizing agent, e.g. potassium dichromate, potassium permanganate, hydrogen peroxide or other peroxides, osmium tetroxide and ammonium persulphate. However, the use of these oxidizing agents may lead to an inadequate doping of the electronic conductive polymer by the heteropolyacid anions.
Furthermore, when oxidizing by the chemical route, preference is given to the use as the oxidizing agent B 9547.3 MDT
~.
'-'':"~' .
. .
.``" `' ' .
.
1 33~643 of either the heteropolyacid if it can fulfll the function of the oxidant, as in the case of H3(PI~10~2W40), or an oxidizing cation able to form a salt with the heteropolyacid. In the latter case, firstly a salt of the heteropolyacid is prepared with the oxidizing cation and this can in particular be constituted by iron or cerium ions.
In this chemical oxidation method, it is possible to use an organic or aqueous solution, as hereinbefore.
Examplesof usable organic solvents are acetonitrile, alcohols, including ethyl alcohol, ethylene carbonate or propyle~e carbonate, nitrobenzene, etc. At the end of the operation, the doped conductive polymer is recovered in the form of a precipitate, which can be separated from the solution by filtration. This polymer can be used directly or can be activated by chemical reduction, e.g. using alkaline metals or electrochemically by reduction at -2 volts (ECS) for 2 hours in acetonitrile (0.5M HC~04). For the chemical reductions, the polymer doped by the hetero-polyanions is stirred for 1 hour with sodium in wire form within tetrahydrofuran.
It is also possible to subject the doped conductive polymer to different treatments, which are a function of the application used. This treatment can consist of washing with a Soxhlet extract or using water and acetonitrile, or drying under v~cuum at temperatures up to e.g. 300O. It is also possible to compact the polymer with various additives, such as carbon or poly-tetrafluoroethylene, or to frit ~t with variousadditives. It is also possible to produce various composites with conventional polymers or ionic con-ductive polymers, such as Nafion*.
Other features and advantages of the invention can be gathered from the description provided in a non-* tra ~ mark . .
:
.;, ' : , ~
---" 1 33~643 limitative, illustrative manner hereinbefore of examples with reference to the attached drawings, wherein:
- Figs. 1 to 3 are cyclic voltametry curves obtained with electronic conductive polymers doped by anions of hetero-polyacids in accordance with the invention.
EXA~lPLE 1: Electrochemical Preparation of Polyaniline Doped by the Anions of Tungstosilicic Acid H4(5iW1240) Firstly a 0.1 mole/~ solution of tungstosilicic acid H4(SiW12040) and 0.02 mole/~ of aniline in aceto-nitrile is prepared. This solution is introduced into a 10 cm3 cell having an arrangement with three electrodes, including a diameter 2 mm vitreous carbon working electrode, an auxiliary platinum electrode and an Ag/Ag+ reference electrode, together with a potentiostat. The working electrode is raised to a potential of 0.85V and 20 mC passes into the circuit.
Under these conditions, on the working electrode is formed a deposit of polyaniline doped by the anion of tungstosilicic acid. The electrode is then washed with acetonitrile and its behaviour is studied in cyclic voltametry in a 0.5 mole/l perchloric acid aceto-nitrile solution at a scan rate of 20 mV/s.
The results obtained are given in Fig. 1 showing the cyclic voltametry curve relative to said electrode.
It can be seen that in the range of positive potentials, there is an important redox exchange, which is characteristic of polyaniline and in the range of negative potentials, there are two reversible transfers, .
which are characteristic of tungstosilicic acid.
However, although the medium is very acid, there is no B 9547.3 MDT
~..
. ~ :
, . ~
.
- lo- 1332643 reduction of protons in the negative range due to the high overvoltage of the protons on the vitreous carbon of the electrode and the difficulty which the latter may have in diffusing into the polymer, whilst there is a considerable release of hydrogen as from slightly negative potentials with a platinum electrode only having a small overvoltage at the discharge of the hydrogen.
Moreover, to obtain a reduction current of the protons with the electrode according to the invention, it is necessary to activate the same. This is carried out by applying a cathode potential of -2V for 2h to the electrode immersed in the 0.5 mole/l perchloric acid acetonitrile solution. Following this treatment~ a study takes place to the behaviour of the electrode by cyclic voltametry under the same con-ditions as hereinbefore.
fig. 2 shows cyclic voltametry curves obtained with said electrode (curve 1), as well as with the vitreous carbon electrode coated with polyaniline doped by the anions of the tungstosilicic acid, but not activated (curve 2) and with a bare vitreous carbon electrode (curve 3).
Thus, in Fig. 2, curve 1 represents the reduction of protons on the electrode following its activation at -2V for 2 hours. Curve 2 shows the reduction curve of the protons on the electrode modifled by the deposition of polyaniline doped by the tungstosilicic acid anion.
Curve 3 represents the intensity - potential curve of the reduction of the protons (HC~04) in the acetonitrile on a vitreous carbon electrode. In curve 3, there is seen to be high overvoltage at the reduction sf the protons, whereas in the case of curve 2, there is a catalytic effect on the reduction of the protons. In the case of curve 1, a reduction of the protons is obtained virtually as easily with the activated electrode B 9547.3 MDT
.. , .. -. :
... . . . . .
.. .
: . . :
. .
, . - . . .. -' ' ' ' . ' : ! ' . . . .
as with a platinum electrode.
~hus, the activated electrode according to the invention has an electrochemical behaviour similar to that of platinum with, in addition, a volume characteristic of the transport modes, which makes it very advantageous because it is made from an inexpensive material, such as carbon. Thus, said electrode can be used for the electrolysis of water, as the anode or as the cathode in neutral and acid media, because the conductive polymer may undergo deterioration in a basic medium.
This electrode can also be used in fuel cells, both as a positive electrode and as a negative electrode.
For the oxygen electrode, it would be advantageous to use a polyaniline-based electrode, which already has a satisfactory behaviour for the catalysis of the oxygen reduction. The fuel can advantageously be constituted by alcohols, e.g. methanol in an acid medium.
This electrode can also be used on a porous material such as carbon, or on a pulverulent material such as acetylene black, for a fluidized or stationary bed system.
The polyaniline doped by the anions of the tungsto-silicic acid obtained in this example consequently has numerous uses.
EXAMPLE 2: Electrochemical Preparation of Poly- -(N-methylpyrrole) Doped by the Anions of L
Molybdophosphoric (V) Acid: H3(P+~Mol2040).
The procedure of example I is adopted, but using 10 cm3 of acetonitrile containing 0.1 mole/l of molybdo-phosphoric acid (V): H3(P+5Mol2040) and 0.05 mole/l of B 9547.3 MDT
''. ' :
.,,, ~ . .
- `~
- 12 - 133?643 N-methylpyrrole and 10 mC is passed into the circuit.
Following this operation, the electrode is washed in acetonitrile and its electrochemical behaviour is studied during a cyclic voltametry scan in an aceto-nitrile solution containing 0.1 mole/l of LiClO4.
Fig. 3 shows the cyclic voltametry curve obtained at 50 mV/s. In the positive range, it is possible to see the anode peak and the cathode peak characteristic of the redox behaviour of poly-(N-methylpyrrole). In the negative range there are three reversible peaks, which are characteristic of molybdophosphoric acid.
This electrode can be used as it is, or can be activated by bringing it to a negative potential of -1 to -2 V for 120 min in an acid solution. It can be used for catalyzing all the reaction types described hereinbefore.
EXA~PLE 3: Chemical Preparation of Polypyrrole Doped by the Anions of Tungstophosphoric Acid:
H4(SiW1240) A solution of 10 cm3 of acetonitrile containing 200 mg of pyrrole is prepared and to it is added, at ambient temperature, 5.8 9 of iron tungstosilicate:
Fe4(SiW12040) for oxidizing all the pyrrole by the exchange of 2.5 electrons per pyrrole unit. The product obtained is filtered, washed with acetonitrile and dried under vacuum. This leads to polypyrrole doped by 33~ tungstosilicic anions with a polymerization reaction yield of 81%.
The doping anion from the tungstosilicic acid remains remarkably immobilized within the polypyrrole due to its large size. Thus, if an attempt is made to exchange it by perchlorate anions by immerslng the product in a perchloric acid solution in acetonitrile for several days, the weight loss observed only ;
B 9547.3 MDT ;~
: .:
... . , , ~;, .. . . .
.
- .- . . ~ . . : ~ ~, .. .. .. ~ .. :
, - . .
-' 1 33~643 corresponds to a 10~ exchange of the heteropolyacid anion.
The infrared spectra by Fourier transform and percentage analysis confirm a polypyrrole structure doped by the anion of acid H4(SiW1204o).
This material can be used as a chemical or electrochemical catalyst, in the vapour phase or in the prese~,ce of an aqueous or organic solution, without ha~ing been ~ctivated or after activation by chemical Qr electrochemical reduction.
EXAMPLE 4: Chemical Preparation of Polypyrrole Doped by the Anions of Molybdophosphoric Ac_d (V):
H3(P5+Mol2040).
The starting product is a solution constituted by 10 cm3 of acetonitrile containing 200 mg of pyrrole to which are added 10 9 of molybdophosphoric acid (V):
H3(P5+Mol2040), which is sufficiently oxidizing to oxidize the pyrrole into polypyrrole.
The mixture is stirred for 1 hour under nitrogen, it is then filtered and the filtered product is then washed abundantly with acetonitrile. In this way 80 mg - ` i of polypyrrole doped by the anions of molybdophosphoric acid (V): H3(P5+Mol2040) are recovered.
This material can be used as a chemical or electro-chemical catalyst, in the vapour phase or in the presence of an aqueous or organic solution, without supplementary activation or after activation by chemical or electrochemical reduction.
EXAMPLE S: Use of a Yitreous Carbon Electrode Covered with Polydniline Doped by the Anions of Tungstosilicic Acid for the Electrolysis of_Water.
As in example 1, a 10 cm2 vitreou~ carbon electrode B 9547.3 MDT
~ 15 ~643 is prepared covered with polyaniline doped by the anions of tungstosilicic acid H4(SiW12040) and it is subjected to the activation treatment used in example 1 for obtaining curve 1 of Fig. 2. This electrode is then used for the electrolysis of water in an acid medium with a current density of I to 100 mA/cm2 for several hours, the electrode voltage between the cathode and anode being approximately 2Y.
B 9547.3 MDT
. i .. . .
,, . ,,, ! :
~ , . . . ' ' , , ' '. ~ ' :
.,' . ? . ' - . : .
Oxidation of alcohols in an acid medium.
Oxidation of cyclohexanol in cyclohexanone and adipic acid.
Oxidation of diols in diacids.
Oxidation of methacrolein in methacrylic acid.
Synthesis of methyl formate by the electro-catalytic oxidation of methanol Anode and cathode for fuel cells in ~n acid medium.
Oxidation o~ carbon monoxide and reduction of nitrogen oxide.
Catalysts for the purification of exhaust gases of internal combustion engines.
Hydrodesulphurization of hydrocarbons.
Oxidation of benzene in phenol.
Preparation of saturated carbonyl compounds.
Dehydration of alcohols in olefins.
Hydration of propene.
~onversion of methanol into hydrocarbon.
Activation and photochemical functionalization of alkanes.
Friedel-Crafts catalyst.
~atalyst for the polymerization of benzyl alcohols.
Photoelectrochemical photosensiti7er for the photooxidation of organic substrates, including alcohols, ethers, amides, etc. and more generally photo-electrochemical dehydrogenation.
Dehydrogenating oxidation of isobutyric acid.
Epoxidation of olefins.
Proton conductors for electrolyzer membranes or fuel cells.
The electronic conductive polymers according to the invention doped by anions of heteropolyacids can be prepared by a process comprising:
8 9547.3 MDTI
..i~,, ~. .. .. -~ ... .. . .
. ~ .
. " . , 1) ~irstly preparing a solution containing on the one hand a monomer able to form the polymer matrix by oxidation and on the other a heteropolyacid of formula:
Hn(XMyVy~Oz) in which n is a number between 2 and 6, X is an element chosen from within the group constituted by H, Cu, Be, Zn, B, A~, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, fe, Co, Ni, Rh, Pt and rare earths, M is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70 and 2) forming a polymer doped by the anions of the heteropolyacid from said solution by chemical or electrochemical oxidation.
When it is wished to carry out the oxidation of the monomer electrochemically, it is possible to use an aqueous or organic solution and to make use of the heteropolyacid as the electrolyte. The oxidation of the monomer is carried out by applying a potential difference between two electrodes immersed in the solution. This makes it possible to directly form on one of the electrodes an electronic conductive polymer deposit doped by the anions of the heteropolyacid.
This electrochemical oxidation can be carried out under the condition normally used for the preparation of electronic conductive polymers by the electrochemical oxidation of the corresponding monomers, e.g. using the conditions described in FR-A-2 545 494 and FR-A-2 588 007.
The electrodes used for the deposition of the electronic conductive polymer doped by the anions of the heteropolyacid can be made from platinum, nickel, Monel (nickel - copper alloy), carbon or a material coated with carbon, e.g. stainless steel coated with B 95~7.3 MDT
. . . . ~ ~: ::
- 1 3`~2643 a graphite-containing paint.
The current densities used for carrying out the electrochemical oxidation are more particularly dependent on the monomer to be oxidized and can vary between 0.01 and 200 mAtcm .
This electrochemical oxidation makes it possible to obtain doped electronic conductive polymers in which the anion quantity is relatively high and is e.g.
between 0.01 and 0.3 anion per monomer unit of the polymer.
Thus, at the end of the operation, an electrode is obtained on which is deposited the electronic con-ductive polymer doped by the anions of the heteropoly-acid and said electrode can be used as such for chemical or electrochemical catalysis.
However, in certain cases, it is preferable to subject it to a complementary activation treatment by chemical or electrochemical reduction, particularly when it is intended for the production of hydrogen by the electrolysis of water. This activation treatment can consist of applying a cathode potential of -0.2 to -5 volts for 0.1 to 500 min.
It is also possible to prepare the electronic con-ductive polymers according to the invention doped by anions of the heteropolyacid by carrying out the oxidation of the monomer chemically.
In this case, it is possible to use a conventional oxidizing agent, e.g. potassium dichromate, potassium permanganate, hydrogen peroxide or other peroxides, osmium tetroxide and ammonium persulphate. However, the use of these oxidizing agents may lead to an inadequate doping of the electronic conductive polymer by the heteropolyacid anions.
Furthermore, when oxidizing by the chemical route, preference is given to the use as the oxidizing agent B 9547.3 MDT
~.
'-'':"~' .
. .
.``" `' ' .
.
1 33~643 of either the heteropolyacid if it can fulfll the function of the oxidant, as in the case of H3(PI~10~2W40), or an oxidizing cation able to form a salt with the heteropolyacid. In the latter case, firstly a salt of the heteropolyacid is prepared with the oxidizing cation and this can in particular be constituted by iron or cerium ions.
In this chemical oxidation method, it is possible to use an organic or aqueous solution, as hereinbefore.
Examplesof usable organic solvents are acetonitrile, alcohols, including ethyl alcohol, ethylene carbonate or propyle~e carbonate, nitrobenzene, etc. At the end of the operation, the doped conductive polymer is recovered in the form of a precipitate, which can be separated from the solution by filtration. This polymer can be used directly or can be activated by chemical reduction, e.g. using alkaline metals or electrochemically by reduction at -2 volts (ECS) for 2 hours in acetonitrile (0.5M HC~04). For the chemical reductions, the polymer doped by the hetero-polyanions is stirred for 1 hour with sodium in wire form within tetrahydrofuran.
It is also possible to subject the doped conductive polymer to different treatments, which are a function of the application used. This treatment can consist of washing with a Soxhlet extract or using water and acetonitrile, or drying under v~cuum at temperatures up to e.g. 300O. It is also possible to compact the polymer with various additives, such as carbon or poly-tetrafluoroethylene, or to frit ~t with variousadditives. It is also possible to produce various composites with conventional polymers or ionic con-ductive polymers, such as Nafion*.
Other features and advantages of the invention can be gathered from the description provided in a non-* tra ~ mark . .
:
.;, ' : , ~
---" 1 33~643 limitative, illustrative manner hereinbefore of examples with reference to the attached drawings, wherein:
- Figs. 1 to 3 are cyclic voltametry curves obtained with electronic conductive polymers doped by anions of hetero-polyacids in accordance with the invention.
EXA~lPLE 1: Electrochemical Preparation of Polyaniline Doped by the Anions of Tungstosilicic Acid H4(5iW1240) Firstly a 0.1 mole/~ solution of tungstosilicic acid H4(SiW12040) and 0.02 mole/~ of aniline in aceto-nitrile is prepared. This solution is introduced into a 10 cm3 cell having an arrangement with three electrodes, including a diameter 2 mm vitreous carbon working electrode, an auxiliary platinum electrode and an Ag/Ag+ reference electrode, together with a potentiostat. The working electrode is raised to a potential of 0.85V and 20 mC passes into the circuit.
Under these conditions, on the working electrode is formed a deposit of polyaniline doped by the anion of tungstosilicic acid. The electrode is then washed with acetonitrile and its behaviour is studied in cyclic voltametry in a 0.5 mole/l perchloric acid aceto-nitrile solution at a scan rate of 20 mV/s.
The results obtained are given in Fig. 1 showing the cyclic voltametry curve relative to said electrode.
It can be seen that in the range of positive potentials, there is an important redox exchange, which is characteristic of polyaniline and in the range of negative potentials, there are two reversible transfers, .
which are characteristic of tungstosilicic acid.
However, although the medium is very acid, there is no B 9547.3 MDT
~..
. ~ :
, . ~
.
- lo- 1332643 reduction of protons in the negative range due to the high overvoltage of the protons on the vitreous carbon of the electrode and the difficulty which the latter may have in diffusing into the polymer, whilst there is a considerable release of hydrogen as from slightly negative potentials with a platinum electrode only having a small overvoltage at the discharge of the hydrogen.
Moreover, to obtain a reduction current of the protons with the electrode according to the invention, it is necessary to activate the same. This is carried out by applying a cathode potential of -2V for 2h to the electrode immersed in the 0.5 mole/l perchloric acid acetonitrile solution. Following this treatment~ a study takes place to the behaviour of the electrode by cyclic voltametry under the same con-ditions as hereinbefore.
fig. 2 shows cyclic voltametry curves obtained with said electrode (curve 1), as well as with the vitreous carbon electrode coated with polyaniline doped by the anions of the tungstosilicic acid, but not activated (curve 2) and with a bare vitreous carbon electrode (curve 3).
Thus, in Fig. 2, curve 1 represents the reduction of protons on the electrode following its activation at -2V for 2 hours. Curve 2 shows the reduction curve of the protons on the electrode modifled by the deposition of polyaniline doped by the tungstosilicic acid anion.
Curve 3 represents the intensity - potential curve of the reduction of the protons (HC~04) in the acetonitrile on a vitreous carbon electrode. In curve 3, there is seen to be high overvoltage at the reduction sf the protons, whereas in the case of curve 2, there is a catalytic effect on the reduction of the protons. In the case of curve 1, a reduction of the protons is obtained virtually as easily with the activated electrode B 9547.3 MDT
.. , .. -. :
... . . . . .
.. .
: . . :
. .
, . - . . .. -' ' ' ' . ' : ! ' . . . .
as with a platinum electrode.
~hus, the activated electrode according to the invention has an electrochemical behaviour similar to that of platinum with, in addition, a volume characteristic of the transport modes, which makes it very advantageous because it is made from an inexpensive material, such as carbon. Thus, said electrode can be used for the electrolysis of water, as the anode or as the cathode in neutral and acid media, because the conductive polymer may undergo deterioration in a basic medium.
This electrode can also be used in fuel cells, both as a positive electrode and as a negative electrode.
For the oxygen electrode, it would be advantageous to use a polyaniline-based electrode, which already has a satisfactory behaviour for the catalysis of the oxygen reduction. The fuel can advantageously be constituted by alcohols, e.g. methanol in an acid medium.
This electrode can also be used on a porous material such as carbon, or on a pulverulent material such as acetylene black, for a fluidized or stationary bed system.
The polyaniline doped by the anions of the tungsto-silicic acid obtained in this example consequently has numerous uses.
EXAMPLE 2: Electrochemical Preparation of Poly- -(N-methylpyrrole) Doped by the Anions of L
Molybdophosphoric (V) Acid: H3(P+~Mol2040).
The procedure of example I is adopted, but using 10 cm3 of acetonitrile containing 0.1 mole/l of molybdo-phosphoric acid (V): H3(P+5Mol2040) and 0.05 mole/l of B 9547.3 MDT
''. ' :
.,,, ~ . .
- `~
- 12 - 133?643 N-methylpyrrole and 10 mC is passed into the circuit.
Following this operation, the electrode is washed in acetonitrile and its electrochemical behaviour is studied during a cyclic voltametry scan in an aceto-nitrile solution containing 0.1 mole/l of LiClO4.
Fig. 3 shows the cyclic voltametry curve obtained at 50 mV/s. In the positive range, it is possible to see the anode peak and the cathode peak characteristic of the redox behaviour of poly-(N-methylpyrrole). In the negative range there are three reversible peaks, which are characteristic of molybdophosphoric acid.
This electrode can be used as it is, or can be activated by bringing it to a negative potential of -1 to -2 V for 120 min in an acid solution. It can be used for catalyzing all the reaction types described hereinbefore.
EXA~PLE 3: Chemical Preparation of Polypyrrole Doped by the Anions of Tungstophosphoric Acid:
H4(SiW1240) A solution of 10 cm3 of acetonitrile containing 200 mg of pyrrole is prepared and to it is added, at ambient temperature, 5.8 9 of iron tungstosilicate:
Fe4(SiW12040) for oxidizing all the pyrrole by the exchange of 2.5 electrons per pyrrole unit. The product obtained is filtered, washed with acetonitrile and dried under vacuum. This leads to polypyrrole doped by 33~ tungstosilicic anions with a polymerization reaction yield of 81%.
The doping anion from the tungstosilicic acid remains remarkably immobilized within the polypyrrole due to its large size. Thus, if an attempt is made to exchange it by perchlorate anions by immerslng the product in a perchloric acid solution in acetonitrile for several days, the weight loss observed only ;
B 9547.3 MDT ;~
: .:
... . , , ~;, .. . . .
.
- .- . . ~ . . : ~ ~, .. .. .. ~ .. :
, - . .
-' 1 33~643 corresponds to a 10~ exchange of the heteropolyacid anion.
The infrared spectra by Fourier transform and percentage analysis confirm a polypyrrole structure doped by the anion of acid H4(SiW1204o).
This material can be used as a chemical or electrochemical catalyst, in the vapour phase or in the prese~,ce of an aqueous or organic solution, without ha~ing been ~ctivated or after activation by chemical Qr electrochemical reduction.
EXAMPLE 4: Chemical Preparation of Polypyrrole Doped by the Anions of Molybdophosphoric Ac_d (V):
H3(P5+Mol2040).
The starting product is a solution constituted by 10 cm3 of acetonitrile containing 200 mg of pyrrole to which are added 10 9 of molybdophosphoric acid (V):
H3(P5+Mol2040), which is sufficiently oxidizing to oxidize the pyrrole into polypyrrole.
The mixture is stirred for 1 hour under nitrogen, it is then filtered and the filtered product is then washed abundantly with acetonitrile. In this way 80 mg - ` i of polypyrrole doped by the anions of molybdophosphoric acid (V): H3(P5+Mol2040) are recovered.
This material can be used as a chemical or electro-chemical catalyst, in the vapour phase or in the presence of an aqueous or organic solution, without supplementary activation or after activation by chemical or electrochemical reduction.
EXAMPLE S: Use of a Yitreous Carbon Electrode Covered with Polydniline Doped by the Anions of Tungstosilicic Acid for the Electrolysis of_Water.
As in example 1, a 10 cm2 vitreou~ carbon electrode B 9547.3 MDT
~ 15 ~643 is prepared covered with polyaniline doped by the anions of tungstosilicic acid H4(SiW12040) and it is subjected to the activation treatment used in example 1 for obtaining curve 1 of Fig. 2. This electrode is then used for the electrolysis of water in an acid medium with a current density of I to 100 mA/cm2 for several hours, the electrode voltage between the cathode and anode being approximately 2Y.
B 9547.3 MDT
. i .. . .
,, . ,,, ! :
~ , . . . ' ' , , ' '. ~ ' :
.,' . ? . ' - . : .
Claims (15)
1. Electronic conductive conjugate polymer incorporating a polymer matrix doped by anions, characterized in that said anions comprise anions of at least one heteropolyacid of formula:
Hn(XMyVy,Oz) in which n is a number between 2 and 6, X is an element chosen from the group constituted by H, Cu, Be, Zn, B, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and the rare earths, M, is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70.
Hn(XMyVy,Oz) in which n is a number between 2 and 6, X is an element chosen from the group constituted by H, Cu, Be, Zn, B, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and the rare earths, M, is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70.
2. Polymer according to claim 1, characterized in that X is P or Si.
3. Polymer according to claim 2, characterized in that the heteropolyacid is in accordance with formula:
H4(SiW12O40)
H4(SiW12O40)
4. Polymer according to claim 2, characterized in that the heteropolyacid is in accordance with the formula:
H3(PMo12O40)
H3(PMo12O40)
5. Polymer according to claim 1, characterized in that the polymer matrix is a polymer obtained from monomers chosen from the group constituted by pyrrole, thiophene, aniline, paraphenylene-diamine, acetylene, benzene and their substituted derivatives.
6. Polymer according to claim 5, characterized in that the polymer matrix is of poly-(N-methylpyrrole).
7. Polymer according to claim 5, characterized in that the polymer matrix is of polyaniline.
8. Polymer according to claim 5, characterized in that the polymer matrix is of polypyrrole.
9. Polymer according to claim 1, characterized in that the quantity of anions present in the con-ductive polymer is 0.01 to 0.3 anion per monomer unit of the polymer matrix.
10. Process for the preparation of an electronic conductive polymer according to claim 1, characterized in that it comprises:
a) firstly preparing a solution containing on the one hand a monomer able to form the polymer matrix by oxidation and on the other a heteropolyacid of formula:
Hn(XMyVy,Oz) in which n is a number between 2 and 6, X is an element chosen from within the group constituted by H, Cu, Be, Zn, B, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and rare earths, M is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70 and b) forming a polymer doped by the anions of the heteropolyacid from said solution by chemical or electrochemical oxidation.
a) firstly preparing a solution containing on the one hand a monomer able to form the polymer matrix by oxidation and on the other a heteropolyacid of formula:
Hn(XMyVy,Oz) in which n is a number between 2 and 6, X is an element chosen from within the group constituted by H, Cu, Be, Zn, B, Al, Ga, Si, Ge, Sn, Ti, Zr, Th, Hf, Ce, N, P, As, V, Sb, Bi, Cr, S, Te, Mn, I, Fe, Co, Ni, Rh, Pt and rare earths, M is Mo or W, y is a number between 6 and 18, y' is a number from 0 to 12 with y+y' ranging between 6 and 18 and z is a number between 24 and 70 and b) forming a polymer doped by the anions of the heteropolyacid from said solution by chemical or electrochemical oxidation.
11. Process according to claim 10, characterized in that oxidation is carried out electrochemically using the heteropolyacid as the electrolyte.
12. Process according to claim 10, characterized in that oxidation is carried out chemically using as the oxidizing agent the heteropolyacid or a hetero-polyacid salt having an oxidizing cation.
13. Process according to claim 12, characterized in that the oxidizing cation is Fe3+ or Ce4+.
14. Process according to any one of the claims 10 to 13, characterized in that the conductive polymer doped by the anions of the heteropolyacid then undergoes an activation treatment by chemical or electrochemical reduction.
15. Chemical or electrochemical catalyst, characterized in that it is constituted by an electronic conductive polymer doped by the anions of a heteropolyacid according to claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8718385 | 1987-12-30 | ||
| FR8718385A FR2625598B1 (en) | 1987-12-30 | 1987-12-30 | ELECTRONIC CONDUCTIVE POLYMERS DOPED BY HETEROPOLYANIONS, PROCESS FOR THEIR PREPARATION AND THEIR USE IN CHEMICAL AND ELECTROCHEMICAL CATALYSIS |
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| Publication Number | Publication Date |
|---|---|
| CA1332643C true CA1332643C (en) | 1994-10-18 |
Family
ID=9358454
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000586460A Expired - Fee Related CA1332643C (en) | 1987-12-30 | 1988-12-20 | Electronic conductive polymers doped by heteropolyanions, their preparation process and their use in chemical and electrochemical catalysis |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0323351B1 (en) |
| JP (1) | JPH01252666A (en) |
| CA (1) | CA1332643C (en) |
| DE (1) | DE3875333T2 (en) |
| FR (1) | FR2625598B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006125325A1 (en) * | 2005-05-27 | 2006-11-30 | University Of Manitoba | Metastable reaction mixtures for the in situ polymerization of conducting polymers |
| US9049771B2 (en) | 2008-11-19 | 2015-06-02 | Nissan Chemical Industries, Ltd. | Charge-transporting material and charge-transporting varnish |
| TWI492999B (en) * | 2008-11-19 | 2015-07-21 | Nissan Chemical Ind Ltd | Charge transport material and charge transport varnish |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218140A (en) * | 1988-08-02 | 1993-06-08 | Union Carbide Chemicals & Plastics Technology Corporation | Carbonylation reaction and catalyst therefor |
| PL163857B1 (en) * | 1990-08-31 | 1994-05-31 | Politechnika Warszawska | Method of making catalysts with acid-base and redox properties composed of heteropolanions on a polymer carrier |
| FR2703463B1 (en) * | 1993-03-29 | 1995-05-19 | Commissariat Energie Atomique | Conductive polymer film doped with mixed heteropolyanions, usable for the detection of nitrite ions. |
| BE1006963A3 (en) * | 1993-04-01 | 1995-02-07 | Cockerill Rech & Dev | PROCESS FOR FILING BY electropolymerisation FILM COMPOSITE MATERIAL ON A SURFACE CONDUCTIVE ELECTRICITY. |
| BE1008086A3 (en) * | 1994-01-20 | 1996-01-16 | Cockerill Rech & Dev | PROCESS FOR FILING BY electropolymerisation FILM ON CONDUCTING ORGANIC SURFACE OF ELECTRICITY. |
| DE4424625A1 (en) * | 1994-07-13 | 1996-01-18 | Degussa | Microporous hetero:poly:oxo:metallate(s) useful as shape-selective catalysts |
| CN1073645C (en) * | 1995-10-06 | 2001-10-24 | 陶氏化学公司 | Composite membrane and use thereof for chemical synthesis |
| DE10164467A1 (en) * | 2001-12-20 | 2003-07-10 | Inst Angewandte Chemie Berlin | Catalyst for epoxidation of olefinic compounds comprises tungsten, molybdenum, vanadium or titanium bound to a polyaniline support |
| FR2843050B1 (en) * | 2002-08-01 | 2005-04-15 | Inst Francais Du Petrole | METAL CATALYST OF GROUP VI AND GROUP VIII AT LEAST IN PART IN THE FORM OF HETEROPOLYANIONS IN THE OXIDE PRECURSOR |
| JP5760334B2 (en) * | 2009-06-19 | 2015-08-05 | 大日本印刷株式会社 | Organic electronic device and manufacturing method thereof |
| GB201111742D0 (en) * | 2011-07-08 | 2011-08-24 | Cambridge Display Tech Ltd | Solution |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2573779B1 (en) * | 1984-11-28 | 1987-08-28 | Centre Nat Rech Scient | NOVEL ELECTRODES ACTIVATED USING HETEROPOLYACIDS, THEIR PREPARATION AND THEIR APPLICATION, IN PARTICULAR AS CATHODES FOR THE ELECTROLYSIS OF WATER IN ACID MEDIA |
-
1987
- 1987-12-30 FR FR8718385A patent/FR2625598B1/en not_active Expired - Lifetime
-
1988
- 1988-12-20 CA CA000586460A patent/CA1332643C/en not_active Expired - Fee Related
- 1988-12-27 EP EP88403338A patent/EP0323351B1/en not_active Expired - Lifetime
- 1988-12-27 DE DE8888403338T patent/DE3875333T2/en not_active Expired - Fee Related
- 1988-12-29 JP JP63332708A patent/JPH01252666A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006125325A1 (en) * | 2005-05-27 | 2006-11-30 | University Of Manitoba | Metastable reaction mixtures for the in situ polymerization of conducting polymers |
| US8288507B2 (en) | 2005-05-27 | 2012-10-16 | University Of Manitoba | Metastable reaction mixtures for the in situ polymerization of conducting polymers |
| US9049771B2 (en) | 2008-11-19 | 2015-06-02 | Nissan Chemical Industries, Ltd. | Charge-transporting material and charge-transporting varnish |
| TWI492999B (en) * | 2008-11-19 | 2015-07-21 | Nissan Chemical Ind Ltd | Charge transport material and charge transport varnish |
| TWI499649B (en) * | 2008-11-19 | 2015-09-11 | Nissan Chemical Ind Ltd | Charge transport material and charge transport varnish |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0323351B1 (en) | 1992-10-14 |
| EP0323351A1 (en) | 1989-07-05 |
| DE3875333T2 (en) | 1993-04-22 |
| JPH01252666A (en) | 1989-10-09 |
| FR2625598A1 (en) | 1989-07-07 |
| FR2625598B1 (en) | 1990-05-04 |
| DE3875333D1 (en) | 1992-11-19 |
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