Method for coating the surface of an organic or metallic material with particular organic compounds by means of a pulsed-current electrochemical reduction of the diazonium ions of said organic compounds
View Patent ↗The invention relates to a method for coating an organic or metallic material by covalent grafting of at least one organic compound A having at least one aromatic group substituted with a diazonium function, on a surface of said material, characterized in that the material is porous or fibrillar having a geometric surface area of at least 10 cm 2 of material, and in that said method includes a step of continuous imposition of a non-zero pulsed current in an intensiostatic mode on the surface of the material in order to electrochemically reduce the diazonium ion or ions. The invention further relates to the resulting composite materials and to the use of such materials for manufacturing electrodes.
1. A method for coating an organic or metallic material by covalent grafting of at least one organic compound A, possessing at least one aromatic group substituted by a diazonium function, on a surface of said material, characterized in that said material is porous or fibrillar and has a geometrical surface area of at least 10 cm 2 of material; and the method of coating comprises a step of continuous imposition of a non-zero pulsed current in an intentiostatic mode on the surface of the material in order to electrochemically reduce the diazonium ion or ions, wherein the step of imposition of the non-zero pulsed current is carried out in successive cycles, each cycle comprising:
a grafting phase with a duration Δt 1 during which a first intensity of the non-zero pulsed current (i 1 ) applied is chosen so as to polarize the surface of the material to a potential E 1 enabling the reduction of the diazonium salt and the grafting of the aromatic group, substituted by said diazonium salt, on to the surface of said material for a non-zero duration of imposition Δt 1 , and
an idle phase of a duration Δt 2 during which a second intensity of the non-zero pulsed current applied (i 2 ) is smaller than the first intensity of the non-zero pulsed current (i 1 ), for a non-zero idle duration Δt 2 , wherein the second intensity of the non-zero pulsed current (i 2 ) is non-zero.
2. The method according to claim 1 , characterized in that a value of the first intensity i 1 is given in amperes by the following relationship:
i 1 =k×m,
where:
m=mass of organic or metallic material in grams; and
k=2 amperes per gram of metallic material and k=5 amperes per gram of organic material.
3. The method according to claim 1 , characterized in that a value of the second intensity i 2 is lower than or equal to 0.05 times a value of the first intensity of the non-zero pulsed current (i 1 ).
4. The method according to claim 1 , characterized in that the duration of imposition Δt 1 is given by the following relationship:
Δ t 1 =k t ×t b ,
in which:
k t =(A)/C min , where (A) represents a concentration of the organic compound A in moles per liter and C min represents the minimum concentration in diazonium atoms, and
t b represents a value constant in time.
5. The method according to claim 1 , characterized in that the duration of imposition Δt 1 ranges from 100 microseconds to 30 seconds, the duration of the idle time Δt 2 ranges from 1 second to 5 minutes, or a combination of both.
6. The method according to claim 1 , characterized in that the material is an organic material chosen from foams, felts, and superimposition of fabrics.
7. The method according to claim 6 , characterized in that it comprises a step of metallization of the organic material by electrodeposition of at least one metal prior to the step of continuous imposition of the non-zero pulsed current.
8. The method according to claim 1 , characterized in the material is a metallic material chosen from among the metals having a standard potential measured by a standard hydrogen electrode at 25° C. lower than zero.
9. The method according to claim 1 , characterized in that the organic compound A is chosen from molecules that are insoluble or nearly soluble in water and comprise at least one arylamine function.
10. The method according to claim 9 , wherein organic compound A is chosen from among the macrocyclic catalysts possessing a metal-centre at the centre of the molecule and belonging to the group consisting of: phtalocyanine, porphyrine, calixarene, crown ether and cyclopeptide families.
11. The method according to claim 1 , characterized in that it is implemented in an appropriate medium comprising a protic solvent, an aprotic solvent and a supporting electrolyte.
12. The method according to claim 11 , characterized in that the aprotic solvent is an organic solvent, in that the protic solvent is water and in that the appropriate medium is a mixture of organic solvent and water in a volume ratio of at least 90/10.
13. The method according to claim 5 , characterized in that the duration of imposition Δt 1 ranges from 0.5 to 10 seconds.
14. The method according to claim 6 , characterized in that the felt is selected from the group consisting of carbon fiber felts and graphite fiber felts.
15. The method according to claim 7 , further comprising that the step of metallization of the organic material by electrodeposition of at least one metal is performed in situ.
16. The method according to claim 8 , characterized in that the metallic material is selected from the group consisting of tin, indium, molybdenum, gallium, vanadium, nickel, cobalt, thallium, cadmium, iron, bismuth, chromium, zinc and copper.
17. The method according to claim 16 , characterized in that the metallic material is selected from the group consisting of nickel, cobalt and copper.