Catalytic etching of carbon fibers
View Patent ↗The present invention relates to a method for etching carbon fibers, in particular carbon nanofibers and to the carbon nanofibers obtainable by this method, and the use thereof.
1. A process for etching the surface of carbon fibers, which comprises the following steps:
(a) functionalizing the surface of the carbon fibers by oxidation to yield carbon fibers having a functionalized surface,
(b) depositing metal particles on the functionalized surface to yield carbon fibers having metal particles deposited on the functionalized surface thereof,
(c) etching of the surface of the carbon fibers resulting from (b) by treatment with water vapor, and
(d) removing the metal particles by acid treatment.
2. The process as claimed in claim 1 , wherein the carbon fibers are carbon nanofibers which,
(i) can be obtained from hydrocarbons and/or
(ii) have an external diameter from 50 to 500 nm, and/or
(iii) have a surface area of from 10 to 60 m 2 /g.
3. The process as claimed in claim 1 , wherein the carbon fibers are microfibers which,
(i) can be obtained from polyacrylonitrile (PAN), and/or
(ii) have an external diameter of from 3 to 10 μm and/or
(iii) have a surface area of less than 1 m 2 /g.
4. The process according to claim 1 , wherein the surface is functionalized by oxidative treatment, heating with oxidizing acids, oxygen plasma treatment, or heating with nitric acid.
5. The process as claimed in claim 1 , wherein
(i) the metal particles are selected from among Fe, Co and Ni, and/or
(ii) the metal loading is from 1 to 20% by weight, based on the total weight of the laden carbon nanofibers, and/or
(iii) the depositing of the metal particles is effected by contacting of the fibers with dissolved metal salts or metallocenes, at a temperature of from 100 to 600° C., and subsequent reduction with hydrogen at a temperature of from 300 to 800° C.
6. The process as claimed in claim 1 , wherein etching is effected by treatment with water vapor in a helium atmosphere, with optionally
(i) the water vapor content of the helium atmosphere being from 0.1 to 10% by volume, and/or
(ii) etching being carried out at a temperature of from 500 to 800° C., and/or
(iii) the helium atmosphere containing from 1 to 20% by volume of H 2 in order to keep the metal catalyst active.
7. The process as claimed in claim 1 , wherein the removing of the metal particles is effected by treatment with an acid or a mixture of HNO 3 /H 2 SO 4 .
8. The process as claimed in claim 1 , wherein the etched carbon fibers are carbon nanofibers which have a specific surface area of from 90 to 100 m 2 /g or carbon microfibers which have a specific surface area of from 5 to 50 m 2 /g.