Derivatisation of carbon

Patent metadata

Field	Value
Publication number	US-9630851-B2
Application number	US-201013142515-A
Country	US
Kind code	B2
Filing date	Feb 12, 2010
Priority date	Mar 20, 2009
Publication date	Apr 25, 2017
Grant date	Apr 25, 2017

Abstract

A molecular species is covalently attached to elemental carbon by exposing the carbon to a reaction mixture containing a strong base and a compound of the formula (I) or (II) in which X denotes a covalently attached atom or group capable of forming an X − anion and each Z is a moiety comprising a plurality of atoms, but which does not have a hydrogen atom directly attached to the atom which itself is directly attached to the —CH 2 X or —CHX group. The carbon substrate may be graphite or carbon nanotubes.

First claim

The invention claimed is:

1. A process for making an electrochemical sensor comprising exposing an elemental carbon substrate to an aprotic reaction mixture containing a base and a compound with a general formula
Z—CH 2 X or

in which X denotes a covalently attached atom or group which forms an X − anion and each Z is a covalently attached moiety comprising a plurality of atoms, which remains attached and does not have a hydrogen atom directly attached to the atom which is directly attached to the —CH 2 X or —CHX group;
wherein each Z is such that said compound has any of the following five general formulae

wherein R 1 to R 6 each independently denote attached aliphatic, cycloaliphatic or aromatic groups, or two or more of the groups R 1 to R 6 may together form a ring, and
wherein the base is strong enough to remove a hydrogen atom from the carbon atom to which X is attached,
and thereafter incorporating the carbon with the attached species into an electrochemical sensor in which the attached species undergoes reversible electrochemical reduction and oxidation.

2. The process of claim 1 wherein the pKa of the base, in acetonitrile as solvent, is at least 22.

3. The process of claim 1 wherein the pKa of the base, in acetonitrile as solvent, is at least as high as that of 1,5-diazabicyclo[4.3.0]non-5-ene.

4. The process of claim 1 wherein the base is either 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene.

5. The process of claim 1 wherein X is such that the pKa of the acid HX in water is no greater than the pKa of HCl in water.

6. The process of claim 1 wherein X is chlorine, bromine or iodine.

7. The process of claim 1 wherein the carbon substrate is carbon nanotubes.

8. The process of claim 1 including a chemical alteration of the species attached to the carbon substrate, so as to convert the attached species to a form which undergoes reversible electrochemical reduction and oxidation.

9. A process for making an electrochemical sensor, the process comprising exposing an elemental carbon substrate to an aprotic reaction mixture containing a base and a derivatising compound with any of the following five general formulae

wherein R 1 to R 6 each independently denote attached aliphatic, cycloaliphatic or aromatic groups and two or more of the groups R 1 to R 6 may together form a ring,
wherein X denotes a covalently attached atom or group which forms an X anion, and
wherein the base is strong enough to remove a hydrogen atom from the carbon atom to which X is attached,

thereby attaching a species of one of the following formulae to the elemental carbon

and incorporating the carbon with the attached species into an electrochemical sensor in which the attached species undergoes reversible electrochemical reduction and oxidation.

10. The process of claim 9 wherein the base is an organic compound containing nitrogen.

11. The process of claim 9 wherein the pKa of the base, in acetonitrile as solvent, is at least 22.

12. The process of claim 9 wherein the pKa of the base, in acetonitrile as solvent, is at least as high as that of 1,5-diazabicyclo[4.3.0]non-5-ene.

13. The process of claim 9 wherein the base is either 1,5-diazabicyclo[4.3.0]non-5-ene or 1,8-diazabicyclo[5.4.0]undec-7-ene.

14. The process of claim 9 wherein the derivatising compound has a general formula

and the groups R 1 and R 2 form an aromatic ring.

15. The process of claim 14 wherein the aromatic ring has a nitro group as a substituent thereon and the process includes an irreversible conversion of the nitro group to the attached species to a form which undergoes reversible electrochemical reduction and oxidation.

16. The process of claim 9 wherein the derivatising compound has a general formula

and the groups R 1 and R 2 form a cyclopentadienyl ring of a ferrocene.

17. The process of claim 9 wherein X is such that the pKa of the acid HX in water is no greater than the pKa of HCl in water.

18. The process of claim 17 wherein X is chlorine, bromine or iodine.

19. The process of claim 9 wherein the carbon substrate is carbon nanotubes.

20. The process of claim 9 including a chemical alteration of the species attached to the carbon substrate, so as to convert the attached species to a form which undergoes reversible electrochemical reduction and oxidation.

Assignees

• Zou Fenglou
• Lawrence Nathan
• Jones Timothy
• Schlumberger Technology Corp

Inventors

• Zou Fenglou
• Lawrence Nathan
• Jones Timothy

Classifications

• C01B32/21

  After-treatment · CPC title

• G01N27/308

  at least partially made of carbon · CPC title

• C01B32/194

  After-treatment · CPC title

• C01B32/05 Primary

  Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30 · CPC title

• C01B32/174

  Derivatisation; Solubilisation; Dispersion in solvents · CPC title