HETEROATOM-ENRICHED PARTIALLY-GRAPHITIC NANO-CARBONS

• US 20170113934A1
• Filed: 06/24/2016
• Published: 04/27/2017
• Est. Priority Date: 08/17/2009
• Status: Abandoned Application

• Current Assignee: Carnegie Mellon University
• Original Assignee: Carnegie Mellon University
• Inventors: Zhong, Mingjiang, Gottlieb, Eric, Kopec, Maciej, Mohin, Jacob, Kowalewski, Tomasz, Matyjaszewski, Krzysztof
• Application Number:
  US15/191,918
• Publication Number:
  US 20170113934A1
• Time in Patent Office: Days
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C01B 32/184 Preparation
• CPC Class Codes: H01G 9/2022 characterized by he counter electrode
• CPC Class Codes: Y02E 10/542 Dye sensitized solar cells
• CPC Class Codes: Y02E 60/13 Energy storage using capacitors
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product
• CPC Class Codes: Y10S 977/734 Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
• CPC Class Codes: Y10S 977/842 for carbon nanotubes or fullerenes

Abstract

Carbon-based nanomaterials comprising graphitic domains that are doped with heteroatoms are disclosed. Processes for the production the nanomaterials, methods of using the nanomaterials, and articles or devices comprising the nanomaterials are also disclosed.

Claims

1. A process for producing a carbon nanomaterial comprising:

forming a phase separated (co)polymer having a carbon precursor phase and a sacrificial phase, wherein the carbon precursor phase comprises a (co)polymer comprising covalently bonded nitrogen atoms;

chemically or thermally removing the sacrificial phase from the phase separated (co)polymer; and

heating the (co)polymer comprising the carbon precursor phase at a temperature of 500-1,000°

C., thereby pyrolyzing the (co)polymer comprising the carbon precursor phase and converting the (co)polymer comprising the carbon precursor phase into a carbon nanomaterial comprising nitrogen-doped nanographene structures having edge-on topology to an outer surface of the carbon nanomaterial or to a surface of a pore in the carbon nanomaterial, wherein the nanographene structures comprise nitrogen atoms located along the edges of the nanographene sheets bordering the outer surface of the carbon nanomaterial or the surface of a pore in the carbon nanomaterial.

2. The process for producing a carbon nanomaterial of claim 1, further comprising heating the (co)polymer comprising the carbon precursor phase in an oxidizing atmosphere at a temperature of 200-300°

C., and thereafter heating the (co)polymer comprising the carbon precursor phase at a temperature of 500-1,000°

C. to pyrolyze the (co)polymer comprising the carbon precursor phase.

3. The process for producing a carbon nanomaterial of claim 1, further comprising grinding or milling the carbon nanomaterial into a powder.

4. The process for producing a carbon nanomaterial of claim 3, wherein the carbon nanomaterial is ground or milled into a powder having a particle size of 1-100 nanometers.

5. The process for producing a carbon nanomaterial of claim 1, wherein the (co)polymer comprising the carbon precursor phase is heated at a temperature of 600-800°

C. to pyrolyze the (co)polymer comprising the carbon precursor phase.

6. The process for producing a carbon nanomaterial of claim 1, wherein the (co)polymer comprising the carbon precursor phase is heated at a temperature of 500-1,000°

C. for 0.25-5 hours to pyrolyze the (co)polymer comprising the carbon precursor phase.

7. The process for producing a carbon nanomaterial of claim 1, wherein the (co)polymer comprising the carbon precursor phase is heated at a temperature of 500-1,000°

C. for 0.5-3 hours to pyrolyze the (co)polymer comprising the carbon precursor phase.

8. The process for producing a carbon nanomaterial of claim 1, wherein the (co)polymer comprising the carbon precursor phase is heated at a temperature of 500-1,000°

C. in an inert atmosphere to pyrolyze the (co)polymer comprising the carbon precursor phase.

9. The process for producing a carbon nanomaterial of claim 1, wherein the (co)polymer comprising the carbon precursor phase is heated at a temperature of 500-1,000°

C. in an activating atmosphere comprising N₂, CO₂, O₂, steam, chlorine, or ammonia, or a combination of any thereof, to pyrolyze the (co)polymer comprising the carbon precursor phase.

10. The process for producing a carbon nanomaterial of claim 1, wherein the nanographene structures comprise pyridinic nitrogen atoms located along the edges of the nanographene sheets.

11. The process for producing a carbon nanomaterial of claim 10, wherein the full width at the half maximum of the N 1s peak in the X-ray photoelectron spectrum of the pyridinic nitrogens is less than 2 eV.

12. The process for producing a carbon nanomaterial of claim 11, wherein the full width at the half maximum of the N 1s peak in the X-ray photoelectron spectrum of the pyridinic nitrogens is less than 1.75 eV.

13. The process for producing a carbon nanomaterial of claim 1, wherein carbon precursor phase comprises a polymer block formed from acrylonitrile monomer units, vinyl acetylene monomer units, 4-vinyl pyridine monomer units, styrene monomer units, or combinations thereof.

14. The process for producing a carbon nanomaterial of claim 1, wherein carbon precursor phase comprises a polyacrylonitrile block.

15. The process for producing a carbon nanomaterial of claim 1, wherein the sacrificial phase is thermally removed from the phase separated (co)polymer by simultaneously heating the sacrificial phase and the carbon precursor phase at a temperature of 500-1,000°

C.

16. The process for producing a carbon nanomaterial of claim 1, wherein forming the phase separated (co)polymer having the carbon precursor phase and the sacrificial phase comprises forming a hybrid composite further comprising an inorganic phase.

17. The process for producing a carbon nanomaterial of claim 1, wherein the carbon precursor phase comprises a discontinuous phase that forms separated carbon nanomaterial structures after pyrolysis.

18. The process for producing a carbon nanomaterial of claim 1, wherein the carbon precursor phase comprises a continuous phase that forms a porous carbon nanomaterial after pyrolysis.

19. The process for producing a carbon nanomaterial of claim 18, wherein the pores are formed from the volume occupied by the removed sacrificial phase and have a size from 5-100 nm.

20. The process for producing a carbon nanomaterial of claim 1, wherein the carbon nanomaterial comprises nanopores, mesopores, micropores, or macropores, or a combination of any thereof, and wherein nitrogen-doped nanographene structures have edge-on topology to the surfaces of the pore in the carbon nanomaterial.

22. The process for producing a carbon nanomaterial of claim 19, wherein the heteroatoms comprise nitrogen, oxygen, phosphorous, or sulfur, or a combination of any thereof.

21. A process for producing a carbon nanomaterial comprising:

forming a phase separated (co)polymer having a carbon precursor phase and a sacrificial phase, wherein the carbon precursor phase comprises a (co)polymer comprising covalently bonded heteroatoms;

chemically or thermally removing the sacrificial phase from the phase separated (co)polymer; and

heating the (co)polymer comprising the carbon precursor phase at a temperature of 500-1,000°

C., thereby pyrolyzing the (co)polymer comprising the carbon precursor phase and converting the (co)polymer comprising the carbon precursor phase into a carbon nanomaterial comprising heteroatom-doped nanographene structures having edge-on topology to an outer surface of the carbon nanomaterial or to a surface of a pore in the carbon nanomaterial, wherein the nanographene structures comprise heteroatoms located along the edges of the nanographene sheets bordering the outer surface of the carbon nanomaterial or the surface of a pore in the carbon nanomaterial.