GRAPHENE OXIDE MEMBRANES AND RELATED METHODS

• US 20170341034A1
• Filed: 05/11/2017
• Published: 11/30/2017
• Est. Priority Date: 05/11/2016
• Status: Active Grant

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Dave, Shreya H., Keller, Brent, Han, Ggoch Ddeul, Grossman, Jeffrey C.
• Granted Patent: US 10,974,208 B2
• Time in Patent Office: Days
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 2325/04 Characteristic thickness
• CPC Class Codes: B01D 61/02 Reverse osmosis; Hyperfiltration ; Nanofiltration
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 67/00931 by introduction of specific groups after membrane formation, e.g. by grafting
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 71/021 Carbon
• CPC Class Codes: B01D 71/0211 Graphene or derivates thereof
• CPC Class Codes: B01D 71/0212 Carbon nanotubes
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B32B 15/082 comprising vinyl resins; comprising acrylic resins
• CPC Class Codes: B32B 15/085 comprising polyolefins
• CPC Class Codes: B32B 15/09 comprising polyesters
• CPC Class Codes: B32B 2307/20 having particular electrical or magnetic properties, e.g. piezoelectric
• CPC Class Codes: B32B 2307/308 Heat stability dimensional stability B32B2307/734
• CPC Class Codes: B32B 2307/732 Dimensional properties
• CPC Class Codes: B32B 2313/04 Carbon
• CPC Class Codes: B32B 27/283 comprising polysiloxanes
• CPC Class Codes: B32B 27/285 comprising polyethers
• CPC Class Codes: B32B 27/286 comprising polysulphones; polysulfides
• CPC Class Codes: B32B 27/302 : comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• CPC Class Codes: B32B 27/304 : comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
• CPC Class Codes: B32B 27/308 : comprising acrylic (co)polymers
• CPC Class Codes: B32B 27/32 : comprising polyolefins comprising vinyl (co)polymers or acrylic (co)polymers B32B27/30
• CPC Class Codes: B32B 27/322 : comprising halogenated polyolefins, e.g. PTFE
• CPC Class Codes: B32B 3/26 : characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids foam layer B32B5/18; layer of synthetic resin characterised by fillers that create voids or cavities B32B27/205; characterised by an apertured layer
• CPC Class Codes: B32B 3/266 : characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
• CPC Class Codes: B32B 7/10 : at least one layer having inter-reactive properties
• CPC Class Codes: B32B 9/007 : comprising carbon, e.g. graphite, composite carbon
• CPC Class Codes: B32B 9/041 : of metal
• CPC Class Codes: C01B 32/198 : Graphene oxide

Abstract

Membranes comprising graphene oxide sheets and associated filter media and methods are provided. In some embodiments, a membrane may comprise graphene oxide sheets that have undergone one or more chemical treatments. The chemical treatment(s) may impart beneficial properties to the membrane, such as a relatively small d-spacing, compatibility with a broad range of environments, physical stability, and charge neutrality. For example, the graphene oxide sheets may undergo one or more chemical treatments that form chemical linkages between at least a portion of the graphene oxide sheets in the membrane. Such chemical linkages may impart a small d-spacing, broad compatibility, and/or allow relatively thick membranes to be formed. In certain embodiments, the graphene oxide sheets may undergo one or more chemical treatment that imparts relative charge neutrality to the membrane by altering the ionizability of certain functional groups. Graphene oxide membranes, described herein, can be used for a wide range applications.

Claims

1. A membrane, comprising:

crosslinked graphene oxide sheets, wherein a thickness of the membrane is greater than or equal to about 0.2 microns and a weight percentage of graphene oxide in the membrane is greater than or equal to about 70 wt. %.

3. The membrane of claim 1, wherein the crosslinked graphene oxide sheets are covalently crosslinked.

9. The membrane of claim 1, wherein an average d-spacing of the membrane is less than or equal to about 10 Å

when saturated with water.

11. The membrane of claim 1, wherein a difference between an average d-spacing of the membrane when saturated with water and an average d-spacing of the membrane when dry is less than or equal to about 1 Å

.

13. The membrane of claim 1, wherein the membrane has a thickness of greater than or equal to about 10 microns.

14. The membrane of claim 1, wherein a molecular weight cutoff of the membrane is greater than or equal to about 250 g/mol.

15. The membrane of claim 1, wherein the membrane is compatible with one or more oxidizing agents.

18. The membrane of claim 1, wherein the membrane is compatible with one or more chlorinated solvents.

19. The membrane of claim 1, wherein the membrane is compatible with one or more nonpolar solvents.

21. The membrane of claim 1, wherein the membrane has a maximum compatible pH of greater than or equal to about 9.

22. The membrane of claim 1, wherein the membrane has a minimum compatible pH of less than or equal to about 5.

23. The membrane of claim 1, wherein a maximum operating temperature of the membrane in water at pH 7 is greater than or equal to about 65°

C. and less than or equal to about 300°

C.

34. The membrane of claim 1, wherein a maximum operating temperature of the membrane in water at pH 7 is greater than or equal to about 100°

C. and less than or equal to about 300°

C.

2. (canceled)

4-5. -5. (canceled)

6. A membrane, comprising:

a first graphene oxide sheet;

a second graphene oxide sheet; and

a chemical linkage that attaches the first graphene oxide sheet to the second graphene oxide sheet, wherein the chemical linkage is of Formula I;

7-8. -8. (canceled)

10. (canceled)

12. (canceled)

16-17. -17. (canceled)

20. (canceled)

24-33. -33. (canceled)

35-53. -53. (canceled)

54. A method, comprising:

contacting a membrane comprising crosslinked graphene oxide sheets with a mixture comprising a fluid, a first species having a molecular weight of greater than or equal to about 250 g/mol, and a second species having a molecular weight of less than about 250 g/mol; and

passing the fluid and the second species through the membrane, wherein at least a portion of the first species is rejected by the membrane.

55. A method of claim 54, wherein the first species is an organic species.

56. A method of claim 54, wherein the second species is an ionic compound.

57-58. -58. (canceled)