IP Library Granted Patent US 10,913,035
Granted Patent B2
US 10,913,035 · App. 16/085,098 · Granted Feb 9, 2021

Laminate membranes comprising a two-dimensional layer comprising polyaromatic functionalities

Inventors: Robert Dryfe (Manchester, GB); Mark Bissett (Manchester, GB)
Assignee: The University of Manchester
B01D71/02B01D67/0046B01D67/0093B01D69/12B01D61/02B01D2323/36B01D2323/40
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Quick Facts
Patent No.
US 10,913,035
App. No.
16/085,098
Granted
Feb 9, 2021
Kind
B2
Abstract

This invention relates to membranes of two dimensional material and their uses in filtration. The membranes may include polyaromatic molecules which provide a improvement in the rejection observed for small solutes. The two dimensional material may be a transition metal dichalcogenide (TMDC) or hexagonal boron nitride (hBN).

Claims (46)

1. A laminate membrane comprising:

a plurality of nanoplatelets of a two-dimensional material comprising a transition metal dichalcogenide (TMDC) and/or hexagonal boron nitride (hBN), wherein each individual nanoplatelet is impermeable to liquid and the plurality of nanoplatelets are stacked in such a way as to form capillary-like pathways between the faces and sides of the nanoplatelets; and

a plurality of polyaromatic molecules covalently bonded to the two-dimensional material.

2. The membrane of claim 1 , wherein the two-dimensional material is a TMDC.

3. The membrane of claim 1 , wherein the plurality of nanoplatelets is a mixture of a plurality of nanoplatelets of a first two-dimensional material comprising a TMDC and a plurality of nanoplatelets of a second two-dimensional material selected from the group consisting of a TMDC, graphene, and hBN.

4. The membrane of claim 1 , wherein the polyaromatic molecules are dye molecules.

5. The membrane of claim 4 , wherein the dye molecules comprise sunset yellow and/or crystal violet.

6. The membrane of claim 1 , wherein the plurality of nanoplatelets is obtained from the corresponding bulk layered inorganic material using a solvent exfoliation method.

7. The membrane of claim 1 , wherein the laminate membrane is comprised in a composite with a porous material.

8. A method of reducing the amount of one or more solutes in a liquid to produce a product liquid depleted in said solute or solutes; the method comprising:

(a) contacting a first face of a laminate membrane with the liquid comprising the one or more solutes, wherein the laminate membrane comprises a plurality of nanoplatelets of a two-dimensional material comprising a transition metal dichalcogenide (TMDC) and/or hexagonal boron nitride (hBN); and a plurality of polyaromatic molecules covalently bonded to the two-dimensional material; wherein each individual nanoplatelet is impermeable to liquid and the plurality of nanoplatelets are stacked in such a way as to form capillary-like pathways between the faces and sides of the nanoplatelets, causing the liquid to pass through the capillary-like pathways between the faces and sides of the nanoplatelets; and

(b) recovering the product liquid depleted in said solute or solutes from or downstream from a second face of the membrane;

(c) optionally, recovering the solute or solutes from the first face of the membrane.

9. The method of claim 8 , wherein the one or more solutes comprise one or more ions and corresponding counterions in which both ions have a hydration radius that is no larger than 1 nm.

10. The method of claim 8 , wherein the method is a filtration method and wherein the product liquid is recovered as a liquid from or downstream from the second face of the membrane without the liquid having undergone a phase change.

11. The method of claim 8 , wherein the liquid is an aqueous liquid.

12. The method of claim 8 , wherein the one or more solutes comprise one or more ions and corresponding counterions in which both ions have a hydration radius that is no larger than 0.45 nm.

13. The method of claim 12 , wherein the one or more solutes includes NaCl.

14. A method of reducing the amount of one or more non-ionic solutes in a liquid to produce a product liquid depleted in said solute or solutes; the method comprising:

(a) contacting a first face of a laminate membrane with the liquid comprising the one or more solutes, wherein the laminate membrane comprises a plurality of nanoplatelets of a two-dimensional material comprising a transition metal dichalcogenide (TMDC) and/or hexagonal boron nitride (hBN); and a plurality of polyaromatic molecules covalently bonded to the two-dimensional material; wherein each individual nanoplatelet is impermeable to liquid and wherein the plurality of nanoplatelets are stacked in such a way as to form capillary-like pathways between the faces and sides of the nanoplatelets, causing the liquid to pass through the capillary-like pathways between the faces and sides of the nanoplatelets; and

(b) recovering the solute or solutes liquid from or downstream from a second face of the membrane;

(c) optionally, recovering any remaining product from the first face of the membrane;

wherein the one or more solutes are each non-ionic species having a hydration radius that is no larger than 10 nm.

15. The method of claim 14 , wherein the one or more solutes comprise non-ionic species having a hydration radius that is no larger than 1 nm.

16. The method of claim 14 , wherein the method is a filtration method and wherein the product liquid is recovered as a liquid from or downstream from the second face of the membrane without the liquid having undergone a phase change.

17. The method of claim 16 , wherein the non-ionic solute or each non-ionic solute is an organic molecule.

18. The method of claim 14 , wherein the liquid is an organic solvent or solvent mixture.

19. The method of claim 14 , wherein the liquid is an aqueous liquid.

20. The method of claim 14 , wherein the method is a pervaporation method and the method of recovering the product liquid comprises allowing the liquid to evaporate from the second face of the membrane to form a vapour and subsequently condensing the vapour to form the product liquid.

21. The method of claim 20 , wherein the non-ionic solute is an alcohol and the liquid is either water or a second alcohol with a smaller hydration radius than the first alcohol.

22. The method of claim 14 , wherein the concentration of the one or more solutes in the product liquid is reduced by 50% or more relative to the concentration in the starting liquid.

23. The method of claim 14 , wherein the plurality of nanoplatelets is obtained from the corresponding bulk layered inorganic material using a solvent exfoliation method.

24. The method of claim 14 , wherein the plurality of nanoplatelets is a mixture of a plurality of nanoplatelets of a first two-dimensional material selected from the group consisting of a TMDC and hBN and a plurality of nanoplatelets of a second two-dimensional material selected from the group consisting of a TMDC, graphene, and hBN.

25. The method of claim 14 , wherein the two-dimensional material is a TMDC.

26. The method of claim 14 , wherein the two-dimensional material is hBN.

27. The method of claim 14 , wherein the laminate membrane is comprised in a composite with a porous material.

28. A method of producing a laminate membrane of claim 7 ; the method comprising:

a) depositing a plurality of nanoplatelets of a two-dimensional material onto a porous material to form the laminate membrane supported on the porous material; and

b) contacting a first side of the laminate membrane with a first solution comprising a first concentration of the polyaromatic molecules and contacting the second side of the laminate membrane with a second solution comprising a second concentration of the polyaromatic molecules, said second concentration being lower than said first concentration, to covalently bond the plurality of polyaromatic molecules to the two-dimensional material to provide a membrane of claim 7 .

29. The method of claim 28 , wherein the method further comprises:

obtaining the plurality of nanoplatelets of the two-dimensional material from the corresponding bulk layered inorganic material using a solvent exfoliation method.

30. The membrane of claim 1 , wherein the plurality of polyaromatic molecules are charged polyaromatic molecules.

31. The membrane of claim 30 , wherein the polyaromatic molecules are negatively charged.

32. The membrane of claim 1 , wherein the laminate membrane has a thickness between about 100 nm and about 10 μm.

33. The membrane of claim 1 , wherein the polyaromatic molecules are covalently bonded to the two-dimensional material via a nitrogen atom in each polyaromatic molecule.

34. The membrane of claim 7 , wherein the laminate membrane is sandwiched between layers of the porous material.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2019
From: DRYFE, ROBERT; BISSETT, MARK
To: THE UNIVERSITY OF MANCHESTER
Reel/Frame 048239/0122 →
Priority Claims (1)
GB 1605881.0 · Apr 6, 2016 · national
Continuity (1)
Related Publication 20190076792A1 · Mar 14, 2019