Selectively permeable graphene oxide membrane

Patent metadata

Field	Value
Publication number	US-10442709-B2
Application number	US-201615380797-A
Country	US
Kind code	B2
Filing date	Dec 15, 2016
Priority date	Dec 17, 2015
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

Described herein is a graphene material based membrane that provides selective resistance for solutes or gas while providing water permeability. A selectively permeable membrane comprising graphene oxide, reduced graphene oxide, and also functionalized or crosslinked between the graphene, that provides enhanced salt separation from water or gas permeability resistance, methods for making such membranes, and methods of using the membranes for dehydrating or removing solutes from water are also described.

First claim

What is claimed is:

1. A membrane comprising:
a porous substrate; and
a graphene oxide layer comprising a cross-linked graphene oxide in fluid communication with the porous substrate;
wherein the cross-linked graphene oxide comprises a graphene oxide covalently bound to a cross-linkage, wherein the cross-linkage is represented by Formula 1:

wherein the nitrogen atoms of the cross-linkage are directly bonded to a carbon atom of graphene oxide;
wherein the cross-linked graphene oxide is prepared by reacting a mixture comprising a graphene oxide and a cross-linker, wherein the cross-linker is represented by Formula 2:

wherein, in Formula 1 and Formula 2, R is H, CO 2 H, CO 2 Li, CO 2 Na, or CO 2 K;
wherein the weight ratio of the cross-linker to the graphene oxide is in a range of 1 to 10.

2. The membrane of claim 1 , wherein the cross-linkage is:

3. The membrane of claim 1 , wherein the porous substrate comprises a polymer or hollow fibers.

4. The membrane of claim 1 , wherein the cross-linked bonded graphene oxide comprises platelets that have a size that is about 0.05 μm to about 50 μm.

5. The membrane of claim 1 , wherein the cross-linked graphene oxide is about 20 atom % to about 90 atom % carbon.

6. The membrane of claim 1 , further comprising a salt rejection layer.

7. The membrane of claim 6 , wherein the salt rejection layer is disposed on the graphene oxide layer.

8. The membrane of claim 6 , wherein the salt rejection layer comprises a polyamide prepared by reacting meta-phenylenediamine with trimesoyl chloride.

9. The membrane of claim 1 , wherein the membrane further comprises a protective layer, wherein the protective layer comprises a hydrophilic polymer.

10. The membrane of claim 1 , wherein the thickness of the graphene oxide layer is about 5 nm to about 200 nm.

11. A method for removing a solute from an unprocessed solution, comprising passing the unprocessed solution through the membrane of claim 1 , wherein passing the unprocessed solution through the membrane is achieved by applying a pressure gradient across the membrane.

12. A method of making a membrane of claim 1 , comprising:
(a) resting a solution comprising the graphene oxide and the cross-linker for about 30 minutes to about 12 hours to create a coating mixture;
(b) applying the coating mixture to the porous substrate;
(c) repeating step (b) as necessary to achieve the desired thickness or number of layers; and
(d) curing the graphene oxide and the cross-linker upon the substrate at about 50° C. to about 120° C. for about 15 minutes to about 2 hours so that the graphene oxide and the cross-linker are covalently bonded to form the cross-linkage.

Assignees

• Nitto Denko Corp

Inventors

• Zheng Shijun
• Kitahara Isamu
• Kobuke Makoto
• Wang Peng
• Bartels Craig Roger
• Yamashiro Yuji
• Hirose Masahiko
• Noumi Shunsuke
• Lin Weiping

Classifications

• B01D71/56

  Polyamides, e.g. polyester-amides · CPC title

• B01D67/0006 Primary

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title

• B01D61/025

  Reverse osmosis; Hyperfiltration · CPC title

• B01D69/148

  Organic/inorganic mixed matrix membranes · CPC title

• B01D2323/30

  Cross-linking · CPC title