Graphene Oxide Membrane With A Controllable Interlayer Spacing, A Preparation Method And Use Thereof

Patent metadata

Field	Value
Publication number	US-2019282969-A1
Application number	US-201716318616-A
Country	US
Kind code	A1
Filing date	May 25, 2017
Priority date	Jul 20, 2016
Publication date	Sep 19, 2019
Grant date	—

Abstract

A graphene oxide membrane with a controllable interlayer spacing, a preparation method and use thereof are provided. The preparation method provides of infiltrating a graphene oxide membrane in an aqueous solution A of salt to swell, thereby obtaining the graphene oxide membrane with the controllable interlayer spacing. The aqueous solution A of salt is a solution containing metal cation, and the concentration of the metal cation in the aqueous solution A is from 0.25-2.5 mol/L. The application can precisely control the size of the interlayer spacing of the graphene oxide membrane in the range of 11˜14 Å, and the variable range of this spacing can be controlled to within 0.6˜1 Å. The graphene oxide membrane with the controllable interlayer spacing of the application has excellent mechanical strength, which remains a complete membrane state after 5 hours of infiltration. The preparation process is simple and easy to be operated, and the obtained graphene oxide membrane has a function of screening and filtering smaller ions, and thus has a good application prospect.

First claim

1 . A method of preparing a graphene oxide membrane with a controllable interlayer spacing, comprising:
infiltrating a graphene oxide membrane in an aqueous solution A of salt to swell, thereby obtaining the graphene oxide membrane with the controllable interlayer spacing, wherein the aqueous solution A of salt is a solution containing metal cation, and the concentration of the metal cation in the aqueous solution A is from 0.25 to 2.5 mol/L.

2 . The method according to claim 1 , wherein the graphene oxide membrane is prepared from a graphene oxide solution through a drop-cast method or a suction filter method.

3 . The method according to claim 2 , wherein the first drying is at 55˜65° C. for 5˜7 hours;
and/or, the second drying is at 55˜65° C. for 11˜13 hours.

4 . The method according to claim 1 , wherein during the infiltration, ambient temperature is from 17 to 23° C.;
the metal cation is one or more of K + , Na + , Li + , Ca 2+ , and Mg 2+ ;
the pH of the aqueous solution A is 5˜8;
and/or, the time of the infiltration is from 1 to 3 hours.

5 . The method according to claim 1 wherein the aqueous solution A of salt contains an anion which is an anion wherein the size of hydrated anion is smaller than hydrated cation;
in the aqueous solution A of salt, when the metal cation is K + , the anion includes one or more of F − , Cl − , Br − , I − , and NO 3 − in addition to OH − ;
and/or, in the aqueous solution A of salt, when the metal cation is Na + , Li + or Ca 2+ , the anion includes one or more of F − , Cl − , Br − , I − and NO 3− in addition to OH − ;
and/or, in the aqueous solution A of salt, when the metal cation is Mg 2+ , the anion includes one or more of F − , Cl − , Br − , I − , SO 4 2− , and NO 3 − in addition to OH − .

6 . A graphene oxide membrane with a controllable interlayer spacing produced by the method according to claim 1 .

7 . The graphene oxide membrane according to claim 6 , wherein the graphene oxide membrane with the controllable interlayer spacing is selected from any one of following membranes:
1) in the aqueous solution A of salt, the metal cation is K + , and the size of the interlayer spacing of the graphene oxide membrane with the controllable interlayer spacing is 11.4±0.1 Å; 2) in the aqueous solution A of salt, the metal cation is Na + , and the size of the interlayer spacing of the graphene oxide membrane with the controllable interlayer spacing is 12.1±0.2 Å; 3) in the aqueous solution A of salt, the metal cation is Ca 2+ , and the size of the interlayer spacing of the graphene oxide membrane with the controllable interlayer spacing is 12.9±0.2 Å; 4) in the aqueous solution A of salt, the metal cation is Li + , and the size of the interlayer spacing of the graphene oxide membrane with the controllable interlayer spacing is 13.5±0.2 Å; 5) in the aqueous solution A of the salt, the metal cation is Mg 2+ , and the size of the interlayer spacing of the graphene oxide membrane with the controllable interlayer spacing is 13.6±0.1 Å.

8 . A method wherein the graphene oxide membrane with the controllable interlayer spacing according to claim 7 is used in filtering an aqueous solution B of salt.

9 . The method according to claim 8 , wherein the aqueous solution B of salt has a concentration of from 0.25 to 2.5 mol/L;
the operation of filtering is carried out according to following steps: controlling the interlayer spacing of the graphene oxide membrane by the aqueous solution A of salt, and then filtering the aqueous solution B of the salt by the graphene oxide membrane with the controlled interlayer spacing; and/or, the amount of the aqueous solution B of salt is the same as the amount of the aqueous solution A for controlling the interlayer spacing.

10 . The method according to claim 9 , wherein the graphene oxide membrane with the controllable interlayer spacing is prepared by any one of the following methods:
1) the graphene oxide membrane with the controllable interlayer spacing is prepared by infiltrating a graphene oxide membrane in aqueous solution A of salt containing K + , which entraps K + and ions or molecules with hydrated radii greater than 3.31 Å, but allows water molecules to pass; 2) the graphene oxide membrane with the controllable interlayer spacing is prepared by infiltrating a graphene oxide membrane in aqueous solution A of salt containing Na + , which entraps ions or molecules with hydrated radii greater than 3.58 Å, but allows ions or molecules with a hydrated ionic radius of 3.58 Å or less to pass; 3) the graphene oxide membrane with the controllable interlayer spacing is prepared by infiltrating a graphene oxide membrane in aqueous solution A of salt containing Ca 2+ , which entraps ions or molecules with a hydrated ionic radius greater than 4.12 Å, but allows ions and molecules with a hydrated ionic radius of 4.12 Å or less to pass; 4) the graphene oxide membrane with the controllable interlayer spacing is prepared by infiltrating a graphene oxide membrane in the aqueous solution A of salt containing Li + , which entraps ions or molecules with a hydrated ionic radius greater than 3.82 Å, but allows ions and molecules with a hydrated ionic radius of 3.82 Å or less to pass; or 5) the graphene oxide membrane with the controllable interlayer spacing is prepared by infiltrating a graphene oxide membrane in the aqueous solution A of salt containing Mg 2+ , which entraps ions or molecules with a hydrated ionic radius greater than 4.28 Å, but allows ions and molecules with a hydrated ionic radius of 4.28 Å or less to pass.

11 . The method according to claim 2 , wherein the method for preparing the graphene oxide membrane through the drop-cast method comprises: dropping 0.8˜1.2 mL of 3˜5 mg/mL graphene oxide solution on a paper sheet, after a first drying, rinsing the paper sheet repeatedly with deionized water, and immersing the paper sheet in deionized water for half an hour and then taking the paper sheet out, after a second drying, obtaining the graphene oxide membrane.

12 . The method according to claim 3 , wherein the first drying is performed at 60° C. for 6 hours.

13 . The method according to claim 3 , wherein the second drying is performed at 60° C. for 12 h.

14 . The method of claim 4 , wherein during infiltrating, the ambient temperature is 20° C.

15 . The method of claim 4 , wherein the pH of the aqueous solution is at 7.

16 . The method of claim 5 , wherein in addition to OH − , the anion is one or more of Cl − , F − , Br − , SO 4 2− , and NO 3 − .

17 . The method of claim 5 , wherein in addition to OH − , the anion is one or more of Cl − , F − , and Br − .

Assignees

• Shanghai Inst Applied Physics Cas
• Univ Shanghai
• Nanjing University Of Technology

Inventors

• Fang Haiping
• Wu Minghong
• Shi Guosheng
• Xu Gang
• Chen Liang
• Jin Wanqin
• Shen Jie

Classifications

• B01D2323/50

  Control of the membrane preparation process · CPC title

• B01D2325/42

  Ion-exchange membranes · CPC title

• C01B32/198 Primary

  Graphene oxide · CPC title

• B01D67/0093 Primary

  Chemical modification · CPC title

• B01D71/024

  Oxides · CPC title