Preparation of layered MXene via elemental halogen etching of MAX phase

Patent metadata

Field	Value
Publication number	US-12054428-B2
Application number	US-202017037883-A
Country	US
Kind code	B2
Filing date	Sep 30, 2020
Priority date	Nov 12, 2019
Publication date	Aug 6, 2024
Grant date	Aug 6, 2024

Abstract

A method of making a layered MXene material comprises a) introducing dried MAX phase powder into a vessel under anhydrous, inert conditions, the MAX phase powder comprising a general formula of M n +1AX n (n=1, 2, 3, or 4), wherein M is a transition metal or p-block metalloid selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Re, Cu, Ni, Ag, Zn, Cd, In, Sn, and Pb; interlayer A is a Group III, IV, or V metalloid selected from the group consisting of Al, Si, Ga, Ge, In, Sn, Pb, As, Bi, Sb, and X is one of C (carbon) and N (nitrogen); b) introducing a halogen and solvent to the dried MAX phase to create a halogen solution having a predetermined concentration; c) allowing a reaction to proceed for about 24 hours between 30-90° C. to create a reaction slurry comprising a MXene material.

First claim

What is claimed is:

1. A method of making a layered MXene material comprising the steps of:
a) introducing a dried MAX phase powder into a vessel under anhydrous, inert conditions, wherein the MAX phase powder comprises a general formula of m n+1 AX n (n=1, 2, 3, or 4),
wherein M is a transition metal or p-block metalloid selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Re, Cu, Ni, Ag, Zn, Cd, In, Sn, and Pb;
interlayer A is a Group III, IV, or V metalloid and is selected from the group consisting of Al, Si, Ga, Ge, In, Sn, Pb, As, Bi, Sb, and
X is one of C (carbon) and N (nitrogen);
b) introducing a halogen and solvent to the dried MAX phase to create a halogen solution having a predetermined concentration;
c) allowing a reaction to proceed for about 24 hours between 30-90° C. to create a reaction slurry comprising a MXene material; and
d) monitoring the reaction to observe interlayer spacing of the MAX phase, wherein the reaction is complete when the ratio of the peak intensities remains constant or when the MAX phase peak disappears;
e) extracting the reaction slurry via addition of anhydrous chloroform, acetone, acetonitrile, or tetrahydrofuran;
f) centrifuging at about 10000 rpm to separate an AX 3 product from the MXene materials;
g) discarding the supernatant containing the AX 3 product, and adding fresh chloroform, acetone, acetonitrile, or tetrahydrofuran and repeating this process as desired, resulting in a MXene slurry.

2. The method of claim 1 , further comprising,
i.) suspending the slurry in a non-polar solvent;
j.) centrifuging at 1000 rpm for 1 hour to sediment any un-exfoliated MAX phase materials;
k.) collecting the supernatant which contains MXene flakes.

3. The method of claim 2 , further comprising,
l.) Quenching or extracting excess halogen with a Lewis base.

4. The method claim 1 , wherein the halogen and solvent of step b) are at least one of non-polar solvents selected from the group consisting of cyclohexane, benzene, toluene, xylenes, naphtha, anthrazene, carbon disulfide, chloroform, and dichloromethane, or polar solvents selected from the group consisting of methanol and acetonitrile, with at least one of iodine (I 2 ) and bromine (Br 2 ) to create a 15-25 wt % halogen solution.

5. The method of claim 4 , wherein the time period of about 24 hours is anywhere between 1 and 36 hours, and when bromine (Br 2 ) is selected the temperature of about 35° C. is anywhere between 30-90° C.

6. The method of claim 2 , wherein the non-polar solvent is at least one of THF (tetrahydrofuran), acetonitrile, and CHCl 3 .

7. The method of claim 2 , wherein the non-polar solvent is at least one of CS 2 , CHCl 3 , cyclohexane, and benzene, with the addition of tetrabutylammonium halide (TBAX; X═F, Cl, Br, I) stabilizer comprising a non-nucleophilic, coordinating Lewis base.

8. The method of claim 1 , wherein introducing a halogen of step b) further comprises:
b1) introducing elemental X 2 , wherein X═F, Cl, Br, or I.

9. The method of claim 1 , wherein introducing a halogen of step b) further comprises:
b1) introducing an in-situ halogen generating species.

10. The method of claim 1 , wherein introducing a halogen of step b) further comprises:
b1) introducing one or more solid state organo or inorganic halogen precursors, such as PX 5 , PX 3 (X═Cl, Br), N-bromohalides (NBX; X═Cl, Br, I).

11. The method of claim 1 , wherein introducing a halogen of step b) further comprises:
b1) introducing one or more mixed halogen species selected from the group consisting of iodine monochloride, iodine monobromide, and bromine monochloride.

12. The method of claim 1 , wherein an etching rate of the A-interlayer is tunable by changing reactant concentrations of 5-20 vol % X, where X═Cl, Br, I and operating temperatures of −70° C. to 80° C. in step c.

Assignees

• Us Gov Air Force
• Us Air Force

Inventors

• Jawaid Ali M
• Vaia Richard A
• Hassan Asra

Classifications

• C01P2002/20

  Two-dimensional structures · CPC title

• C01B32/90

  Carbides · CPC title

• C01B21/0602 Primary

  with two or more other elements chosen from metals, silicon or boron · CPC title

• C04B41/009

  characterised by the material treated · CPC title

• C04B2235/74

  Physical characteristics · CPC title