Metal-free few-layer phosphorous nanomaterial: method for its preparation and use thereof

Patent metadata

Field	Value
Publication number	US-12214336-B2
Application number	US-202418442745-A
Country	US
Kind code	B2
Filing date	Feb 15, 2024
Priority date	Jun 15, 2018
Publication date	Feb 4, 2025
Grant date	Feb 4, 2025

Abstract

A method for preparing a metal-free few-layer phosphorous nanomaterial. The method comprises an ice-assisted exfoliation process (or solvent ice-assisted exfoliation process). The method allows for the preparation of a few-layer phosphorous nanomaterial with improved yield and reduced duration and exfoliation power. The few-layer phosphorous nanomaterial is used in the preparation of a photocatalyst. The photocatalyst exhibits a long-term stability, high photocatalytic H2 evolution efficiency from water, and good stability under visible light irradiation.

First claim

The invention claimed is:

1. A method for preparing a few-layer phosphorous nanomaterial, comprising:
(a) providing a bulk layer-structured phosphorous material;
(b) grinding the bulk phosphorous material;
(c) dispersing the grinded material into a first organic solvent to obtain a first dispersion in a sealed vial;
(d) freezing the first dispersion for a period of time using liquid nitrogen, wherein organic solvent molecules are intercalated between layers of the material and interlayers are expanded;
(e) melting the frozen dispersion via ultrasonication for a period of time to obtain a second dispersion, wherein forces are generated between intercalated organic ice crystals and the layers; and
(f) submitting the second dispersion to a separation step, optionally involving centrifugation for a period of time, to obtain the nanomaterial,

wherein the first organic solvent is selected from the group consisting of N-methyl-2-pyrrolidone (NMP), diethyl ether, chloroform, tetrahydrofuran, cyclohexane, toluene, dimethylformamide, and combinations thereof,
and wherein the method is conducted in a glovebox or with nitrogen bubbling.

2. The method according to claim 1 , further comprising:
(g) washing the nanomaterial using a second organic solvent; and
(h) dispersing the nanomaterial into a third organic solvent,

wherein the second and third organic solvents are each independently selected from the group consisting of diethyl ether, chloroform, tetrahydrofuran, cyclohexane, toluene, dimethylformamide, and combinations thereof.

3. The method according to claim 1 , wherein steps (d) and (e) are repeated a number of time, optionally 2 to 6 times, or 3 times, or 4 times.

4. The method according to claim 1 , wherein the freezing time period at step (d) is 3-15 minutes, or 4-14 minutes, or 5-13 minutes, or 5-12 minutes, or 5-11 minutes, or 5-10 minutes, or 6-8 minutes.

5. The method according to claim 1 , wherein the ultrasonication time period at step (e) is 5-15 minutes, or 6-14 minutes, or 7-13 minutes, or minutes 8-12 minutes, or 9-11 minutes, or 10 minutes.

6. The method according to claim 1 , wherein the centrifugation at step (f) is performed at 7000 rpm and the time period is 10-20 minutes, or 12-18 minutes, or 14-16 minutes, or 15 minutes.

7. The method according to claim 1 , wherein the bulk layered structure phosphorous material is black phosphorous (BP), red phosphorous (RP), or violet phosphorous (VP).

8. The method according to claim 1 , wherein the bulk layer-structured phosphorous material is a black phosphorous (BP) material, and the few-layer phosphorous nanomaterial is a few-layer black phosphorous (BP) nanomaterial.

9. The method according to claim 1 , wherein the first organic solvent comprises N-methyl-2-pyrrolidone (NMP).

10. The method according to claim 2 , wherein the second and third organic solvents each independently comprises isopropanol (IPA).

11. The method according to claim 2 , wherein the second and third organic solvents are the same.

12. The method according to claim 2 , wherein the second and third organic solvents are different.

13. The method according to claim 1 , wherein substantially no oxidation occurs.

14. The method according to claim 1 , wherein the few-layer phosphorous nanomaterial is metal-free.

15. The method according to claim 1 , wherein the few-layer phosphorous material has 4 to 10 layers.

Assignees

• Inst Nat Rech Scient

Inventors

• Zhang Qingzhe
• Ma Dongling
• Chaker Mohamed

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J35/39

  Photocatalytic properties · CPC title

• C01P2004/24

  Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01B25/02

  Preparation of phosphorus · CPC title