Universal preparation method for in-situ growth of layered double hydroxide (ldh) layer on substrate surface

Patent metadata

Field	Value
Publication number	US-2024083763-A1
Application number	US-202318211025-A
Country	US
Kind code	A1
Filing date	Jun 16, 2023
Priority date	Sep 9, 2022
Publication date	Mar 14, 2024
Grant date	—

Abstract

The present disclosure provides a universal preparation method for in-situ growth of a layered double hydroxide (LDH) layer on a substrate surface, and belongs to the technical field of material synthesis. In the present disclosure, an LDH protective layer is grown in situ on a surface of a substrate by means of electrodeposition combined with hydrothermal treatment. Specifically, a seed crystal layer of the LDH is formed on the substrate surface by the electrodeposition, and then obtained LDH seed crystals are crystallized and grown by Ostwald ripening through the hydrothermal treatment. In this way, the LDH protective layer is formed in which an interlayer anion is a nitrate. The protective layer protects the substrate against corrosion. Moreover, since the interlayer anion is the nitrate, the protective layer can be exchanged with other corrosion-inhibiting anions, and is modifiable.

First claim

What is claimed is:

1 . A universal preparation method for in-situ growth of a layered double hydroxide (LDH) layer on a substrate surface, comprising the following steps:
(1) mixing a divalent metal nitrate, a trivalent metal nitrate, and water to obtain a mixed solution; (2) constructing a three-electrode system using the mixed solution obtained in step (1) as an electrodeposition solution and a substrate as a working electrode, and conducting electrodeposition to obtain a deposited substrate; (3) mixing the divalent metal nitrate, the trivalent metal nitrate, water, and ammonia water to obtain a hydrothermal reaction solution; and (4) mixing the deposited substrate obtained in step (2) with the hydrothermal reaction solution obtained in step (3), and then conducting a hydrothermal reaction to obtain an LDH protective layer-containing substrate; wherein there is no time sequence between steps (3) and (1).

2 . The method according to claim 1 , wherein in steps (1) and (3), the divalent metal nitrate is one selected from the group consisting of zinc nitrate, magnesium nitrate, cobalt nitrate, nickel nitrate, copper nitrate, and calcium nitrate.

3 . The method according to claim 1 , wherein in steps (1) and (3), the trivalent metal nitrate is selected from the group consisting of aluminum nitrate and iron nitrate.

4 . The method according to claim 1 , wherein in steps (1) and (3), the divalent metal nitrate and the trivalent metal nitrate are at a molar ratio of (2-4): 1 .

5 . The method according to claim 1 , wherein in step (1), the divalent metal nitrate in the mixed solution has a concentration of 40 mmol/L to 50 mmol/L.

6 . The method according to claim 1 , wherein in step (2), the electrodeposition is conducted at a voltage of −1.2 V to −1.4 V for 200 sec to 800 sec.

7 . The method according to claim 1 , wherein in step (3), the hydrothermal reaction solution has a pH value of 8 to 14.

8 . The method according to claim 1 , wherein in step (3), a salt selected from the group consisting of a molybdate, a vanadate, and a dihydrogen phosphate is further added.

9 . The method according to claim 1 , wherein in step (4), the hydrothermal reaction is conducted at 90° C. to 140° C. for 12 h to 24 h.

10 . An LDH protective layer-containing substrate prepared by the method according to claim 1 .

11 . The LDH protective layer-containing substrate according to claim 10 , wherein in steps (1) and (3), the divalent metal nitrate is one selected from the group consisting of zinc nitrate, magnesium nitrate, cobalt nitrate, nickel nitrate, copper nitrate, and calcium nitrate.

12 . The LDH protective layer-containing substrate according to claim 10 , wherein in steps (1) and (3), the trivalent metal nitrate is selected from the group consisting of aluminum nitrate and iron nitrate.

13 . The LDH protective layer-containing substrate according to claim 10 , wherein in steps (1) and (3), the divalent metal nitrate and the trivalent metal nitrate are at a molar ratio of (2-4):1.

14 . The LDH protective layer-containing substrate according to claim 10 , wherein in step (1), the divalent metal nitrate in the mixed solution has a concentration of 40 mmol/L to 50 mmol/L.

15 . The LDH protective layer-containing substrate according to claim 10 , wherein in step (2), the electrodeposition is conducted at a voltage of −1.2 V to −1.4 V for 200 sec to 800 sec.

16 . The LDH protective layer-containing substrate according to claim 10 , wherein in step (3), the hydrothermal reaction solution has a pH value of 8 to 14.

17 . The LDH protective layer-containing substrate according to claim 10 , wherein in step (3), a salt selected from the group consisting of a molybdate, a vanadate, and a dihydrogen phosphate is further added.

18 . The LDH protective layer-containing substrate according to claim 10 , wherein in step (4), the hydrothermal reaction is conducted at 90° C. to 140° C. for 12 h to 24 h.

Assignees

• Univ Shenzhen

Inventors

• Hong Shuxian
• Dong Biqin
• Zeng Lei
• Xing Feng
• Chen Peiyu

Classifications

• C01F7/784 Primary

  Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions · CPC title

• C01F7/66

  Nitrates, with or without other cations besides aluminium · CPC title

• C01P2002/22

  layered hydroxide-type, e.g. of the hydrotalcite-type · CPC title