Lanthanide fluoride two-dimensional porous nanosheets, and preparation method and applications thereof

• US 10,604,417 B2
• Filed: 06/28/2019
• Issued: 03/31/2020
• Est. Priority Date: 02/09/2018
• Status: Active Grant

• Current Assignee: Tianjin Polytechnic University
• Original Assignee: Tianjin Polytechnic University
• Inventors: Zhang, Yuzhong, Zhang, Leitao, Li, Hong
• Primary Examiner(s): Hailey, Patricia L.
• Application Number:
  US16/457,892
• Publication Number:
  US 20190322541A1
• Time in Patent Office: 277 Days
• Field of Search: 502224, 977700, 977755, 977758
• CPC Class Codes: B01D 2253/10 Inorganic adsorbents
• CPC Class Codes: B01D 2253/112 Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
• CPC Class Codes: B01D 2253/304 Linear dimensions, e.g. particle shape, diameter
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01J 20/0207 Compounds of Sc, Y or Lanthanides
• CPC Class Codes: B01J 20/027 Compounds of F, Cl, Br, I
• CPC Class Codes: B01J 20/28007 with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like carbon nanostructures B01J20/205
• CPC Class Codes: B01J 20/28016 Particle form
• CPC Class Codes: B01J 20/28033 Membrane, sheet, cloth, pad, lamellar or mat
• CPC Class Codes: B01J 20/2808 being less than 2 nm, i.e. micropores or nanopores
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 27/12 Fluorides
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/643 less than 2 nm
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/26 Fluorinating
• CPC Class Codes: B82Y 30/00 : Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 : Manufacture or treatment of nanostructures
• CPC Class Codes: C01F 17/265 : Fluorides
• CPC Class Codes: C01P 2002/77 : by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/04 : obtained by TEM, STEM, STM or AFM
• CPC Class Codes: C01P 2004/24 : Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
• CPC Class Codes: C01P 2004/64 : Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/16 : Pore diameter
• CPC Class Codes: C01P 2006/17 : Pore diameter distribution
• CPC Class Codes: H01M 4/582 : Halogenides
• CPC Class Codes: H01M 50/431 : Inorganic material
• CPC Class Codes: Y02E 60/10 : Energy storage using batteries

Abstract

The present application provides a method for preparing lanthanide fluoride two-dimensional porous nanosheets and belongs to the field of novel materials. In the present application, mixing a water-soluble lanthanide metal salt and an aqueous solution of sodium acetate in a nitrogen atmosphere to obtain a mixed solution, and adding an aqueous solution of fluorine-containing salt to the mixed solution obtained for precipitation reaction to produce lanthanide fluoride two-dimensional porous nanosheets. In the preparation process provided by the present application, no additional surfactant or template agent needs to be added, the pollution of the surfactant to the surface of the prepared material is avoided and the tedious after-treatment steps to template agent are reduced. Accordingly, the large-scale production can be realized, and the lanthanide fluoride two-dimensional porous nanosheets constructed by nanoparticles are prepared in large scale by one step. Moreover, no other organic solvents are required, and the pollution to the environment during the preparation process is avoided.

Claims

1. A method for preparing lanthanide fluoride two-dimensional porous nanosheets, comprising the following steps of:

(1) mixing a water-soluble lanthanide metal salt and an aqueous solution of sodium acetate in a nitrogen atmosphere to obtain a mixed solution; and

(2) adding an aqueous solution of fluorine-containing salt to the mixed solution obtained in the step (1) for precipitation reaction to produce lanthanide fluoride two-dimensional porous nanosheets.

2. The method according to claim 1, wherein

the water-soluble lanthanide metal salt in the step (1) comprises one or more of nitrates, chlorates, chlorides and acetates of lanthanides.

3. The method according to claim 2, wherein

the water-soluble lanthanide metal salt is selected from the group consisting of cerium nitrate, cerium acetate, praseodymium chloride, lanthanum chlorate, neodymium chloride, ytterbium nitrate, erbium nitrate, praseodymium nitrate, neodymium nitrate, cerium chloride, praseodymium chlorate and mixtures thereof.

4. The method according to claim 3, wherein the mixtures are a mixture of cerium nitrate and praseodymium nitrate, a mixture of cerium nitrate, neodymium nitrate and erbium nitrate, a mixture of cerium chloride, praseodymium chlorate and erbium nitrate, or a mixture of lanthanum chlorate, cerium nitrate and neodymium nitrate.

5. The method according to claim 4, wherein a molar ratio of the water-soluble lanthanide metal salt to the sodium acetate is in a range of 1:

1 to 1;

10.

6. The method according to claim 3,

wherein a molar ratio of the water-soluble lanthanide metal salt to the sodium acetate is in a range of 1:

1 to 1;

10.

7. The method according to claim 2, wherein a molar ratio of the water-soluble lanthanide metal salt to the sodium acetate is in a range of 1:

1 to 1;

10.

8. The method according to claim 1, wherein a molar ratio of the water-soluble lanthanide metal salt to the sodium acetate is in a range of 1:

1 to 1;

10.

9. The method according to claim 1, wherein a concentration of the aqueous solution of fluorine-containing salt in the step (2) is in a range of 5 to 100 mg/mL.

10. The method according to claim 9, wherein a molar ratio of the fluorine in the aqueous solution of fluorine-containing salt to the lanthanide in the mixed solution in the step (2) is in a range of 0.1-10:

1.

11. The method according to claim 9, wherein the fluorine-containing salt in the step (2) comprises one or more of ammonium fluoride, sodium fluoride, potassium fluoride, potassium fluoroborate, potassium fluorosilicate and tetrabutylammonium fluoride.

12. The method according to claim 1, wherein a molar ratio of the fluorine in the aqueous solution of fluorine-containing salt to the lanthanide in the mixed solution in the step (2) is in a range of 0.1-10:

1.

13. The method according to claim 1, wherein the fluorine-containing salt in the step (2) comprises one or more of ammonium fluoride, sodium fluoride, potassium fluoride, potassium fluoroborate, potassium fluorosilicate and tetrabutylammonium fluoride.

14. The method according to claim 1, wherein a time for the precipitation reaction in the step (2) is in a range of 0.5 h to 24 h.

15. Lanthanide fluoride two-dimensional porous nanosheets prepared by the method of claim 1, wherein the lanthanide fluoride two-dimensional porous nanosheets comprise alternately stacked fluorine-lanthanide metal monoatomic layers and interlayer acetates, and an average pore diameter of the lanthanide fluoride two-dimensional porous nanosheets is in a range of 0.1 to 30 nm.

16. The lanthanide fluoride two-dimensional porous nanosheets according to claim 15, wherein the average pore diameter of the lanthanide fluoride two-dimensional porous nanosheets is in a range of 0.1 to 10 nm.

17. The lanthanide fluoride two-dimensional porous nanosheets according to claim 15, wherein the lanthanide fluoride two-dimensional porous nanosheets comprise nanoparticles of 0.5-20 nm in diameter.

18. The lanthanide fluoride two-dimensional porous nanosheets according to claim 16, wherein the lanthanide fluoride two-dimensional porous nanosheets comprise assembled nanoparticles of 0.5-20 nm in diameter.