Method for the production of new nanomaterials

Patent metadata

Field	Value
Publication number	US-10960385-B2
Application number	US-201616066025-A
Country	US
Kind code	B2
Filing date	Dec 22, 2016
Priority date	Dec 23, 2015
Publication date	Mar 30, 2021
Grant date	Mar 30, 2021

Abstract

A method for producing new nanomaterials, 80 to 100 mol % of which are composed of TiO 2 and 0 to 20 mol % are composed of another metal or semi-metal oxide that has a specific surface of 100 to 300 m 2 ·g −1 and 1 to 3 hydroxyl groups per nm 2 .

First claim

The invention claimed is:

1. Method of preparing a nanomaterial containing 80 to 100 mole % of TiO 2 and 0 to 20 mole % of another metal or semi-metal oxide chosen particularly from among SiO 2 , ZrO 2 , WO 3 , ZnO, Al 2 O 3 and Fe 2 O 3 , with a specific surface area of between 100 and 300 m 2 ·g −1 and from 1 to 3 hydroxyl groups per nm 2 , said method including the following steps:
a) Synthesis of a material composed of 80 to 100 mole % of TiO 2 and 0 to 20 mole % of another oxide starting from a titanium oxide precursor or a mix of a titanium oxide precursor and a precursor of another oxide, the synthesis being made in an aqueous medium with a pH between 0 and 1 and at a temperature varying from 40 to 95° C. in the presence of a non-ionic surfactant chosen from among ankenyl ethers of polyoxyethylene glycol and poloxamers;
b) Elimination of the surfactant from the material synthesised in the previous step by the following steps:
b1) Preparation of a metallised material by washing the material containing the surfactant with an aqueous solution of a bivalent metal salt and an aqueous solution of ammonia,
b2) Recovery of firstly the metallised material and secondly a washing solution,
b3) Treatment of the metallised material with an inorganic acid to remove the metal from the material,
c) Recovery of firstly a nanomaterial with no surfactant and secondly a residual solution.

2. Method according to claim 1 , in which the material synthesis step a) comprises the following steps:
a1) preparing an acid aqueous solution of the non-ionic surfactant,
a2) adding the titanium oxide precursor or the mixture of the titanium oxide precursor and the precursor of the other oxide to the acid aqueous solution of the non-ionic surfactant, and a precipitate then forms,
a3) vigorously stiring the reaction medium so as to dissolve the precipitate formed in step a2) then polymerising the titanium oxide precursor or the mixture of the titanium oxide precursor and the precursor of the other oxide,
a4) placing the reaction mixture from step a3) under static conditions for at least 24 h, and then
a5) recovering firstly a material composed of 80 to 100 mole % TiO2 and 0 to 20 mole % of the other oxide, and secondly a residual solution.

3. Method according to claim 1 , in which step b) is performed in situ.

4. Method according to claim 1 , in which the bivalent metal salt is chosen from salts of copper (II), cobalt (II), nickel (II) and zinc (II).

5. Method according to claim 1 , in which the other oxide is chosen from SiO 2 and ZrO 2 .

6. Method according to claim 1 , in which the nanomaterial is composed of 100 mole % of TiO 2 .

7. Nanomaterial obtainable by the method according to claim 1 composed of 80 to 100 mole % of TiO 2 and 0 to 20 mole % of another metal or semi-metal oxide chosen from among SiO 2 , ZrO 2 , WO 3 , ZnO and Al 2 O 3 and Fe 2 O 3 , particularly among SiO 2 and ZrO 2 , with
divalent metal cations adsorbed on the surface of the nanomaterial,
surface acidity, coming from step b) of the method,
nitrate ions,
a specific surface area between 100 and 300 m 2 ·g −1 ,
from 1 to 3 hydroxyl groups per nm 2 ,
a pH equal to between 3 and 5
and having a rutile nanocrystalline structure when it composed of 100 mole % of TiO 2 .

8. Nanomaterial according to claim 7 , characterised in that is composed of 80 to 95 mole % of TiO 2 and 5 to 20 mole % of another metal or semi-metal oxide chosen from SiO 2 , ZrO 2 , WO 3 , ZnO and Al 2 O 3 and Fe 2 O 3 , and particularly from SiO 2 and ZrO 2 .

9. A method for the photocatalytic degradation of compounds, comprising bringing the nanomaterial according to claim 7 into contact with a solution containing the compounds and exposing the solution and nanomaterial to at least one of UV radiation and visible radiation thereby to degrade compounds adsorbed onto the surface of the nanomaterial.

10. The method according to claim 9 , characterised in that the compounds are chosen from dyes, pharmaceutical active constituents, herbicides, pesticides, fungicides, hormones, saccharides, such as glucose, and/or hydrocarbons.

11. Nanomaterial according to claim 7 , characterised in that the metal cations are chosen from Zn 2+ , Ni 2+ or Cu 2+ .

Assignees

• Commissariat Energie Atomique
• Univ De Cergy Pontoise

Inventors

• Pasternak Nicolas
• Linder Nancy

Classifications

• B01J2235/00

  Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J2235/10

  Infrared [IR] · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title