Process for preparing a monolith with multimodal porosity

Patent metadata

Field	Value
Publication number	US-11247193-B2
Application number	US-201816608342-A
Country	US
Kind code	B2
Filing date	Apr 23, 2018
Priority date	Apr 28, 2017
Publication date	Feb 15, 2022
Grant date	Feb 15, 2022

Abstract

Process for preparing a porous monolith comprising between 10% and 100% by weight of a semiconductor relative to the total weight of the porous monolith, which process comprises the following steps:a) a first aqueous suspension containing polymer particles is prepared;b) a second aqueous suspension containing particles of least one inorganic semiconductor is prepared;c) the two aqueous suspensions prepared in steps a) and b) are mixed in order to obtain a paste;d) a heat treatment of the paste obtained in step c) is carried out in order to obtain the monolith with multimodal porosity.

First claim

The invention claimed is:

1. A process comprising preparing a porous monolith comprising between 10% and 100% by weight of a semiconductor relative to the total weight of the porous monolith, and comprising a mesoporous volume, the pore diameter of which is between 0.2 and 50 nm, of 0.05 to 1 ml/g, and a macroporous volume, the pore diameter of which is greater than 50 nm and less than or equal to 5000 nm, of between 0.01 and 1 ml/g, which process comprises the following:
a) a first aqueous suspension containing polymer particles is prepared;
b) a second aqueous suspension containing particles of least one inorganic semiconductor is prepared;
c) the two aqueous suspensions prepared in a) and b) are mixed in order to obtain a paste;
d) a heat treatment of the paste obtained in c) is carried out in order to obtain said porous monolith, said heat treatment being carried out under air at a temperature of 300 to 1000° C. for 1 to 72 h.

2. The process as claimed in claim 1 , wherein a heat treatment under air of the paste obtained in c) is carried out by carrying out three temperature plateaus, a first plateau carried out at a temperature of 70 to 130° C. for 1 to 12 h, and a second plateau carried out at a temperature of 130° C. to 220° C. for 1 to 12 h, and a third plateau carried out at a temperature of 250 to 700° C. for 1 to 12 h.

3. The process as claimed in claim 1 , wherein the aqueous suspension obtained in a) contains 20 to 500 g/l of polymer particles.

4. The process as claimed in claim 1 , wherein the aqueous suspension obtained in b) contains 200 to 900 g/l of semiconductor particles.

5. The process as claimed in claim 1 , wherein, in c), the weight ratio between the first aqueous suspension containing the polymer particles and the second aqueous suspension containing the semiconductor particles is 0.05 to 1.

6. The process as claimed in claim 1 , wherein the polymer particles are in the form of spheres with a diameter of 0.1 to 5 μm.

7. The process as claimed in claim 1 , wherein the polymer particles are made of polystyrene.

8. The process as claimed in claim 7 , wherein the polystyrene polymer particles are prepared according to the following:
i) a solution of ethanol and polyvinylpyrrolidone (PVP) is prepared, which solution is degassed under a nitrogen stream for at least one hour, the weight ratio of ethanol to PVP being 50 to 200;
ii) the solution is heated to a temperature of 50 to 90° C.;
iii) a reactive mixture of styrene and of a polymerization initiator is prepared, which mixture is degassed under nitrogen for at least one hour, the weight ratio of styrene to initiator being 30 to 300;
iv) the reactive mixture obtained in iii) is added to the solution obtained in ii) at a temperature of 50 to 90° C., and the mixture obtained is stirred at a temperature of 50 to 90° C. for 1 hour to 48 hours;
v) the suspension obtained in step iv) is washed at least twice with water;
vi) the polymer particles are recovered by filtration or centrifugation.

9. The process as claimed in claim 1 , wherein the inorganic semiconductor is in the form of a powder.

10. The process as claimed in claim 9 , wherein the inorganic semiconductor powder comprises particles with a diameter of 5 to 200 nm.

11. The process as claimed in claim 1 , wherein the semiconductor is a metal oxide.

12. The process as claimed in claim 11 , wherein the metal of the inorganic semiconductor is an element of groups IB, IIB, IVA, VA, VIA, IVB, VB, VIB, VIIIB or IIIA or a mixture thereof.

13. The process as claimed in claim 12 , wherein the semiconductor is Fe 2 O 3 , SnO, SnO 2 , TiO 2 , CoO, NiO, ZnO, Cu 2 O, CuO, Ce 2 O 3 , CeO 2 , In 2 O 3 , WO 3 , V 2 O 5 or a mixture thereof.

14. The process as claimed in claim 1 , wherein the semiconductor is doped with one or more metal elements, non-metal elements, or by a mixture of metal and non-metal elements.

15. The process as claimed in claim 14 , wherein the semiconductor is doped with V, Ni, Cr, Mo, Fe, Sn, Mn, Co, Re, Nb, Sb, La, Ce, Ta, Ti, C, N, S, F, P or a mixture thereof.

Assignees

• Ifp Energies Now

Inventors

• Bernadet Sophie
• Fecant Antoine
• Uzio Denis
• Backov Renal-Vasco
• Ravaine Serge

Classifications

• B01J35/45

  Nanoparticles · CPC title

• B01J35/51

  Spheres · CPC title

• C04B2111/94

  Electrically conducting materials · CPC title

• C04B2235/6567

  Treatment time · CPC title

• C04B2235/3251

  Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof · CPC title