Multicomponent inorganic porous materials and methods of making the same

Patent metadata

Field	Value
Publication number	US-11123713-B2
Application number	US-201916452451-A
Country	US
Kind code	B2
Filing date	Jun 25, 2019
Priority date	Jun 25, 2019
Publication date	Sep 21, 2021
Grant date	Sep 21, 2021

Abstract

Provided herein is a method of preparing a porous composite ceramic material and a porous composite ceramic material made by the method of preparing.

First claim

What is claimed:

1. A method of preparing a porous composite ceramic material comprising nanoparticles embedded in an inorganic matrix, comprising:
immersing a block copolymer having polar and nonpolar domains in a swelling solution comprising solvent and one or more nanoparticle precursors, wherein upon immersion in the swelling solution, the block copolymer swells and the nanoparticle precursor adsorbs onto functional groups in the polar domain of the swelled block copolymer to form a nanoparticle precursor infiltrated swelled block copolymer;
exposing the nanoparticle precursor infiltrated swelled block copolymer to a gaseous inorganic matrix material precursor using one or more cycles of sequential infiltration synthesis (SIS) to infiltrate the polar domain with an inorganic matrix material and form an inorganic matrix infiltrated swelled block copolymer;
removing the block copolymer and converting the nanoparticle precursor to nanoparticles by one or more of thermally annealing the inorganic matrix infiltrated swelled block copolymer in the presence of oxygen at a temperature in the range of 300° C. to 700° C., exposing the inorganic matrix infiltrated swelled block copolymer to O 2 plasma, and irradiating the inorganic matrix infiltrated block copolymer with UV light in the presence of ozone, thereby forming the porous composite ceramic material.

2. The method of claim 1 , wherein the polar domain comprises one or more of poly(vinyl-substituted nitrogen heterocycle)s, poly(alkyl (meth)acrylate)s, poly((meth)acrylic acid)s, poly(alkylene oxide)s, poly(arylene oxide)s, poly(arylene sulfide)s, poly(vinyl alkanoates), poly(vinyl ether)s, poly(vinyl halide)s, poly(vinyl alcohol)s, polyurethanes, poly(meth)acrylonitriles, polyesters, polyamides, polyimides, polycarbonates, polysulfones, and polysiloxanes.

3. The method of claim 1 , wherein the non-polar domain comprises one or more of polyolefins, poly(alkenyl aromatic)s, poly(conjugated dienes, hydrogenated poly (conjugated dienes).

4. The method of claim 1 , wherein the block copolymer is immersed in the swelling solution at a temperature of about 50° C. to about 100° C.

5. The method of claim 1 , wherein the nanoparticle precursor comprises a metal complex and the metal complex comprises a transition metal salt.

6. The method of claim 1 , comprising exposing the nanoparticle precursor infiltrated swelled block copolymer to the gaseous inorganic matrix material precursor at a temperature of about 50° C. to about 150° C.

7. The method of claim 1 , wherein the gaseous inorganic matrix material precursor comprises one or more of trimethyl aluminum, AlBr 3 , AlCl 3 , aluminum nitride, aluminum hydroxide, diethyl zinc, (N,N-dimethylamino)trimethylsilane, vinyltrimethoxysilane, trivinylmethoxysilane, tetrakis(dimethylamino)silane, tris(dimethylamino)silane (TDMAS), TiCl 4 , titanium tetraisopropoxide (TTIP), and tetrakis(ethylmethylamino)hafnium.

8. The method of claim 1 , comprising thermally annealing the inorganic matrix infiltrated swelled block copolymer in the presence of oxygen.

9. The method of claim 1 , comprising irradiating the inorganic matrix infiltrated swelled block copolymer with UV light in the presence of ozone.

10. A porous composite ceramic material as prepared by the method of claim 1 .

11. The porous composite ceramic material of claim 10 , wherein the porous composite ceramic material is resistant to sintering at a temperature of up to about 900° C.

12. A method of preparing a porous composite ceramic material comprising nanoparticles embedded in an inorganic matrix, comprising:
immersing nanoparticles and a block copolymer having polar and nonpolar domains in a swelling solution comprising solvent, wherein upon immersion in the swelling solution, the block copolymer swells and the nanoparticles adsorb onto functional groups in the nonpolar domains of the swelled block copolymer to form a nanoparticle infiltrated swelled block copolymer;
exposing the nanoparticle infiltrated swelled block copolymer to a gaseous inorganic matrix material precursor using one or more cycles of sequential infiltration synthesis to infiltrate the polar domains with an inorganic matrix material and form an inorganic matrix infiltrated swelled block copolymer;
removing the block copolymer by one or more of thermally annealing the inorganic matrix infiltrated swelled block copolymer in the presence of oxygen at a temperature in the range of 300° C. to 700° C., exposing the inorganic matrix infiltrated swelled block copolymer to O 2 plasma, and irradiating the inorganic matrix infiltrated swelled block copolymer with UV light in the presence of ozone, to thereby form the porous composite ceramic material.

13. The method of claim 12 , wherein the polar domain comprises one or more of poly(vinyl-substituted nitrogen heterocycle)s, poly(alkyl (meth)acrylate)s, poly((meth)acrylic acid)s, poly(alkylene oxide)s, poly(arylene oxide)s, poly(arylene sulfide)s, poly(vinyl alkanoates), poly(vinyl ether)s, poly(vinyl halide)s, poly(vinyl alcohol)s, polyurethanes, poly(meth)acrylonitriles, polyesters, polyamides, polyimides, polycarbonates, polysulfones, and polysiloxanes.

14. The method of claim 12 , wherein the non-polar domain comprises one or more of polyolefins, poly(alkenyl aromatic)s, poly(conjugated dienes), hydrogenated poly (conjugated dienes).

15. The method of claim 12 , further comprising heating during immersion of the block copolymer in the solvent to a temperature of about 50° C. to about 100° C. during swelling of the block copolymer.

16. The method of claim 12 , wherein the nanoparticles comprise one or more transition metals and transition metal oxides.

17. The method of claim 16 , wherein the nanoparticles comprise one or more of Ag, Au, Pd x O y , Pt x O y , Co x O y , Ru x O y , Mn x O y Fe x O y , and Mg x O y wherein x is from 0.1 to 4 and y is from 0.1 to 7.

18. The method of claim 12 , comprising exposing the nanoparticle infiltrated swelled block copolymer to the gaseous inorganic precursor at a temperature of about 50° C. to about 150° C.

19. The method of claim 12 , wherein the gaseous inorganic matrix material precursor comprises one or more of trimethyl aluminum, AlBr 3 , AlCl 3 , aluminum nitride, aluminum hydroxide, diethyl zinc, (N,N-dimethylamino)trimethylsilane, vinyltrimethoxysilane, trivinylmethoxysilane, tetrakis(dimethylamino)silane, tris(dimethylamino)silane (TDMAS), TiCl 4 , titanium tetraisopropoxide (TTIP), and tetrakis(ethylmethylamino)hafnium.

Assignees

• Uchicago Argonne Llc
• Univ North Texas
• Univ Leland Stanford Junior

Inventors

• Berman Diana
• Shevchenko Elena
• Cargnello Matteo
• Diroll Benjamin
• Goodman Emmett

Classifications

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J2235/00

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

• B01J2235/10

  Infrared [IR] · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J23/75 Primary

  Cobalt · CPC title