# US 8,569,391 B2 · Ordered porous mesostructured materials from nanoparticle-block copolymer self-assembly

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- Number: US 8,569,391 B2
- Document ID: US8569391B2
- Status: Granted
- Kind: B2
- Application number: 12/812,714
- Filed: 2009-01-13
- Published: 2011-06-02
- Granted: 2013-10-29
- Earliest claimed: 2008-01-14
- Assignees: Cornell University
- Applicants: Scott Warren; Ulrich Wiesner; Francis J. DiSalvo, Jr.
- Inventors: Scott Warren; Ulrich Wiesner; Francis J. DiSalvo, Jr.
- Web page: https://patentgrep.com/patent/US8569391B2

## CPC

- C08F 297/02: using a catalyst of the anionic type
- B22F 9/02: using physical processes
- C04B 38/0022: {obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors}
- C08F 297/026: {polymerising acrylic acid, methacrylic acid or derivatives thereof}
- C08L 53/00: Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C09D 153/00: Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- B22F 2998/00: Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F 2998/10: Processes characterised by the sequence of their steps
- B22F 2999/00: Aspects linked to processes or compositions used in powder metallurgy
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B22F: WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER (making alloys by powder metallurgy C22C); APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The invention provides mesostructured materials and methods of preparing mesostructured materials including metal-rich mesostructured nanoparticle-block copolymer hybrids, porous metal-nonmetal nanocomposite mesostructures, and ordered metal mesostructures with uniform pores. The nanoparticles can be metal, metal alloy, metal mixture, intermetallic, metal-carbon, metal-ceramic, semiconductor-carbon, semiconductor-ceramic, insulator-carbon or insulator-ceramic nanoparticles, or combinations thereof. A block copolymer/ligand-stabilized nanoparticle solution is cast, resulting in the formation of a metal-rich (or semiconductor-rich or insulator-rich) mesostructured nanoparticle-block copolymer hybrid. The hybrid is heated to an elevated temperature, resulting in the formation of an ordered porous nanocomposite mesostructure. A nonmetal component (e.g., carbon or ceramic) is then removed to produce an ordered mesostructure with ordered and large uniform pores.

## Claims

### Claim 1

A method of preparing a nanocomposite mesostructure which comprises:
(a) providing a block copolymer/ligand-stabilized nanoparticle solution;
(b) casting said solution resulting in the formation of a mesostructured nanoparticle-block copolymer hybrid; and
(c) heating said hybrid in an inert atmosphere to an elevated temperature for pyrolysis, thereby achieving pyrolysis and resulting in the formation of an ordered porous nanocomposite mesostructure,
wherein:
in step (a), the block copolymer/ligand-stabilized nanoparticle solution is a block copolymer/ligand-stabilized metallic nanoparticle solution in which nanoparticles are selected from the group consisting of semiconductor, insulator, metal, metal alloy, metal mixture, and intermetallic nanoparticles or combinations of metal, metal alloy, metal mixture and intermetallic nanoparticles; and
in step (c) the porous nanocomposite mesostructure is a porous semiconductor-carbon, insulator-carbon, or metal-carbon nanocomposite mesostructure.

### Claim 2 (depends on 1)

The method of claim 1 wherein the ligand-stabilized nanoparticle solution comprises metallic nanoparticles, semiconductor nanoparticles, insulator nanoparticles or combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1 wherein said block copolymer includes a hydrophobic portion which comprises sp or sp2 hybridized carbon atoms.

### Claim 4 (depends on 1)

The method of claim 1 wherein the ligand-stabilized metallic nanoparticle further comprises a nonmetallic component selected from the group consisting of a semiconductor and an insulator.

### Claim 5 (depends on 4)

The method of claim 4 wherein the semiconductor is selected from the group consisting of a transition metal oxide, a type IV semiconductor, a type III-V semiconductor and a type II-VI semiconductor.

### Claim 6 (depends on 1)

The method of claim 1 in which following step (c), carbon is removed to produce an ordered porous metal, semiconductor or insulator mesostructure.

### Claim 7 (depends on 6)

The method of claim 6 in which the carbon is removed by the use of a plasma, by acid etch or by heat treatment in air.

### Claim 8 (depends on 1)

The method of claim 1 wherein the ordered porous nanocomposite mesostructure has a unit cell size of ≧10 nm.

### Claim 9 (depends on 1)

The method of claim 1 wherein the ordered porous nanocomposite mesostructure has structural feature sizes of ≧10 nm.

### Claim 10 (depends on 6)

The method of claim 6 wherein the ordered porous metal, semiconductor or insulator mesostructure has a unit cell size of ≧10 nm.

### Claim 11 (depends on 6)

The method of claim 6 wherein the ordered porous metal, semiconductor or insulator mesostructure has structural features sizes of ≧10 nm.

### Claim 12 (depends on 1)

The method of claim 1 in which the ordered porous metal-carbon nanocomposite mesostructure is an ordered porous platinum nanocomposite mesostructure.

### Claim 13 (depends on 12)

The method of claim 12 in which in step (a), the block copolymer/ligand-stabilized nanoparticle solution is a PI-b-PDMAEMA block copolymer-ligand-stabilized platinum nanoparticle solution;
in step (b), casting the solution results in the formation of a platinum rich mesostructured nanoparticle-block copolymer hybrid; and
in step (c), heating the hybrid in the inert atmosphere to the elevated temperature results in the formation of an ordered porous platinum-carbon nanocomposite mesostructure.

### Claim 14 (depends on 13)

The method of claim 13 in which following step (c), the carbon is removed to produce an ordered porous platinum mesostructure.

### Claim 15 (depends on 1)

The method of claim 1 in which the metal is selected from the group consisting of platinum, palladium, gold, silver, copper, rhodium, ruthenium, iridium and bismuth.

### Claim 16 (depends on 1)

The method of claim 1 in which the metal component comprises at least two distinct metals.

### Claim 17 (depends on 16)

The method of claim 16 in which the at least two metals comprise an alloy, a metal mixture or an intermetallic.

### Claim 18 (depends on 1)

The method of claim 1 in which the ligand comprises N,N-di-2-propoxyethyl-N-3-mercaptopropyl-N-methylammonium chloride or N,N-diethoxyethyl-N-methyl-N-3-mercaptopropyl ammonium chloride.

### Claim 19 (depends on 1)

The method of claim 1 in which the nanoparticle has high solubility in organic solvents.

### Claim 20 (depends on 1)

The method of claim 1 in which the nanoparticle has a metal volume fraction of at least 3%.

### Claim 21 (depends on 1)

The method of claim 1 in which the nanoparticle has a semiconductor or insulator volume fraction of at least 3%.

### Claim 22 (depends on 1)

The method of claim 1 in which the nanoparticle has dispersion in a block of the block copolymer from 5-95 vol. %.

### Claim 23 (depends on 1)

The method of claim 1 in which the diameter of the nanoparticle is equal or below the root mean square end-to-end distance relative to the size of the block of the block copolymer with which it mixes.

### Claim 24

A composition comprising an ordered porous metal-carbon nanocomposite mesostructure having:
a unit cell size in the range of about 10 nm to about 80 nm,
metal nanoparticles in a concentration above 5% by volume,
block copolymer-type morphology, and
a high degree of structural order (periodicity) as characterized by analysis of said nanocomposite mesostructure in reciprocal space.

### Claim 25 (depends on 24)

The composition of claim 24 having metal nanoparticles in a concentration above 10% by volume.

### Claim 26

An ordered porous metal mesostructure having:
a pore size in the range of about 5 nm to about 70 nm,
block copolymer-type morphology, and
a high degree of structural order (periodicity) as characterized by analysis of said nanocomposite mesostructure in reciprocal space.

### Claim 27 (depends on 24, 26)

The compositions of claim 24 or 26 wherein the block copolymer-type morphology is selected from the group consisting of cubic micellar, hexagonal cylinder, lamellar, and bicontinuous cubic morphology.

### Claim 28 (depends on 1)

The method of claim 1 wherein the metallic nanoparticle solution comprises metallic nanoparticles made from different metals or from a combination of different metals.

### Claim 29 (depends on 1)

The method of claim 1 wherein the semiconductor is selected from the group consisting of a transition metal oxide, a type IV semiconductor, a type III-V semiconductor and a type II-VI semiconductor.