# US 11,027,260 B2 · Low pressure nanowire membrane for catalytic reactions and methods of making and using the same

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- Number: US 11,027,260 B2
- Document ID: US11027260B2
- Status: Granted
- Kind: B2
- Application number: 16/275,047
- Filed: 2019-02-13
- Published: 2020-08-13
- Granted: 2021-06-08
- Earliest claimed: 2019-02-13
- Assignees: Uchicago Argonne, LLC
- Applicants: Uchicago Argonne, LLC
- Inventors: Xiao-Min Lin; Jiangwei Wen; Kun Wu; Jun Tian
- Web page: https://patentgrep.com/patent/US11027260B2

## CPC

- B01J 23/8926: {Copper and noble metals}
- B01J 35/395: {Thickness of the active catalytic layer}
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/45: Nanoparticles
- B01J 35/58: Fabrics or filaments
- B01J 35/59: Membranes
- B01J 35/60: characterised by their surface properties or porosity
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/0215: {Coating}
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- C07D 249/04: 1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- B01J 2235/05: Nuclear magnetic resonance [NMR]
- B01J 2235/15: X-ray diffraction
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

In embodiments a metal or metal alloy nanowires are assembled into a nanoporous membrane that can be used in methods for catalyzing various reactions under low pressures and achieving high flow rate of the reactions. In embodiments, the membranes of the disclosure can catalyze CuAAC reactions with high efficiency and minimum leaching of active Cu species.

## Claims

### Claim 1

A membrane for a catalyzing flow reactor, comprising:
metal-containing or metal-alloy containing nanowires self-assembled into a porous nanostructure, wherein the porous nanostructure has a thickness of about 10 nm to about 1 cm, and the nanowires have a diameter of about 1 nm to about 500 nm, and an aspect ratio of about 10 to about 100,000, wherein the metal-containing or metal-alloy containing nanowires each comprises an exterior surface arranged so that the metal or metal alloy of the metal-containing or metal-alloy containing nanowires is exposed to one or more reactants during flow of the reactants through the membrane to catalyze a reaction of the one or more reactants through contact with the exposed metal or metal-alloy during flow-through of the reactants through the membrane.

### Claim 2 (depends on 1)

The membrane of claim 1, wherein the nanowires comprise gold-copper alloy.

### Claim 3 (depends on 2)

The membrane of claim 2, wherein the Au/Cu molar ratio is about 1:4 to about 4:1.

### Claim 4 (depends on 1)

The membrane of claim 1, wherein the nanowires comprise one or more of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir, Pt, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, Tc, Cd, Hf, Ta, W, Re, Os, Ir, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, and combinations thereof, and alloys thereof.

### Claim 5 (depends on 1)

The membrane of claim 1, where the nanowires comprise one or more of metal carbides, metal nitrides, metal chalcogenides, and metal oxides.

### Claim 6 (depends on 1)

The membrane of claim 1, wherein the nanostructure comprises a stacked structure of at least two layers of nanowires.

### Claim 7 (depends on 1)

The membrane of claim 1, wherein the nanostructure has a porosity of about 20% to about 80%.

### Claim 8 (depends on 1)

The membrane of claim 1, wherein the nanowires have a branched and/or fractal structure.

### Claim 9 (depends on 1)

A method of catalyzing a reaction under flow conditions, comprising:
flowing a solution comprising one or more reactants through the membrane of claim 1 under a pressure of less than 10 bar and under conditions sufficient to catalyze a reaction of the one or more reactants.

### Claim 10 (depends on 9)

The method of claim 9, wherein the pressure is less than 1 bar.

### Claim 11 (depends on 9)

The method of claim 9, wherein the one or more reactants comprise an azide and an alkyne or wherein the one or more reactants comprises 4-nitrophenol, the method being performed under conditions suitable to reduce the 4-nitrophenol to 4-aminophenol.

### Claim 12 (depends on 11)

The method of claim 11, wherein the alkyne is one or more of 9-ethynylphenanthrene, 3-phenyl-1-propyne, cyclohexylacetylene, and phenylacetylene; and/or the azide is one or more of benzyl azide and dioxaborolane modified azide.

### Claim 13 (depends on 11)

The method of claim 11, wherein the nanostructure comprises copper-gold nanowires.

### Claim 14

A membrane for a catalyzing flow reactor, comprising:
nanowires self-assembled into a porous nanostructure, wherein the nanowires comprise copper, the porous nanostructure has a thickness of about 10 nm to about 1 cm, and the nanowires have a diameter of about 1 nm to about 500 nm, and an aspect ratio of about 10 to about 100,000, wherein the nanowires each comprises one or more copper species arranged on an exterior surface such that the one or more copper species are exposed to one or more reactants during flow of the reactants through the membrane to catalyze a reaction of the one or more reactants through contact with the exposed metal or metal-alloy during flow-through of the reactants through the membrane.
