# US 2013/0158322 A1 · Polymer templated nanowire catalysts

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- Number: US 2013/0158322 A1
- Document ID: US20130158322A1
- Status: Published application
- Kind: A1
- Application number: 13/689,514
- Filed: 2012-11-29
- Published: 2013-06-20
- Earliest claimed: 2011-11-29
- Assignees: Siluria Technologies, Inc.
- Inventors: Greg Nyce; Erik C. Scher; Fabio R. Zurcher; Joel M. Cizeron; Wayne P. Schammel; Joel Gamoras; Anja Rumplecker; Jarod McCormick; Marian Alcid
- Web page: https://patentgrep.com/patent/US20130158322A1

## CPC

- C07C 2/84: catalytic
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 21/10: Magnesium; Oxides or hydroxides thereof
- B01J 23/02: of the alkali- or alkaline earth metals or beryllium
- B01J 23/04: Alkali metals
- B01J 23/10: of rare earths
- B01J 23/22: Vanadium
- B01J 23/30: Tungsten
- B01J 23/34: Manganese
- B01J 35/45: Nanoparticles
- B01J 35/58: Fabrics or filaments
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/031: {Precipitation}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/10: in the presence of water, e.g. steam
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- C01F 5/02: Magnesia
- C01F 5/08: by calcining magnesium hydroxide
- C01F 5/14: Magnesium hydroxide
- C01F 17/206: oxide or hydroxide being the only anion
- C01F 17/224: Oxides or hydroxides of lanthanides
- C01F 17/229: Lanthanum oxides or hydroxides
- C01F 17/241: containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
- C01G 25/02: Oxides
- C01G 31/02: Oxides
- C01G 45/022: Manganese monoxide
- C01G 45/026: Dimanganese trioxide
- C01G 45/028: Trimanganese tetraoxide
- C01G 45/1221: Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C07C 11/04: Ethene
- C01P 2002/52: containing elements as dopants
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/16: Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
- C01P 2004/54: Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/12: Surface area
- C07C 2521/06: Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C 2521/10: Magnesium; Oxides or hydroxides thereof
- C07C 2523/02: of the alkali- or alkaline earth metals or beryllium
- C07C 2523/04: Alkali metals
- C07C 2523/10: of rare earths
- C07C 2523/22: Vanadium
- C07C 2523/30: Tungsten
- C07C 2523/34: Manganese
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y10S 977/762: Nanowire or quantum wire, i.e. axially elongated structure having two dimensions of 100 nm or less
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

Nanowires useful as heterogeneous catalysts are provided. The nanowire catalysts are prepared by polymer templated methods and are useful in a variety of catalytic reactions, for example, the oxidative coupling of methane to ethane and/or ethylene. Related methods for use and manufacture of the same are also disclosed.

## Claims

### Claim 1

A method for preparing a nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the method comprising:
a) providing a solution comprising a plurality of polymer templates;
(b) introducing at least one metal ion and at least one anion to the solution under conditions and for a time sufficient to allow for nucleation and growth of a nanowire comprising a plurality of metal salts (MmXnZp) on the template; and
(c) optionally converting the nanowire (MmXnZp) to a metal oxide nanowire comprising a plurality of metal oxides (MxOy), metal oxy-hydroxides (MxOyOHz), metal oxycarbonates (MxOy(CO3)z), metal carbonate (Mx(CO3)y) or combinations thereof
wherein:
M is, at each occurrence, independently a metal element from any of Groups 1 through 7, lanthanides or actinides;
X is, at each occurrence, independently hydroxide, carbonate, bicarbonate, phosphate, hydrogenphosphate, dihydrogenphosphate, sulfate, nitrate or oxalate;
Z is O;
n, m, x and y are each independently a number from 1 to 100; and
p is a number from 0 to 100.

### Claim 2 (depends on 1)

The method of claim 1, wherein the polymer template comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene glycol)-polypropylene glycol)-poly(ethylene glycol) or copolymers or combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1, further comprising freeze drying the nanowire.

### Claim 4 (depends on 1)

The method of claim 1, wherein the solution comprising the polymer template is in the form of a gel.

### Claim 5 (depends on 4)

The method of claim 4, further comprising a step of base treatment and precipitating at least one metal.

### Claim 6 (depends on 1)

The method of claim 1, further comprising use of two or more different metal ions.

### Claim 7

A method for preparing a nanowire comprising a metal oxide, a metal oxy-hydroxide, a metal oxycarbonate or a metal carbonate, the method comprises:
a) providing a solution comprising a plurality of a multifunctional coordinating ligands;
(b) introducing at least one metal ion to the solution, thereby forming a metal ion-ligand complex; and
(c) introducing a polyalcohol to the solution, wherein the polyalcohol polymerizes with the metal-ion ligand complex to form a polymerized metal ion-ligand complex.

### Claim 8 (depends on 7)

The method of claim 7, wherein the multifunctional coordinating ligand is an alpha-hydroxycarboxylic acid.

### Claim 9 (depends on 8)

The method of claim 8, wherein the multifunctional coordinating ligand is citric acid.

### Claim 10 (depends on 7)

The method of claim 7, wherein the polyalcohol is ethylene glycol or glycerol.

### Claim 11 (depends on 7)

The method of claim 7 further comprising heating the polymerized metal ion-ligand complex to remove substantially all organic material.

### Claim 12 (depends on 7)

The method of claim 7 further comprising heating the polymerized metal ion-ligand complex to obtain a metal oxide.

### Claim 13

A method for preparing metal oxide, metal oxy-hydroxide, metal oxycarbonate or metal carbonate catalytic nanowires in a core/shell structure, the method comprising:
(a) providing a solution that includes a plurality of polymer templates;
(b) introducing a first metal ion and a first anion to the solution under conditions and for a time sufficient to allow for nucleation and growth of a first nanowire (M1m1X1n1Zp1) on the template; and
(c) introducing a second metal ion and optionally a second anion to the solution under conditions and for a time sufficient to allow for nucleation and growth of a second nanowire (M2m2X2n2Zp2) on the first nanowire (M1m1X1n1Zp1);
(d) converting the first nanowire (M1m1X1n1Zp1) and the second nanowire (M2m2X2n2Zp2) to the respective metal oxide nanowires (M1x1Oy1) and (M2x2Oy2), the respective metal oxy-hydroxide nanowires (M1x1Oy1OHz1) and (M2x2Oy2OHz2) the respective metal oxycarbonate nanowires (M1x1Oy1(CO3)z1) and (M2x2Oy2(CO3)z2) or the respective metal carbonate nanowires (M1x1(CO3)y1) and (M2x2(CO3)y2),
wherein:
M1 and M2 are the same or different and independently selected from a metal element;
X1 and X2 are the same or different and independently hydroxide, carbonate, bicarbonate, phosphate, hydrogenphosphate, dihydrogenphosphate, sulfate, nitrate or oxalate;
Z is O;
n1, m1n2, m2, x1, y1, z1, x2, y2 and z2 are each independently a number from 1 to 100; and
p1 and p2 are independently a number from 0 to 100.

### Claim 14 (depends on 13)

The method of claim 13, wherein the polymer template comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers or combinations thereof.

### Claim 15 (depends on 13)

The method of claim 13, wherein M1 and M2 are different.

### Claim 16

A method for preparing a catalytic nanowire, the method comprising:
admixing (A) with a mixture comprising (B) and (C);
admixing (B) with a mixture comprising (A) and (C); or
admixing (C) with a mixture comprising (A) and (B)
to obtain a mixture comprising (A), (B) and (C), wherein (A), (B), and (C) comprise, respectively:
(A) a polymer template;
(B) one or more salts comprising one or more elements selected from Groups 1 through 7, lanthanides and actinides and hydrates thereof; and
(C) one or more anion precursors.

### Claim 17 (depends on 16)

The method of claim 16, wherein the mixture comprising (B) and (C) has been prepared by admixing (B) and (C), the mixture comprising (A) and (C) has been prepared by admixing (A) and (C) or the mixture comprising (A) and (B) has been prepared by admixing (A) and (B).

### Claim 18 (depends on 16)

The method of claim 16, wherein the one or more salts comprise chlorides, bromides, iodides, nitrates, sulfates, acetates, oxides, oxalates, oxyhalides, oxynitrates, phosphates, hydrogenphosphate, dihydrogenphosphate or mixtures thereof.

### Claim 19 (depends on 16)

The method of claim 16, wherein the one or more salts comprise MgCl2, LaCl3, ZrCl4, WCl4, MoCl4, MnCl2MnCl3, Mg(NO3)2, La(NO3)3, ZrOCl2, Mn(NO3)2, Mn(NO3)3, ZrO(NO3)2, Zr(NO3)4 or mixtures thereof.

### Claim 20 (depends on 16)

The method of claim 16, wherein the one or more salts comprise Mg, Ca, Mg, W, La, Nd, Sm, Eu, W, Mn, Zr or mixtures thereof.

### Claim 21 (depends on 16)

The method of claim 16, wherein the one or more anion precursors comprises alkali metal hydroxides, alkaline earth metal hydroxides, carbonates, bicarbonates, ammonium hydroxides, or mixtures thereof.

### Claim 22 (depends on 21)

The method of claim 21, wherein the one or more anion precursors comprises LiOH, NaOH, KOH, Sr(OH)2, Ba(OH)2, Na2CO3, K2CO3, NaHCO3, KHCO3, and NR4OH, wherein R is selected from H, and C1-C6 alkyl.

### Claim 23 (depends on 16)

The method of claim 16, wherein the polymer template comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene glycol)-polypropylene glycol)-poly(ethylene glycol) or copolymers or combinations thereof.

### Claim 24 (depends on 16)

The method of claim 16, further comprising allowing the mixture comprising (A), (B), and (C) to stand at a temperature of from about 4° C. to about 80° C. for a period of time sufficient to allow nucleation of the catalytic nanowires

### Claim 25 (depends on 16)

The method of claim 16, further comprising adding a doping element comprising metal elements, semi-metal elements, non-metal elements or combinations thereof to the mixture comprising (A), (B), and (C).

### Claim 26 (depends on 16)

The method of claim 16, further comprising calcining the nanowires.

### Claim 27 (depends on 26)

The method of claim 26, wherein calcining the nanowires comprises heating the nanowires at 450° C. or greater for at least 60 min.

### Claim 28 (depends on 16)

The method of claim 16, further comprising doping the nanowires, wherein doping the nanowires comprises contacting the nanowires with a solution comprising a dopant and evaporating any excess liquid, wherein the dopant comprises a metal element, a semi-metal element, a non-metal element or combinations thereof.

### Claim 29

A method for preparing metal oxide nanowires, the method comprising:
(a) providing a solution comprising a plurality of polymer templates; and
(b) introducing a compound comprising a metal to the solution under conditions and for a time sufficient to allow for nucleation and growth of a nanowire (MmYn) on the template;
wherein:
M is a metal element from any of Groups 1 through 7, lanthanides or actinides;
Y is O,
n and m are each independently a number from 1 to 100.

### Claim 30 (depends on 29)

The method of claim 29, wherein the polymer template comprises PVP (polyvinlpyrrolidone), PVA (polyvinylalcohol), PEI (polyethyleneimine), PEG (polyethyleneglycol), polyethers, polyesters, polyamides, dextran, sugar polymers, functionalized hydrocarbon polymers, functionalized polystyrene, polylactic acid, polycaprolactone, polyglycolic acid, poly(ethylene glycol)-poly(propylene glycol)-poly(ethylene glycol) or copolymers or combinations thereof.

### Claim 31 (depends on 1)

A nanowire prepared according to the method of claim 1.

### Claim 32 (depends on 31)

A catalytic material comprising the nanowire of claim 31.

### Claim 33 (depends on 31)

A method for the preparation of a downstream product of ethylene, the method comprising converting methane into ethylene in the presence of the nanowire of claim 31 and further oligomerizing the ethylene to prepare a downstream product of ethylene.

### Claim 34 (depends on 31)

A process for the preparation of ethylene from methane comprising contacting a mixture comprising oxygen and methane at a temperature below 900° C. with the nanowire of claim 31.

### Claim 35 (depends on 16)

The method of any of claim 16, wherein the polymer template is functionalized with at least one of amine, carboxylic acid, sulfate, alcohol or thiol groups.

### Claim 36 (depends on 35)

The method of claim 35, wherein the polymer template comprises a hydrocarbon polymer or a polystyrene polymer.