# US 11,078,148 B2 · Methods for the reduction of carbon dioxide

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- Number: US 11,078,148 B2
- Document ID: US11078148B2
- Status: Granted
- Kind: B2
- Application number: 16/803,027
- Filed: 2020-02-27
- Published: 2020-09-03
- Granted: 2021-08-03
- Earliest claimed: 2019-02-28
- Assignees: University of Louisville Research Foundation, Inc.
- Applicants: University of Louisville Research Foundation, Inc.
- Inventors: Steve P. Cronin; Craig A. Grapperhaus; Robert M. Buchanan; Jacob M. Strain; Joshua M. Spurgeon
- Web page: https://patentgrep.com/patent/US11078148B2

## CPC

- C07C 51/41: Preparation of salts of carboxylic acids ({C07C51/093 - C07C51/34 take precedence} preparation of soap C11D)
- C25B 3/26: of carbon dioxide
- B01J 31/181: {Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine}
- C25B 3/25: Reduction
- B01J 31/1815: {with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine}
- B01J 2531/0238: Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J 2531/26: Zinc
- C07C 53/06: Salts thereof
- C25B 11/043: Carbon, e.g. diamond or graphene
- C25B 11/057: consisting of a single element or compound
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C25B: ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR (anodic or cathodic protection C23F13/00; single-crystal growth C30B)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Some embodiments of the invention include methods of using a compound (e.g., Formula (I)) for the reduction of carbon dioxide to formate by contacting the carbon dioxide with a composition comprising a compound. In certain embodiments, the source of the carbon dioxide is air or is flue gas. Additional embodiments of the invention are also discussed herein.

## Claims

### Claim 1

A method for producing formate from carbon dioxide comprising
contacting carbon dioxide with a composition, where the composition comprises (a) a compound selected from Formula (I), salts, optical isomers, geometric isomers, salts of isomers, derivatives thereof, and solvent associated complexes thereof, (b) a solution solvent, and (c) an acid;
wherein
Formula (I) is
R1 is monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
R2 can be monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
R3 can be monovalent H, halogen, —CN, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
R4 can be monovalent H, halogen, —CN, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which methanoyl (—COH), carboxy (—CO2H), C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C1-C9 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluorinated alkyl, —CF3, —OCF3, or C1-C3 alkoxy;
R3 and R4 are optionally bonded together to form a ring, where the ring that is formed can be cycloalkyl, heterocyclyl, aryl, or heteroaryl, which cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluorinated alkyl, —CF3, —OCF3, or C1-C3 alkoxy; and
M is iron (Fe), nickel (Ni), palladium (Pd), cadmium (Cd), manganese (Mn), cobalt (Co), copper (Cu), gallium (Ga), or zinc (Zn).

### Claim 2 (depends on 1)

The method of claim 1, wherein R1 is monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C7 alkyl, C1-C6 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C7 alkyl, C1-C6 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy.

### Claim 3 (depends on 1)

The method of claim 1, wherein R1 is H, Cl, Br, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), methyl, ethyl, n-propyl, or phenyl.

### Claim 4 (depends on 1)

The method of claim 1, wherein R2 is monovalent H, halogen, —CN, nitro (—NO2), —NH2, —N(CH3)2, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), C1-C7 alkyl, C1-C6 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl, which —NH2, —N(CH3)2, methanoyl (—COH), carboxy (—CO2H), C1-C7 alkyl, C1-C6 alkoxy, cycloalkyl, heterocyclyl, aryl, or heteroaryl can optionally be substituted with one or more of halogen, oxo (═O), hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), nitro (—NO2), —NH2, —N(CH3)2, cyano (—CN), ethynyl (—CCH), propynyl, sulfo (—SO3H), morpholinyl, —CO-morpholin-4-yl, phenyl, —CONH2, —CON(CH3)2, C1-C3 alkyl, C1-C3 perfluoronated alkyl, —CF3, —OCF3, or C1-C3 alkoxy.

### Claim 5 (depends on 1)

The method of claim 1, wherein R2 is H, Cl, Br, hydroxy (—OH), methanoyl (—COH), carboxy (—CO2H), methyl, ethyl, n-propyl, or phenyl.

### Claim 6 (depends on 1)

The method of claim 1, wherein R3 is H, Cl, hydroxy (—OH), methyl, ethyl, C1-5 alkyl, C3 alkyl, —CN, ethynyl, —CONH2, —CON(CH3)2, 2-(morpholinyl)ethoxy, —CO-morpholin-4-yl, ethoxy, methoxy, 5-hydroxy pyridyl, indolyl, 1,2,3,4-tetrahydroisoquinolyl, 1,2-methylenedioxyphenyl, 2,3-methylenedioxyphenyl, furyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-trifluoromethyl phenyl, 3-trifluoromethyl phenyl, 4-trifluoromethyl phenyl, 2-trifluoromethoxy phenyl, 3-trifluoromethoxy phenyl, 4-trifluoromethoxy phenyl, 3,5-dimethoxyphenyl, 3,5-diethoxyphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-dihydroxyphenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, 3,5-bis-trifluoromethyl phenyl, phenyl, naphthyl, tolyl, xylyl, benzyl, pyridyl, 3-pyridyl, methylenedioxyphenyl, perfluorinated methyl, or perfluorinated ethyl.

### Claim 7 (depends on 1)

The method of claim 1, wherein R3 is H, methyl, ethyl, n-propyl, or phenyl.

### Claim 8 (depends on 1)

The method of claim 1, wherein R4 is H, Cl, hydroxy (—OH), methyl, ethyl, C1-5 alkyl, C3 alkyl, —CN, ethynyl, —CONH2, —CON(CH3)2, 2-(morpholinyl)ethoxy, —CO-morpholin-4-yl, ethoxy, methoxy, 5-hydroxy pyridyl, indolyl, 1,2,3,4-tetrahydroisoquinolyl, 1,2-methylenedioxyphenyl, 2,3-methylenedioxyphenyl, furyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-trifluoromethyl phenyl, 3-trifluoromethyl phenyl, 4-trifluoromethyl phenyl, 2-trifluoromethoxy phenyl, 3-trifluoromethoxy phenyl, 4-trifluoromethoxy phenyl, 3,5-dimethoxyphenyl, 3,5-diethoxyphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-dihydroxyphenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, 3,5-bis-trifluoromethyl phenyl, phenyl, naphthyl, tolyl, xylyl, benzyl, pyridyl, 3-pyridyl, methylenedioxyphenyl, perfluorinated methyl, or perfluorinated ethyl.

### Claim 9 (depends on 1)

The method of claim 1, wherein R4 is H, methyl, ethyl, n-propyl, or phenyl.

### Claim 10 (depends on 1)

The method of claim 1, wherein R3 and R4 are bonded together to form cyclobutyl, cyclopentyl, cyclohexyl, chlorocyclohexyl, fluorocyclohexyl, methoxycyclohexyl, ethoxycyclohexyl, methylcyclohexyl, trifluoromethylcyclohexyl, cycloheptyl, cyclooctyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl, piperidyl, piperazinyl, indolinyl, morpholinyl, 5-hydroxy pyridyl, indolyl, 1,2,3,4-tetrahydroisoquinolyl, furyl, 1,2-methylenedioxyphenyl, 2,3-methylenedioxyphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-trifluoromethyl phenyl, 3-trifluoromethyl phenyl, 4-trifluoromethyl phenyl, 2-trifluoromethoxy phenyl, 3-trifluoromethoxy phenyl, 4-trifluoromethoxy phenyl, 3,5-dimethoxyphenyl, 3,5-diethoxyphenyl, 3,5-dimethylphenyl, 3,5-diethylphenyl, 3,5-dihydroxyphenyl, 3,5-difluorophenyl, 3,5-dichlorophenyl, 3,5-bis-trifluoromethyl phenyl, phenyl, naphthyl, tolyl, xylyl, benzyl, pyridyl, 3-pyridyl, or methylenedioxyphenyl.

### Claim 11 (depends on 1)

The method of claim 1, wherein R3 and R4 are not bonded together.

### Claim 12 (depends on 1)

The method of claim 1, wherein M is cadmium (Cd), manganese (Mn), gallium (Ga), or zinc (Zn).

### Claim 13 (depends on 1)

The method of claim 1, wherein M is zinc (Zn).

### Claim 14 (depends on 1)

The method of claim 1, wherein the solution solvent is selected from CH3CN, water, a C1-C8 alcohol, methanol, ethanol, propanol, butanol, n-butanol, pentanol, hexanol, or a combination thereof.

### Claim 15 (depends on 1)

The method of claim 1, wherein the solution solvent is selected from CH3CN, methanol, ethanol, propanol, n-butanol, pentanol, or a combination thereof.

### Claim 16 (depends on 1)

The method of claim 1, wherein the acid has a pKa of no more than about 14.

### Claim 17 (depends on 1)

The method of claim 1, wherein the acid is acetic acid, Et3NHBF4, piperidinium tetrafluoroborate, phosphoric acid, or a combination thereof.

### Claim 18 (depends on 1)

The method of claim 1, wherein the acid is acetic acid.

### Claim 19 (depends on 1)

The method of claim 1, wherein the composition further comprises a hydride source.

### Claim 20 (depends on 1)

The method of claim 1, wherein the composition further comprises a hydride source and the hydride source is a chemical hydride source or an electrochemical hydride source.

### Claim 21 (depends on 1)

The method of claim 1, wherein the composition further comprises a chemical hydride source and the chemical hydride source is a metal hydride, NaBH4, or LiAlH4.

### Claim 22 (depends on 1)

The method of claim 1, wherein the composition further comprises an electrochemical hydride source and the electrochemical hydride source is a platinum (Pt) electrode, a palladium (Pd) electrode, or a glassy carbon electrode.

### Claim 23 (depends on 1)

The method of claim 1, wherein the composition further comprises an electrode.

### Claim 24 (depends on 1)

The method of claim 1, wherein the composition further comprises an electrode and the electrode is a platinum (Pt) electrode, a palladium (Pd) electrode, or a glassy carbon electrode.

### Claim 25 (depends on 1)

The method of claim 1, wherein the temperature of the composition is from 0° C. to 99° C.

### Claim 26 (depends on 1)

The method of claim 1, wherein the source of carbon dioxide is from air, from the waste gas of a powerplant, from the byproduct of a chemical reaction, from the byproduct of a catalytic reaction, or a combination thereof.

### Claim 27 (depends on 1)

The method of claim 1, wherein the source of the carbon dioxide is from a gas and the concentration of carbon dioxide in the gas is from about 0.01% to about 90%.

### Claim 28 (depends on 1)

A method for producing formate from carbon dioxide comprising
(1) contacting carbon dioxide with a first composition to provide a second composition, where the first composition comprises (a) a compound selected from Formula (I), salts, optical isomers, geometric isomers, salts of isomers, derivatives thereof according to claim 1, and solvent associated complexes thereof and (b) a solution solvent, and
(2) adding acid to the second composition to produce formate.