# US 9,435,042 B2 · System and method for selective electrochemical reduction of carbon dioxide employing an anodized silver electrode

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,435,042 B2
- Document ID: US9435042B2
- Status: Granted
- Kind: B2
- Application number: 14/523,070
- Filed: 2014-10-24
- Published: 2016-04-28
- Granted: 2016-09-06
- Earliest claimed: 2014-10-24
- Assignees: Toyota Motor Engineering & Manufacturing North America, Inc.
- Applicants: Toyota Motor Engineering & Manufacturing North America, Inc.
- Inventors: Li Qin Zhou; Chen Ling; Hongfei Jia
- Web page: https://patentgrep.com/patent/US9435042B2

## CPC

- C25B 11/051: Electrodes formed of electrocatalysts on a substrate or carrier
- C25B 1/00: Electrolytic production of inorganic compounds or non-metals
- C25B 1/23: Carbon monoxide or syngas
- C25B 11/057: consisting of a single element or compound
- C25B 11/081: the element being a noble metal
- Y02E 60/36: Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Systems and methods for the electrochemical reduction of carbon dioxide are disclosed. The systems involve an electrochemical cell having a cathode of anodized silver and the methods involve introducing carbon dioxide into such a system and applying a potential. The disclosed systems and methods have improved carbon monoxide production selectivity, support higher current density, and have improved efficiency in comparison to existing silver-based CO2 electroreduction devices.

## Claims

### Claim 1

A method for electrochemical reduction of carbon dioxide, the method comprising:
anodizing a precursor electrode containing elemental silver at constant electric potential to produce an anodized silver component;
providing an electrochemical cell having:
a cathode chamber containing:
a catholyte; and
a cathode in contact with the catholyte, the cathode containing the anodized silver component; and
an anode chamber containing:
an anolyte; and
an anode in contact with the anolyte;
supplying carbon dioxide to the cathode chamber; and
applying a potential between the anode and the cathode, the potential sufficient to electrochemically reduce carbon dioxide present in the cathode chamber.

### Claim 2 (depends on 1)

The method as recited in claim 1, wherein a surface of the cathode is characterized by an x-ray diffraction pattern having a peak centered at about 118° and a peak centered at about 43°; and wherein a ratio of intensity of the peak centered at about 118° to intensity of the peak centered at about 43° is at least 1:1.

### Claim 3 (depends on 1)

The method as recited in claim 1, wherein the cathode chamber further includes a gas input member, the gas input member configured to supply a stream of gas to the catholyte, the stream of gas including carbon dioxide.

### Claim 4 (depends on 1)

The method as recited in claim 1, wherein the catholyte, the anolyte, or both is an aqueous solution of at least one electrolytic salt, the electrolytic salt comprising an alkali metal or alkaline earth metal salt of carbonate or bicarbonate, nitrate, nitrite, sulfate, sulfite, or phosphate.

### Claim 5 (depends on 1)

The method as recited in claim 1, wherein the electrochemical reduction of carbon dioxide results in production of carbon monoxide and production of hydrogen gas in the cathode chamber; wherein the method is characterized by a CO selectivity, the CO selectivity definable as a percent molar ratio of carbon monoxide to hydrogen gas produced; and wherein the CO selectivity is at least 50%.

### Claim 6 (depends on 5)

The method as recited in claim 5, wherein the CO selectivity is greater than 60%.

### Claim 7 (depends on 1)

The method as recited in claim 1, wherein the anodizing step is characterized by a multiplication product of the constant electric potential and a duration of time for which the constant electric potential is applied; and wherein said multiplication product is at least 3.75 V•min relative to Ag/AgCl.

### Claim 8 (depends on 7)

The method as recited in claim 7, wherein the multiplication product of the constant electric potential and the duration of time is at least 7.5 V•min relative to Ag/AgCl.

### Claim 9

A method for making an electrochemical cell for electrochemically reducing carbon dioxide, the method comprising:
anodizing a precursor electrode comprising elemental silver at a constant electric potential to produce an anodized silver component;
preparing a cathode chamber containing:
a catholyte; and
a cathode in contact with the catholyte, the cathode containing the anodized silver component; and
placing an anode chamber in ionic contact with the cathode chamber, the anode chamber containing:
an anolyte; and
an anode in contact with the anolyte.

### Claim 10 (depends on 9)

An electrochemical cell produced by the method of claim 9.

### Claim 11 (depends on 10)

The electrochemical cell as recited in claim 10, wherein a surface of the cathode is characterized by an x-ray diffraction pattern having a peak centered at about 118° and a peak centered at about 43°; and wherein a ratio of intensity of the peak centered at about 118° to intensity of the peak centered at about 43° is at least 1:1.

### Claim 12 (depends on 10)

The electrochemical cell as recited in claim 10, wherein the cathode chamber further includes a gas input member, the gas input member configured to supply a stream of gas to the catholyte, the stream of gas including carbon dioxide.

### Claim 13 (depends on 10)

The electrochemical cell as recited in claim 10, wherein the catholyte, the anolyte, or both is an aqueous solution of at least one electrolytic salt, the at least one electrolytic salt comprising an alkali metal or alkaline earth metal salt of carbonate or bicarbonate, nitrate, nitrite, sulfate, sulfite, or phosphate.

### Claim 14 (depends on 10)

The electrochemical cell as recited in claim 10, wherein the anodizing step is characterized by a multiplication product of the constant electric potential and a duration of time for which the constant electric potential is applied; and wherein said multiplication product is at least 3.75 volt•minutes (V•min) relative to Ag/AgCl.

### Claim 15 (depends on 14)

The electrochemical cell as recited in claim 14, wherein the multiplication product of the constant electric potential and the duration of time is at least 7.5 V•min relative to Ag/AgCl.

### Claim 16 (depends on 10)

The electrochemical cell as recited in claim 10, wherein the electrochemical cell is operable for production of both carbon monoxide and hydrogen gas in the cathode chamber; wherein the electrochemical cell is characterized by a CO selectivity, the CO selectivity definable as a percent molar ratio of carbon monoxide to hydrogen gas produced; and wherein the CO selectivity is at least 50%.

### Claim 17 (depends on 16)

The electrochemical cell as recited in claim 16, wherein the CO selectivity is greater than 60%.