Surface-modified electrodes and their use in co2 and co reduction

Patent metadata

Field	Value
Publication number	US-2022106692-A1
Application number	US-202017422328-A
Country	US
Kind code	A1
Filing date	Jan 29, 2020
Priority date	Jan 29, 2019
Publication date	Apr 7, 2022
Grant date	—

Abstract

Disclosed are surface modified electrodes, their process of preparation and their use in the electrolytic reduction of carbon dioxide and/or carbon monoxide, as well as an electrochemical cell including the electrode.

First claim

1 . An electrode comprising or consisting of:
a metallic nanostructure, the metal of which is selected from the group of Cu, Zn, Ni, Fe, and Ag or mixtures thereof, said metallic nanostructure being part of a metallic hierarchical structure containing both micro and nanostructuration, said metallic hierarchical structure being of the same metal as defined above, a hydrophobic layer of compounds partially or totally covering the surface of said metallic hierarchical structure, said compounds being chemisorbed to said surface, wherein of from 0 to 50% of the surface of said metallic hierarchical structure is devoid of hydrophobic layer,
said metallic hierarchical structure being porous,
said compounds being chosen from the group of:
a compound of Formula 1,
R—A  Formula 1

wherein,
A represents,
—SH,
—P(O)(OH)2,
—CO2H,
—SeH,
—TeH,
—Si(OH)3,
—SiX3, wherein X represents a halogen,

an acetylacetone group having the structure of Formula 2,

R is chosen from the groups of,
(C2-C100)-alkyl linear or branched,
(C2-C100)-alkenyl linear or branched,
(C2-C100)-alkynyl linear or branched,
(C2-C100)-heteroralkyl linear or branched,
(C2-C100)-heteroalkenyl linear or branched,
(C2-C100)-heteroalkynyl linear or branched,

said alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl can be further substituted by one or more groups selected from:
amines,
—ORa, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
halogen,
aryl,
—CO2Rb, wherein Rb represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
—CX3 groups, wherein X represents a halogen,
a compound of Formula 3,

wherein,
A represents Se or S,
R is a group as defined above,
polysiloxane compounds chosen from the groups of (C1-C100)-polyalkylsiloxane, or polyarylsiloxane, said polyalkylsiloxane and polyarylsiloxane can be further substituted by one or more groups selected from:
amines,
—ORa, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
halogen, wherein X represents a halogen,
—CO2Ra, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,

said electrode having a hydrophobicity as determined by contact angle measurement from 130° to 175°,
said electrode having an electrochemically active surface area (EASA) lower than 10% of the geometric surface area of said metallic hierarchical structure.

2 . The electrode according to claim 1 , wherein said hydrophobic layer covers at least 80% of said surface of said metallic hierarchical structure, the electrochemically active surface area being from of 0 to 1% of the geometric surface area.

3 . The electrode according to claim 1 ,
wherein said surface of the metallic hierarchical structure is partially devoid of said compound, and wherein the parts of the surface of the metallic hierarchical structure that are not covered by the compounds are regions of the structure that are part of the electrochemically active surface area, wherein a portion greater than 0% and no more than 50% of the surface of said metallic hierarchical structure is devoid of hydrophobic layer, the electrochemically active surface area being greater than 0% and no more than 10% of the geometric surface area.

4 . The electrode according to claim 1 , wherein said metal is chosen from Cu or Zn, or mixtures of Cu and Ag or mixtures of Zn and Ag.

5 . The electrode according to claim 1 , wherein said compound is chosen from a compound of Formula 1, wherein A represents —SH.

6 . The electrode according to claim 1 ,
wherein said metal is chosen from Cu, and wherein said compound is chosen from a compound of Formula 1, wherein A represents —SH, and wherein said metallic hierarchical structure is dendritic.

7 - 15 . (canceled)

16 . The electrode according to claim 1 , wherein said metallic nanostructure contains dendritic hierarchical structures.

17 . The electrode according to claim 3 , wherein a portion of the surface of said metallic hierarchical structure is devoid of hydrophobic layer, said portion being greater than 0% and no more than 30% of the surface of said metallic hierarchical structure is devoid of hydrophobic layer.

18 . The electrode according to claim 5 , wherein said compound is 1-octadecanethiol or 1-dodecanethiol.

19 . A method for the implementation of an electrochemical reaction, said electrochemical reaction being the reduction of CO2 or CO gas or mixture thereof into hydrocarbon(s) or alcohol(s) or mixtures thereof in aqueous medium, or the reduction of CO2 gas into CO in aqueous medium, wherein the method comprises a step of contacting said CO2 gas, or said CO gas, with an electrode comprising or consisting of:
a metallic nanostructure, the metal of which is selected from the group of Cu, Zn, Ni, Fe, and Ag or mixtures thereof, said metallic nanostructure being part of a metallic hierarchical structure containing both micro and nanostructuration, said metallic hierarchical structure being of the same metal as defined above, a hydrophobic layer of compounds partially or totally covering the surface of said metallic hierarchical structure, said compounds being chemisorbed to said surface, wherein of from 0 to 50% of the surface of said metallic hierarchical structure is devoid of hydrophobic layer,
said metallic hierarchical structure being porous,
said compounds being chosen from the group of:
a compound of Formula 1,
R—A  Formula 1

wherein,
A represents,
—SH,
—P(O)(OH)2,
—CO2H,
—SeH,
—TeH,
—Si(OH)3,
—SiX3, wherein X represents a halogen, preferably fluorine, chlorine or bromine,
an acetylacetone group having the structure of Formula 2,

R is chosen from the groups of,
(C2-C100)-alkyl linear or branched,
(C2-C100)-alkenyl linear or branched,
(C2-C100)-alkynyl linear or branched,
(C2-C100)-heteroralkyl linear or branched,
(C2-C100)-heteroalkenyl linear or branched,
(C2-C100)-heteroalkynyl linear or branched,

said alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl and heteroalkynyl can be further substituted by one or more groups selected from:
amines,
—ORa, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
halogen,
aryl,
—CO2Rb, wherein Rb represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
—CX3 groups, wherein X represents a halogen,
a compound of Formula 3,

wherein,
A represents Se or S,
R is a group as defined above,
polysiloxane compounds chosen from the groups of (C1-C100)-polyalkylsiloxane, or polyarylsiloxane, said polyalkylsiloxane and polyarylsiloxane can be further substituted by one or more groups selected from:
amines,
—ORa, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-alkyl group,
halogen, wherein X represents a halogen,
—CO2Ra, wherein Ra represents a hydrogen atom, a (C1-C20)-alkyl group, a (C1-C10)-alkyl group, or a (C1-C5)-al

Assignees

• Paris Sciences Et Lettres
• College France
• Centre Nat Rech Scient

Inventors

• Fontecave Marc
• Mougel Victor
• Wakerley David
• Lamaison Sarah

Classifications

• C25B3/03

  Acyclic or carbocyclic hydrocarbons · CPC title

• C25B3/26

  of carbon dioxide · CPC title

• C25B3/07

  Oxygen containing compounds · CPC title

• C25B11/04

  characterised by the material · CPC title

• C25B11/031 Primary

  Porous electrodes · CPC title