Gas Diffusion Electrode with Pyridine-Functionalized Copper for Formate

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Solution Overview

Problem

Existing electrochemical carbon dioxide reduction (CO2R) technologies face challenges in achieving high selectivity and production rate for formate, particularly with cheaper catalysts, and often require high pressures or specific conditions.

Innovation Solution

A gas diffusion electrode (GDE) comprising copper nanoparticles functionalized with pyridine-containing ligands, such as 4-mercaptopyridine, is used for carbon dioxide electrolysis, enhancing selectivity and production rate of formate.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional CO2R catalysts are used, then the equipment complexity is low, but the selectivity into formate is poor and product distribution is broad

Engineering Contradiction:
Improveselectivity into formateVSAvoidcatalyst structure complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent uses Cu/Au bimetallic composite catalyst where copper and gold nanoparticles are combined to achieve synergistic effects. The copper provides formate production activity while gold enhances selectivity, resolving the contradiction between manufacturing simplicity and formate selectivity by creating a composite material with superior properties.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent applies thiol ligand modification specifically at the surface of copper nanoparticles, creating localized functional regions with different properties. The thiol-tethered ligands (such as 4-pyridylethylmercaptan) are anchored at specific sites on the Cu surface, providing local selectivity enhancement without requiring complete structural complexity throughout the entire catalyst.

Inventive Principle:
Principle #3Local quality

2Manufacturing precision

If high pressure conditions are applied, then the Faradaic efficiency for formate increases, but the energy consumption and operational complexity increase

Engineering Contradiction:
ImproveFaradaic efficiency for formateVSAvoidenergy consumption
Core Design Contradiction:
Manufacturing precisionVSUse of energy by moving object

Solution Approach 1:

The patent changes the chemical parameters of the catalyst surface by introducing thiol ligands and creating Cu/Au bimetallic structures, which fundamentally alters the reaction pathway and intermediate stabilization. This allows achieving high Faradaic efficiency (up to 97.7% at 4.5 MPa) through catalyst design rather than relying solely on pressure increase, thereby reducing the energy penalty associated with high-pressure operation.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs a gas diffusion electrode configuration with catalyst ink deposited on a conductive support, creating a cost-effective and replaceable catalyst system. This approach allows using simpler, cheaper materials that can be optimized for specific reactions without requiring expensive, complex high-pressure equipment, thus reducing overall energy consumption and operational complexity.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

3Manufacturing precision

If thiol ligands are introduced to modify selectivity, then the formate Faradaic efficiency improves, but the partial current density decreases

Engineering Contradiction:
Improveformate Faradaic efficiencyVSAvoidpartial current density for formate
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent combines Cu/Au bimetallic composite with thiol ligand modification to resolve the selectivity-productivity trade-off. The gold component maintains high catalytic activity for CO2 reduction while the thiol-modified copper surface provides selective formate production pathways, achieving both high Faradaic efficiency (81% at -0.6 V vs RHE) and high partial current density (10.4 mA/cm²) simultaneously.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The thiol ligands are introduced at specific local sites on the copper nanoparticle surfaces rather than uniformly throughout the entire catalyst system. This localized modification preserves the bulk copper's high activity while providing selective surface sites for formate production, thus maintaining high partial current density while improving Faradaic efficiency.

Inventive Principle:
Principle #3Local quality

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The GDE achieves a faradaic efficiency of at least 75% and a formate production rate of at least 200 mA/cm², surpassing previous results without the need for high pressures.

Implementation Method 1

Electrochemical carbon dioxide reduction (CO2R) offers an attractive route to upgrade greenhouse gases such as CO2 to valuable fuels and feedstocks

Methodology Applied
Scientific EffectElectrochemical reduction: Electrolysis

Implementation Method 2

copper nanoparticles functionalized with one or more pyridine-containing ligands... for electrochemical carbon dioxide reduction (CO2R) reactions to produce formate

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 3

gas diffusion electrode (GDE) suitable for carbon dioxide electrolysis

Methodology Applied
Scientific EffectDiffusion: Diffusion

Data Source

PatentEP4405519B1Electrochemical carbon dioxide reduction catalyst for formate production
Publication Date: 2025.07.09 TOTALENERGIES ONETECH
  • EP4405519B1 patent drawingFigure 1
  • EP4405519B1 patent drawingFigure 2~3
  • EP4405519B1 patent drawingFigure 4

AI summary

The disclosure relates to a gas diffusion electrode - GDE - suitable for carbon dioxide electrolysis, said gas diffusion electrode having a gas diffusion membrane, the gas diffusion electrode further comprising an ink (19) deposited on the gas diffusion membrane; wherein the ink comprises an ion-conducting polymer and copper nanoparticles functionalized with one or more pyridine-containing ligands, wherein the one or more pyridine-containing ligands have an anchoring group comprising one sulphur atom tethered to the copper nanoparticles. The disclosure also relates to a gas-fed flow cell comprising such gas diffusion electrode and to a method for producing such GDE as well to the electrolysis of carbon dioxide using such GDE.