Dopant-induced electron localization drives CO₂ reduction to C₂ hydrocarbons

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Electrochemical reduction of carbon dioxide (CO2) to multi-carbon products offers a sustainable route to valuable fuels and feedstocks using renewable energy.
• Current CO2 conversion efficiencies to C2 products are insufficient for large-scale industrial application.
• Modifying the electronic structure of copper catalysts, particularly with positively charged sites (Cuδ+), is a promising strategy to enhance C2 selectivity.

Purpose of the Study:

• To investigate the effect of boron doping on copper catalysts for electrochemical CO2 reduction.
• To improve the efficiency and stability of copper-based catalysts for selective C2 product synthesis.
• To understand the mechanism by which boron influences the copper active sites and CO2 conversion pathways.

Main Methods:

• Utilized boron doping to tune the ratio of Cuδ+ to Cu0 active sites on copper catalysts.
• Employed simulations to analyze the influence of copper oxidation states on CO adsorption and dimerization.
• Experimentally evaluated the performance of boron-doped copper catalysts in electrochemical CO2 reduction.

Main Results:

• Achieved a C2 Faradaic efficiency of 79 ± 2% using boron-doped copper catalysts.
• Demonstrated enhanced catalyst stability, with sustained performance for over 40 hours.
• Simulations confirmed that tuning copper's average oxidation state controls CO adsorption and dimerization, favoring C2 electrosynthesis.

Conclusions:

• Boron doping is an effective strategy to enhance the performance of copper catalysts for electrochemical CO2 reduction to multi-carbon products.
• The modified electronic structure of boron-doped copper promotes selective C2 product formation and improves catalyst longevity.
• This work provides a pathway for developing efficient and stable catalysts for sustainable carbon capture and utilization technologies.