Accelerating proton relay via fluorine-modified bismuth for efficient carbon dioxide electroreduction to formate

Area of Science:

• Electrochemistry
• Catalysis
• Materials Science

Background:

• Optimizing carbon dioxide (CO2) reduction requires precise control over proton supply for intermediate hydrogenation.
• Interfacial water dissociation is key to governing proton availability in CO2 electroreduction.

Purpose of the Study:

• To develop a catalyst that efficiently regulates interfacial water dissociation for enhanced CO2 reduction.
• To improve catalytic activity and product selectivity towards formate production.

Main Methods:

• Synthesis of fluorine-doped bismuth nanosheet (F-Bi NS) catalyst via in-situ electrochemical reconstruction.
• Utilizing theoretical calculations to understand the mechanism of F doping on Bi active sites.
• Coupling CO2 reduction with glycerol oxidation in a two-electrode system.

Main Results:

• F-Bi NS demonstrated exceptional selectivity (>90%) for formate production over a wide pH range.
• Theoretical calculations confirmed that F doping modulates Bi electronic structure, enhancing water adsorption/activation and proton supply.
• The F-Bi NS catalyst effectively lowered the reaction energy barrier for formate generation.
• Coupled electrocatalysis achieved efficient and synergistic formate production with glycerol oxidation.

Conclusions:

• Fluorine doping in bismuth nanosheets is an effective strategy to regulate interfacial water for improved CO2 electroreduction to formate.
• The F-Bi NS catalyst offers high activity and selectivity, presenting a promising approach for value-added chemical synthesis.
• Coupled electrocatalytic systems show potential for simultaneous production of multiple chemicals from CO2 and other feedstocks.