Operando Strain Modulation Amplifies Asymmetric C─C Coupling for CO-to-Acetate Transformation

Area of Science:

• Electrochemistry
• Materials Science
• Catalysis

Background:

• Electrochemical carbon monoxide reduction reaction (CORR) is a promising route for sustainable chemical production, like acetate.
• Current CORR systems face limitations in selectivity and current density, hindering industrial viability.
• Electrocatalyst design is crucial for improving CORR performance.

Purpose of the Study:

• To develop an operando strain engineering strategy for electrocatalyst design.
• To enhance the performance of copper oxide (Cu2O) based electrocatalysts for CORR.
• To improve acetate production selectivity and current density.

Main Methods:

• Operando strain engineering by introducing aluminum (Alδ+) into Cu2O lattice.
• Electrochemical characterization in a flow cell.
• In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS).
• Density functional theory (DFT) calculations.

Main Results:

• Al (0.5)/Cu2O catalyst demonstrated a partial current density of 198 mA cm⁻² and 60% Faradaic efficiency for acetate production.
• Operando strain engineering induced tensile strain in Cu2O, which was reduced to metallic Cu.
• ATR-SEIRAS and DFT confirmed enhanced *CO and *CHO adsorption and facilitated *CO-*CHO coupling.

Conclusions:

• Strain engineering of Cu2O by Al introduction is an effective strategy to boost CORR performance.
• The developed catalyst shows significant potential for industrial acetate production.
• Understanding intermediate adsorption and coupling mechanisms is key for catalyst optimization.