A-Site Cation-Regulated Operando Restructuring of Cu-Based Perovskite Oxides for Selective Carbon Monoxide...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Designing electrocatalysts requires understanding active site dynamics under operating conditions.
• Copper-based perovskites are promising for carbon monoxide reduction (COR).

Purpose of the Study:

• Investigate how A-site cation chemistry in copper perovskites influences copper structural dynamics.
• Determine the effect of A-site variations on the carbon monoxide reduction (COR) pathway and product selectivity.

Main Methods:

• Synthesized a series of Cu-based perovskite oxides with varied A-site cations.
• Utilized operando spectroscopic analyses to study catalyst behavior under reaction conditions.
• Performed theoretical calculations to understand structure-activity relationships.

Main Results:

• Alkaline-earth A-site cations promoted Cu clustering into metallic states, favoring multicarbon products.
• Rare-earth A-site cations stabilized surface Cu+ species via strong Cu-O interactions, enhancing methane selectivity.
• A-site composition modulated Cu-O bond strength, influencing the electrochemical stability of Cu active sites.

Conclusions:

• A-site chemistry is pivotal in steering catalyst reconstruction and product distribution in perovskite-based COR catalysts.
• Local coordination environments dictate the performance of electrocatalysts.
• Provides guiding principles for A-site engineering in perovskite electrocatalysts for COR.