Plasmonic Gold Antenna-Copper Molecular Complex Reactor Assembly for Exclusive CO₂ to Formate Conversion under...

Area of Science:

• Materials Science
• Electrochemistry
• Catalysis

Background:

• Photoelectrochemical CO2 reduction faces challenges in achieving high product selectivity with molecular electrocatalysts.
• Developing efficient and durable catalysts is crucial for CO2 conversion technologies.

Purpose of the Study:

• To design and investigate a plasmonic-molecular hybrid catalyst for highly selective photoelectrochemical CO2 reduction.
• To understand the mechanism behind the enhanced selectivity and durability of the hybrid catalyst.

Main Methods:

• Fabrication of a hybrid catalyst (AuTNP@Cu(PAP)2) by immobilizing a copper complex onto gold triangular nanoprisms.
• Photoelectrochemical measurements to assess CO2 reduction performance (Faradaic efficiency, yield, durability).
• Spectroscopic techniques (transient absorption, in situ Raman) and DFT calculations for mechanistic studies.

Main Results:

• Achieved high selectivity for CO2-to-formate conversion with a Faradaic efficiency of ~95%.
• Demonstrated remarkable durability over 25 hours of continuous operation.
• Identified Au-Cu interfacial interactions as key to promoting hot-electron transfer and stabilizing intermediates.

Conclusions:

• The plasmonic-molecular hybrid catalyst offers a promising platform for selective and durable CO2 reduction.
• The study provides a design principle for plasmon-driven molecular architectures for CO2 conversion.
• Scalability was demonstrated in a photoelectrochemical flow reactor.