Controlled Synthesis of EDTA-Modified Porous Hollow Copper Microspheres for High-Efficiency Conversion of CO₂ to Multicarbon Products

Electrochemical reduction of CO₂ into value-added products is an effective approach to relieve environmental and energetic issues. Herein, EDTA anion-modified porous hollow copper microspheres (H-Cu MPs) were constructed by EDTA-2Na-assisted electrodeposition. The faradic efficiency (FE) of ethylene doubled from 23.3% to 50.1% at -0.82 V vs RHE in nearly neutral 0.1 M KHCO₃ solution, one of the highest values among copper-based electrodeposited catalysts. Apart from the favorable influence from morphology regulated by EDTA-2Na, theoretical calculations revealed that the adsorbed EDTA anions were able to create a local charged copper surface to stabilize the transition state and dimer and to assist in the stabilization by interacting with OCCO adsorbate synergistically, which contributed to the outstanding catalytic performance together.