Breaking Scaling Relationships in CO2 Reduction on Copper Alloys with Organic Additives

Boundary conditions for catalyst performance in the conversion of common precursors such as N₂, O₂, H₂O, and CO₂ are governed by linear free energy and scaling relationships. Knowledge of these limits offers an impetus for designing strategies to alter reaction mechanisms to improve performance. Towards a more sustainable carbon economy, understanding the basis of catalytic selectivity for CO₂ conversion to chemical feedstocks/fuels is key. Herein, high-throughput experimentation on 14 bulk copper bimetallic alloys allowed for data-driven identification of a fundamental linear scaling relationship between methane and C₂₊ products that constrains the Faradaic efficiency for C–C coupling. We have furthermore demonstrated that coating the electrodes with a molecular film breaks the scaling relationship to promote C₂₊ product formation.