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.