Multidimensional Design of Metal-Nitrogen-Carbon Electrocatalysts for Direct Propylene Epoxidation

Abstract

Propylene oxide is a major industrial chemical whose production currently relies on hazardous chlorine- or peroxide-based oxidants. Direct electrochemical epoxidation using water as the oxygen source offers a sustainable alternative, but controlling oxygen-atom transfer against the competing oxygen evolution reaction remains a fundamental challenge. Here, we show that propylene epoxidation selectivity cannot be described by oxygen binding energy alone, but is jointly governed by oxygen adsorption, the potential of zero charge, and applied potential. By combining theoretical calculations with pH-field-coupled microkinetic modeling across 41 metal-nitrogen-carbon single-atom catalysts, we first identified an optimal oxygen-binding window and Co as the most favorable metal center. We then found that peripheral substituents can tune the PZC while largely preserving the optimal oxygen adsorption energetics, thereby providing an independent design dimension to further optimize the already favorable Co active site. This sequential, multidimensional design strategy identified CoPc-NH2-CNT as the optimal catalyst, delivering a record PO Faradaic efficiency of 70-80 percent for direct propylene epoxidation in aqueous electrolyte under ambient conditions. These results establish interfacial electrostatics as an independently tunable design dimension for controlling selective oxygen-atom transfer in electrocatalysis.