True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity
Christoph Grießer, Haobo Li, Eva‐Maria Wernig, Daniel Winkler, Niusha Shakibi Nia, Thomas Mairegger, Thomas Götsch, Thomas Schachinger, Andreas Steiger‐Thirsfeld, Simon Penner, Dominik Wielend, David A. Egger, Christoph Scheurer, Karsten Reuter, Julia Kunze‐Liebhäuser
Abstract
Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CO 2 RR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CO 2 RR at parent TMs. Here, we evaluate these prospects for hexagonal Mo 2 C in aqueous electrolytes in a multimethod experiment and theory approach. We find that surface oxide formation completely suppresses the CO 2 activation. The oxides are stable down to potentials as low as -1.9 V versus the standard hydrogen electrode, and solely the hydrogen evolution reaction (HER) is found to be active. This generally points to the absolute imperative of recognizing the true interface establishing under operando conditions in computational screening of catalyst materials. When protected from ambient air and used in nonaqueous electrolyte, Mo 2 C indeed shows CO 2 RR activity.