Single-Atom-Substituted Mo₂CT:Fe-Layered Carbide for Selective Oxygen Reduction to Hydrogen Peroxide: Tracking the...

This work critically assesses the electrocatalytic activity, stability, and nature of the active phase of a two-dimensional molybdenum carbide (MXene) with single-atomic iron sites, Mo₂CT:Fe (T are surface terminating groups O, OH, and F), in the catalysis of the oxygen reduction reaction (ORR). X-ray absorption spectroscopy unequivocally confirmed that the iron single sites were incorporated into the Mo₂CT structure by substituting Mo atoms in the molybdenum carbide lattice with no other detectable Fe-containing phases. Mo₂CT:Fe, the first two-dimensional carbide with isolated iron sites, demonstrates a high catalytic activity and selectivity in the oxygen reduction to hydrogen peroxide. However, an analysis of the electrode material after the catalytic tests revealed that Mo₂CT:Fe transformed in situ into a graphitic carbon framework with dispersed iron oxyhydroxide (ferrihydrite, Fh) species (Fh/C), which are the actual active species. This experimental observation and the results obtained for the titanium and vanadium 2D carbides challenge previous studies that discuss the activity of the native MXene phases in oxygen electrocatalysis. Our work showcases the role of 2D metal carbides as precursors for active carbon-based (electro)catalysts and, more fundamentally, highlights the intrinsic evolution pathways of MXenes in electrocatalysis.