Design of Atomic Ordering in Mo₂Nb₂C₃T MXenes for Hydrogen Evolution Electrocatalysis

The need for novel materials for energy storage and generation calls for chemical control at the atomic scale in nanomaterials. Ordered double-transition-metal MXenes expanded the chemical diversity of the family of atomically layered 2D materials since their discovery in 2015. However, atomistic tunability of ordered MXenes to achieve ideal composition-property relationships has not been yet possible. In this study, we demonstrate the synthesis of Mo_2+αNb_2-αAlC₃ MAX phases (0 ≤ α ≤ 0.3) and confirm the preferential ordering behavior of Mo and Nb in the outer and inner M layers, respectively, using density functional theory, Rietveld refinement, and electron microscopy methods. We also synthesize their 2D derivative Mo_2+αNb_2-αC₃T MXenes and exemplify the effect of preferential ordering on their hydrogen evolution reaction electrocatalytic behavior. This study seeks to inspire further exploration of the ordered double-transition-metal MXene family and contribute composition-behavior tools toward application-driven design of 2D materials.