Electrocatalytic CO₂ Reduction Empowered by 2D Hexagonal Transition Metal Borides

Electrocatalysis holds immense promise for producing high-value chemicals and fuels through the carbon dioxide reduction reaction (CO₂RR), advancing global sustainability and carbon neutrality. However, conventional electrocatalysts based on transition metals are often limited by significant overpotentials. Since the discovery of the first hexagonal MAB (h-MAB) phase, Ti₂InB₂, and its 2D derivative in 2019, 2D hexagonal transition metal borides (h-MBenes) have emerged as promising candidates for various electrochemical applications. This study presents the first theoretical investigation into the CO₂RR catalytic properties of pristine h-MBenes (h-MB) and their ─O (h-MBO) and ─OH (h-MBOH) terminated counterparts, focusing on metals such as Sc, Ti, V, Zr, Nb, Hf, and Ta. These results reveal while h-MB and h-MBO exhibit poor catalytic performance due to overly strong or weak interactions with CO₂, h-MBOH shows great promise. Notably, ScBOH, TiBOH, and ZrBOH display exceptionally low limiting potentials (U_L) of −0.46, −0.53, and −0.64 V, respectively. These findings uncover the unique role of ─OH in tuning the electronic properties of h-MBenes, thereby optimizing intermediate adsorption, which prevents excessive binding and enhances catalytic efficiency. This research offers valuable insights into the potential of h-MBenes as highly efficient CO₂RR catalysts, underscoring their versatility and significant prospects for electrochemical applications.