Electrochemical Nitrogen Reduction Reaction Performance of Single-Boron Catalysts Tuned by MXene Substrates

A boron (B) center, which has an electronic structure mimicking the filled and empty d orbitals in transition metals, can effectively activate the triple bond in N₂ so as to catalyze the nitrogen reduction reaction (NRR). Here, by means of density functional theory, we have systematically investigated the catalytic performance of a single B atom decorated on two-dimensional transition metal carbides (MXenes). The B-doped Mo₂CO₂ and W₂CO₂ MXenes exhibit outstanding catalytic activity and selectivity with limiting potentials of -0.20 and -0.24 V, respectively. Importantly, we have found that, although a high tendency of B-to-adsorbate electron donation can promote the hydrogenation of *N₂ to *N₂H, it would also severely hamper the *NH₂ to *NH₃ conversion due to the strong B-N bonding. Such an electron-donation effect can be reasonably tuned by the transition metal in the MXene substrate, which enables us to achieve optimized catalytic performance with a certain moderate degree of electron donation.