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 N 2 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 Mo 2 CO 2 and W 2 CO 2 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 *N 2 to *N 2 H, it would also severely hamper the *NH 2 to *NH 3 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.

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Systematic study on the doping effects of anatase TiO2 doped with 40 kinds of elements by high-throughput HSE06 calculations.