Work function regulation of surface-engineered Ti2CT2MXenes for efficient electrochemical nitrogen reduction reaction

Electrochemical conversion of nitrogen to ammonia is a promising method in modern agriculture and industry due to its suitability and feasibility under mild conditions. Therefore, seeking electrocatalysts and understanding the catalytic mechanisms are of great importance. In this work, by combining the concept of the synergetic effect of the terminal vacancy and transition metal active center, we studied the whole catalytic mechanism of defective Ti₂CT₂ MXenes with functional groups (T = O, F, H, OH) by employing first-principles calculations. It is demonstrated that the electron transfer behavior of 2D transition metal carbides can be tuned by modifying the surface functional groups. Herein, the rarely investigated work function regulation is proved to effectively alter the electron transfer ability, thus the binding strength of key intermediates on the surface can be optimized. Besides, Ti₂CO₂ with an oxygen vacancy is identified as a promising candidate through a distal mechanism, where the calculated electronic properties reveal that the introduction of in-gap states is responsible for activating N₂ with physical adsorption. In addition, obvious orbital splitting of the σ and π* orbitals of N₂ is observed due to the hybridization of frontier orbitals. The symmetry matching rule of the frontier orbitals of π* 2p and the σ 2p orbitals of N with Ti d orbitals further illustrates the "acceptance-donation" interaction. These theoretical insights highlight the underlying mechanism of the synergetic effect of surficial vacancy and exposed transition metal atoms, and provide an alternative view of designing efficient NRR electrocatalysts.