A DFT study on regulating the active center of v-Ti2XT2 MXene through surface modification for efficient nitrogen fixation.

[Display omitted] • The surface modification can significantly raise the limiting potential with −1.24 V (Ti 2 NF 2) to −0.21 V (Ti 2 BSe 2). • hybridization of the σ 2 p and π* 2 p with Ti 3 d orbitals leads to the evident splitting and downshifting of the σ and π* orbitals. • The work function plays a crucial role to predict the NRR performance by the Gibbs free energy change of the rate-determining step, which can be regulated through the surface termination of MXenes. The electrochemical conversion of nitrogen to ammonia provides an encouraging method to substitute the traditional Haber-Bosch process, owing to its high efficiency and mild reaction conditions. The search for high-performance catalysts and comprehension of catalytic mechanisms remains significant challenges. Herein, we conduct a systematic theoretical calculation of the NRR performance and mechanism of 24 Ti 2 XT 2 (X = B, C, N; T = F, Cl, Br, I, O, S, Se, Te) MXenes with a T -vacancy to explore the influence of surface functional terminations and non-metallic center elements. Our findings demonstrate that surface functionalization significantly reduces the limiting potential by altering the rate-determining step. This change ranges from −1.24 V (Ti 2 NF 2) to −0.21 V (Ti 2 BSe 2), signifying the remarkable efficacy of modification of the surrounding environment of the exposed transition metal active center in promoting electrocatalytic performance. Detailed investigation of the charge density difference and orbital interaction reveals that the different NRR performance originates from the surface termination and non-metallic atoms regulate the electronic properties of the active Ti atoms. We also introduce the free energy change of *NNH 2 (Δ G *NNH2) as a descriptor to predict the performance of NRR, which exhibits satisfactory linear relationship with free energy change of different intermediates and displays favourable volcano plot with limiting potential. Moreover, we highlight the pivotal role of work function in tuning the energy barrier of the rate-determining step, which can be regulated through the surface modification of MXenes. Our study not only offers a comprehensive understanding of the crucial impact of surface modification on the catalytic activities of defective MXenes, but also provides a rational perspective for designing efficient NRR catalysts. [ABSTRACT FROM AUTHOR]