Revealing the Adsorption Behavior of Nitrogen Reduction Reaction on Strained Ti2CO2 by a Spin-Polarized d-band Center Model

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

4 Scopus Citations
View graph of relations


Original languageEnglish
Article number2306840
Journal / PublicationSmall
Issue number9
Online published20 Oct 2023
Publication statusPublished - 1 Mar 2024


Electrocatalytic reduction of dinitrogen to ammonia has attracted significant research interest. Herein, it reports the boosting performance of electrocatalytic nitrogen reduction on Ti2CO2 MXene with an oxygen vacancy through biaxial tensile strain engineering. Specifically, tensile strain modified electronic structures and formation energy of oxygen vacancy are evaluated. The exposed Ti atoms with additional electron states near the Fermi level serve as active site for intermediate adsorption, leading to superior catalytic performance (Ulimit = −0.44 V) under 2.5% biaxial tensile strain through a distal mechanism. However, the two sides of the “Sabatier optimum” in volcano plot are not limited by two different electronic steps, but are induced by the diverse adsorption behaviors of intermediates. Crucially, the “Sabatier optimum” results from the different response speeds of the adsorption energy for *N2 and *NNH to strains. Moreover, the authors observe conventional d-band adsorption for *N2 and *NNH, non-linear adsorption for *NNH2, and abnormal d-band adsorption for *N, *NH, *NH2, and *NH3, which can be explained by the competition between attractive orbital hybridization and repulsive orbital orthogonalization with the spin-polarized d-band model, which further clarifies the contributions of 3σdz2 and dxz/dyz → 2π* to the overall population of bonding and anti-bonding states. © 2023 Wiley-VCH GmbH.

Research Area(s)

  • adsorption mechanism, d-orbital, nitrogen reduction, tensile strain, Ti2CO2 MXene