Impact of Vacancy Defects on Electrochemical Nitrogen Reduction Reaction Performance of MXenes

Abstract

AbstractWe investigated electrochemical nitrogen reduction reaction (eNRR) on MXenes consisting of the vacancy defects in the functional layer using density functional theory calculations. We considered Mo2C, W2C, Mo2N, and W2N MXenes with F, N, and O functionalization and investigated distal and alternative associative pathways. We analyzed these MXenes for eNRR based on N2 adsorption energy, NH3 desorption energy, NRR selectivity, and electrochemical limiting potential. While we find that most of the considered MXenes surfaces are more favorable for eNRR compared to hydrogen evolution, these surfaces also have strong NH3 binding (>−1.0 eV) and thus will be covered with NH3 during operating conditions. Amongst all considered MXenes, only W2NF2 is found to have a low NH3 desorption energy along with low eNRR overpotential and selectivity towards eNRR. The obtained eNRR overpotential and NH3 desorption energy on W2NF2 are superior to those reported for pristine W2N3 as well as functionalized MXenes.