Work

Tailoring the d ‐Band Center of WS 2 by Metal and Nonmetal Dual‐Doping for Enhanced Electrocatalytic Nitrogen Reduction

Year: 2024

Type: article

Abstract: Tuning the adsorption energy of nitrogen intermediates and lowering the reaction energy barrier is essential to accelerate the kinetics of nitrogen reduction reaction (NRR), yet remains a great challenge. Herein, the electronic structure of WS 2 is tailored based on a metal and nonmetal dual‐doping strategy (denoted Fe, F‐WS 2 ) to lower the d ‐band center of W in order to optimize the adsorption of nitrogen intermediates. The obtained Fe, F‐WS 2 nanosheet catalyst presents a high Faradic efficiency (FE) of 22.42% with a NH 3 yield rate of 91.46 µg h −1 mg cat. −1 . The in situ characterizations and DFT simulations consistently show the enhanced activity is attributed to the downshift of the d ‐band center, which contributes to the rate‐determining step of the second protonation to form N 2 H 2 * key intermediates, thereby boosting the overall nitrogen electrocatalysis reaction kinetics. This work opens a new avenue to enhanced electrocatalysis by modulating the electronic structure and surrounding microenvironment of the catalytic metal centers.

Source: Small

DOI: 10.1002/smll.202407594