2020/10/27 by Shaobin Tang, Qian Dang, Tianyong Liu +7 · 1 citation
Chemical Engineering · Energy · #Advanced Photocatalysis Techniques #Ammonia Synthesis and Nitrogen Reduction #Electrocatalysts for Energy Conversion
paper · doi:10.1021/jacs.0c09527
openalex publication_date 2020/10/27 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/30
Developing efficient single-atom catalysts (SACs) for nitrogen fixation is of great importance while remaining a great challenge. The lack of an effective strategy to control the polarization electric field of SACs limits their activity and selectivity. Here, using first-principles calculations, we report that a single transition metal (TM) atom sandwiched between hexagonal boron nitride (h-BN) and graphene sheets (namely, BN/TM/G) acts as an efficient SAC for the electrochemical nitrogen reduction reaction (NRR). These sandwich structures realize stable and tunable interfacial polarization fields that enable the TM atom to donate electrons to a neighboring B atom as the active site. As a result, the partially occupied p z orbital of a B atom can form B-to-N π-back bonding with the antibonding state of N 2, thus weakening the N≡N bond. The not-strong-not-weak electric field on the h-BN surface further promotes N 2 adsorption and activation. The NRR catalytic activity of the BN/TM/G system is highly correlated with the degree of positively polarized charges on the TM atom. In particular, BN/Ti/G and BN/V/G are identified as promising NRR catalysts with high stability, offering excellent energy efficiency and suppression of the competing hydrogen evolution reaction.