Interfacial Polarization Triggered by Covalent‐Bonded MXene and Black Phosphorus for Enhanced Electrochemical Nitrate to Ammonia Conversion

MXenes have recently emerged as a new class of electrocatalysts for diverse energy conversion reactions, but they are generally considered to be catalytically inert. Herein, a strategy of interfacial polarization is put forward to improve the catalytic activity of MXenes, with the construction of an interfacial structure consisting of black phosphorus (BP) nanoflakes and Nb2C MXene nanosheets for electrochemical nitrate reduction to ammonia as a proof of concept. The experimental and computational results reveal that a strong interfacial polarization is built between BP nanoflakes and Nb2C nanosheets in the prepared BP/Nb2C composite. The polarization of Nb centers by adjacent BP sites gives rise to the formation of positively centered Nb atoms and BP‐polarized Nb atoms, which synergistically catalyze the cleavage of N–O bonds in HNO2* to form NO*. In addition, the stabilization of monatomic *N by the BP/Nb2C composite is also enhanced compared with BP nanoflakes and Nb2C nanosheets. As a result, both the ammonia yield rate and Faraday efficiency of the BP/Nb2C composite are much higher than that of BP nanoflakes and Nb2C nanosheets. Overall, this work shows the great potential for constructing a strong interfacial polarization to improve the catalytic performance of MXenes‐based electrocatalysts. The study reveals that the interfacial polarization between black phosphorus (BP) nanoflakes and Nb2C nanosheets is vital to the enhanced nitrate reduction performance of the BP/Nb2C composite. The resulting black phosphorus‐polarized Nb and positively centered Nb tend to bind with both sides of N–O bonds in HNO2*, respectively, synergistically promoting the cleavage of N–O bonds to form NO*.