Boosting the Faraday Efficiency of Electrochemical Ammonia Synthesis via the Strain Effect Induced by Interfacial Hybrid Formation between BN and Carbon Nanotubes.

The electrochemical nitrogen reduction reaction (eNRR) is a highly promising alternative to the Haber-Bosch (H-B) process, but its commercial development is limited by the high bond energy of N 2 molecules and the presence of the competitive hydrogen evolution reaction (HER). Here, a metal-free composite electrocatalyst of boron nitride (h-BNNs) and carbon nanotubes (CNTs) was explored through the interfacial hybridization of h-BNNs and CNTs, which showed a highly improved eNRR Faraday efficiency (FE) of 63.9% and an NH 3 yield rate of 36.5 μg h -1 mg cat. -1 at -0.691 V (vs RHE). New chemical bonds of C-B and C-N were observed, indicating a strong interaction between CNTs and h-BNNs. According to the Raman spectra and the optimized model of h-BNNs/CNTs, an obvious strain effect between h-BNNs and CNTs was supposed to play a significant role in the highly improved FE, compared with the FE of h-BNNs alone (4.7%). Density functional theory (DFT) calculations further showed that h-BNNs/CNTs had lower energy barriers in eNRR, giving them higher N 2 to NH 3 selectivity, while h-BNNs have lower energy barriers in the HER. This work shows the important role of the strain effect in boosting the selectivity in the eNRR process.