Boosting Nitrogen Activation via Ag Nanoneedle Arrays for Efficient Ammonia Synthesis

Electrocatalytic N₂ reduction reaction (eNRR) provides a promising carbon-neutral and sustainable ammonia-synthesizing alternative to the Haber-Bosch process. However, the nonpolar N₂ has significant thermodynamic stability and requires ultrahigh energy to break down the N≡N bond. Here, we report the construction of local enhanced electric fields (LEEFs) by Ag nanoneedle arrays to promote N≡N fracture thus assisting the eNRR. The LEEFs could induce charge polarization on nitrogen atoms and reduce the energy barrier in the N₂ first-protonation step. The detected N─N and N─H intermediates prove the cleavage of the N≡N bond and the hydrogenation of N₂ by LEEFs. The increased LEEFs lead to logarithmic growth rates for the targeted eNRR and exponential growth rates for the unavoidable competitive hydrogen evolution reaction. Thus, regulation and tuning of LEEFs to ∼4 × 10⁴ kV m^-1 endows the raise of eNRR to the summit, achieving high ammonia selectivity with a Faradaic efficiency of 72.3 ± 4.0%.