Aryl sulfur ligand-modulated silver catalysts with tailored binding affinity for selective nitrate-to-ammonia conversion

Manipulating the selectivity-determining step in the hydrogenation of nitrogen-containing intermediates is critical to achieving high ammonia selectivity in electrocatalytic nitrate reduction. Here, we propose a molecular interface engineering strategy that functionalized with thiol-anchored aromatic ligands to regulate the interfacial binding affinity and activation of key nitrogen-containing intermediates on silver nanocube surfaces. By systematically varying the electronic properties of the substituents, we identify 4-(methylthio)benzaldehyde as the most effective ligand, increasing the ammonia Faradaic efficiency from 50.8% to 98.9% and achieving a yield rate of 14,366.1 μg h–1 cmgeo–2 at –0.63 V versus…

• NR
  National Research Foundation
• NR
  National Research Foundation Singapore

  Award: 370184872
• NN
  National Natural Science Foundation of China

  Award: 22425804
• SU
  Sichuan University
• NS
  Natural Science Foundation of Sichuan Province

  Awards: 2025ZNSFSC0923, 2025ZNSFSC0899