Na+ and Cl− adsorption derived enhancement in 4-nitrophenol reduction using Au/Ag nanoparticle: An experimental and theoretical study

4-Nitrophenol (4-NP) is an organic contaminant attached to textiles, pharmaceuticals, and pesticides. Its presence has been increasingly detected in various water bodies such as lakes, rivers, and occasionally in drinking water. The present work shows the reduction of 4-NP using a hybrid catalytic system composed of gold and silver nanoparticles supported onto the biogenic porous silica (AgAu–SiO₂). The AgAu nanoparticles were fabricated in situ onto the salinized biogenic silica substrates through a green synthesis. The catalytic reaction was analyzed with NaBH₄ and the proposed AgAu–SiO₂ catalyst. Mimicking 4-NP reduction reaction in different spiked river/marine water samples revealed superior catalytic activity in marine water. Subsequently, interference studies performed in the presence of different metal salts and pHs (found in the marine water) showed the vital role played by NaCl in the 4-NP reduction as the increase in the NaCl concentration enhances the catalytic activity of the proposed catalyst. Additional reusability of the proposed catalyst demonstrated its efficacy up to 10 cycles. The density functional theory (DFT) results supported the experimental findings, confirming the crucial role of Na⁺ and Cl⁻ in the catalytic process. Our experimental results, which have significant implications for the field, have been explained by comparing them with DFT calculations. The main reason behind the enhanced catalysis performance in our systems was deduced at the atomic scale. The study included the adsorption energies and electronic density of molecular structures (4-NP and 4-AP) on different surface coverages. In exceptional cases, at the intermediate of 4-NP on Au(111)-NaCl, a displacement of the electronic density is observed, leading to a quinoline-type ring weakening the N–O bond and favoring the catalytic performance.