ArticlePloS one2025
Efficient removal of silver ions from wastewater via chelation with dithiooxamide-functionalized polymeric adsorbent.
Article in PloS one, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
This study investigates Ag(I) adsorption on a dithiooxamide/glutaraldehyde resin (DTG-R) using both experimental and theoretical approaches. Characterization confirmed the resin's porous structure and sulfur/nitrogen active sites. Batch experiments revealed high Langmuir capacity (27.2 mmol/g at 25°C), with kinetics following a pseudo-second-order model (R2 > 0.99), indicating chemisorption. Thermodynamic analysis showed endothermic (ΔH° = 121.25 kJ/mol), spontaneous adsorption (ΔG° = -12.8 to -17.3 kJ/mol), driven by entropy gains (ΔS° = 449.9 J/mol.K) from Ag(I) dehydration and polymer swelling. DFT calculations demonstrated preferential Ag(I) binding to deprotonated sulfur (S-Ag: 2.50-2.60 Å, bond order: 0.76-0.86) over nitrogen, with mononuclear complexes being most stable (ΔE = -175.6 kcal/mol). The resin exhibited high selectivity, reusability of 96% efficiency over five cycles, and optimal performance at pH 5.75. NBO analysis revealed charge transfer to Ag(I) (partial charge less than +1), while binding energy trends explained the observed temperature-dependent capacity. DTG-R combined high capacity, rapid kinetics, and molecular-level affinity for Ag(I) make it better than existing adsorbents for industrial wastewater remediation. This work bridges macroscopic adsorption properties with quantum-chemical mechanisms, offering a template for rational adsorbent design.
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