Trace cisplatin adsorption by thiol-functionalized sponge (TFS) and Sn/SnO2-coated TFS: adsorption study and mechanism investigation

Journal of Hazardous Materials(2024)

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摘要
To remove trace cisplatin from aqueous solution, commercial sponges were functionalized by esterification with 3-mercaptopropionic acid, followed by reduction with Na2S·9H2O or SnCl2·2H2O. The resulting thiol-functionalized sponges (TFSs), TFS_1 and TFS_2, were tested for the removal of cisplatin (235μgL-1) achieving maximum removal of 95.5±0.8% and 99.5±0.1% respectively, which were significantly higher than the non-functionalized counterpart. The successful grafting of thiol groups, verified through FTIR, elemental analysis, SEM-EDS, and XPS characterization, facilitated Pt−S complexation during adsorption. The aqua-derivatives of cisplatin, formed through hydration, complexed with thiol sites through ligand displacement. Additionally, the presence of Sn/SnO2 coating on TFS_2 further enhanced the adsorption process. The rapid adsorption process conformed to pseudo-second-order kinetic model, involving both diffusion and chemisorption. While the Langmuir isotherm model generally described the monolayer adsorption behavior of cisplatin, the aggregation of Sn/SnO2 onto TFS_2 at 343K introduced surface heterogeneity, rendering the Freundlich model a better fit for the adsorption isotherm. Differential pH dependence and the evaluation of mean free energy, derived from the Dubinin-Radushkevich isotherm model, indicated that cisplatin adsorption onto TFS_1 involved physisorption, including electrostatic attraction, while chemisorption predominated for TFS_2. Increasing the temperature notably promoted adsorption by facilitating the thermal-favored formation of Pt−S bonds. Environmental Implication This research aims to address the environmental implications of emerging pollutant, cisplatin, found in trace amounts in hospital wastewater. Even at extremely low concentrations, this cytostatic exhibits significant ecological toxicity, yet the environmental concern remains largely underemphasized, with limited reported treatment methods. This study holds substantial significance in the field of pollutant management and water purification as it proposes an effective approach to treating wastewater containing low levels of cisplatin. It underscores the growing environmental risks associated with the discharge of platinum cytostatics or other pharmaceutical contaminants, seeking to raise awareness and highlight the need for improved disposal solutions.
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关键词
cisplatin,cytostatics,adsorption,functionalized materials,emerging pharmaceutical pollutants
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