PVC plasticized membranes modified with Fe3O4 nanoparticles for potentiometric sensing of sulfate

Abstract

Potentiometric sensing is one of the most wide spread platforms for analysis of aqueous solutions. The development of potentiometric sensors for hydrophilic anions such as sulfate, phosphate and bicarbonate is a challenging problem, since their high hydration energy results in a low affinity for non-polar polymer membranes – a standard material for potentiometric sensor production.In this study we propose a new type of polymeric sensor membranes for ion-selective sensors with pronounced selectivity to hydrophilic anions. The membranes are based on inorganic Fe3O4 nanoparticles (NP) embedded into plasticized poly(vinyl chloride). Six different formulations of membranes with various combinations of Fe3O4 nanoparticles and other membrane-active components were synthesized and characterized with a wide range of physico-chemical methods. Contact angle measurements, FTIR spectra, SEM and AFM imaging, magnetization hysteresis curves, ZFC/FC studies were performed. The obtained results proved the formation of nanocomposites and demonstrated a structure with “cavities” in membranes with embedded nanoparticles. Potentiometric sensitivity and selectivity of the developed sensors in aqueous solutions of SO42−, HPO42−, HCO3−, H2PO4−, NO3− and Cl− anions were studied. The developed sensors showed high sensitivity to sulfate ion (-22 mV/dec in the concentration range from 10−5 to 10−3 M) and low sensitivity to the typical interfering anions – chloride and nitrate (-14 mV/dec). The optimized sensor membrane composition demonstrated sulfate selectivity higher than that of commercially available ion-selective sensor formulations. The novel sensors were tested for quantification of SO42− in real samples of natural mineral water and the obtained content of sulfate was in a good agreement with the reference data (relative error < 3%)