Quartz Crystal Microbalance for Selenite Sensing Based on Growth of Cadmium Selenite Crystals Immobilized on a Monolayer of Phosphorylated 11-Mercapto-1-Undecanol

Abstract

A quartz crystal microbalance (QCM) sensor for selenite ions in aqueous solution was constructed based on crystal formation of cadmium selenite, immobilized with a self-assembly monolayer (SAM) of phosphorylated 11-mercapto-1-undecanol (MUD) on a QCM gold electrode surface. The mass change caused by the selective adsorption of selenite ions on the cadmium selenite crystals at the solid/solution interface was detected by the QCM. The response (−ΔF) of the modified QCM oscillator increased with increasing selenite ion concentrations in sample solutions, ranging from 9.7×10−5 to 9.0×10−4 M at pH 7.4. The synthetic process of anchoring cadmium selenite crystals on the phosphorylated MUD organic film was also followed by using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The atomic concentrations measured by XPS confirmed the crystal growth of cadmium selenite on the phosphorylated MUD SAM at the QCM gold electrode surface. From the AFM images, changes in surface topographic features were followed: the MUD SAM and phosphorylated MUD on the QCM gold electrode had similar surface roughness; however the difference for the cadmium selenite film on the phosphorylated MUD SAM was clearly seen. The observed QCM frequency change of the modified QCM oscillator per unit time was found to be proportional to the square of the supersaturation of cadmium selenite, indicating the crystal growth of cadmium selenite at the solid/solution interface. The modified QCM oscillator exhibited selectively strong QCM response to SeO32− ion. In contrast, the responses to tested interfering anions were almost negligible. The order of anion selectivities of the present modified QCM sensor was SeO32−≫CO32−>SeO2−4, SO42−, Br−, I−, NO3−. These selectivities were basically attributable to the differences in solubility products and solubilities for the salts of each anion with cadmium (II) ion.