ABSTRACT
Two ferrite series were synthesized. One series has nanosize samples that have been prepared by the co-precipitation method, and the second series has the corresponding bulk samples that have been sintered at 1000 °C for 6 h. X-ray diffraction has been used to estimate the cubic spinel structure of both series. The crystallite size, theoretical density, and porosity of the nanomaterials are larger than those of the bulk materials. HRTEM analysis demonstrated the aggregation of nanoscale samples, including an average particle size of 9-22.5 nm. However, bulk specimens have a limited surface area. The agglomeration of the nanoparticles was seen in TEM images, in which the mean particle size was within the limit of the crystallite size (R) result and ranged from 14 to 20 nm. The appearance of the spinel phase in the samples was validated through Raman spectroscopy. Different cation occupation ratios in either tetrahedral or octahedral sites have been identified to be associated with an observable systematic shift and asymmetric flattening in Raman spectra with a variation in Cr3+ concentration. The optical characterization was performed using the UV/Vis methodology, and the results reveal that the absorption cutoff frequency declines as the chromium content rises. It was also estimated that the optical bandgap averaged 3.6 eV for nanosamples and 4.6 eV for overall bulk materials. The highest photoluminescence emission was seen at wavelengths between λem = 415 and 460 nm. The photoluminescence emission peaks of both bulk and nanoscale materials were red-shifted. These results accurately reflect the corresponding energy gap values for almost the same ranges. Sintering leads to a rise in photoluminescence.
ABSTRACT
The adoption of chlorine in drinking water disinfection with the determination of residual chlorine in the form of hypochlorite ion (ClO-) is in widespread demand. Several sensors including colorimetric, fluorometric, and electrochemical methods are currently in use, but detection limits and ease of application remain a challenge. In this work, two new cyanine derivatives-based ClO- sensors, that were prepared by solvent-free microwave synthesis, are reported. The two sensors are highly sensitive and selective to ClO-, exhibiting a noticeable color change visible to the naked eye. Additionally, the sensors can detect ClO- without interference from other potential water pollutants, with low detection limits of 7.43 ppb and 0.917 ppb based on absorption performance. When using fluorometric methods, the sensors' detection limits are pushed down to 0.025 ppb and 0.598 ppb for sensors I and II, respectively. The sensors can be loaded with paper strips for field and domestic detection of ClO- in tap water treatment installations. Using the quartz crystal microbalance (QCM) technique, these sensors showed strong detection sensitivity to ClO-, with detection limits of 0.256 ppm and 0.09 ppm for sensors I and II, respectively. Quantum chemical studies using density functional theory (DFT) calculations, natural bond orbital (NBO) analysis, molecular electrostatic potential (MESP), and time-dependent density functional theory (TD-DFT) supported the findings. The sensing mechanism is rationalized in terms of radical cation formation upon ClO- oxidation of cyanine sensors I and II.
