Preparation of chemically and thermally modified water caltrop epicarp (Trapa natans L.) adsorbent for enhanced adsorption of Ni(II) from aqueous solution.

The present study aims to prepare waste water caltrop (Trapanatans L.) epicarp (WCS)-based adsorbents such as raw WCS (WCS-Raw), citric acid-grafted WCS (WCS-CA), acrylamide-grafted WCS (WCS-AM), and calcined WCS (WCS-Si) for Ni(II) removal from aqueous solution in batch adsorption process. The physical and chemical properties of the prepared adsorbents were investigated by different characterization techniques such as scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy, nitrogen adsorption-desorption analyses, and pH at the Point of Zero Charge (pHpzc) in order to assess the suitability and effectiveness of the adsorbents for the removal of Ni(II) by understanding their surface morphology, chemical composition, porosity, and surface charge properties. The experimental Ni(II) adsorption data followed both the Langmuir isotherm and the pseudo-second-order kinetic model suggesting the adsorption process on the prepared adsorbents is well-described by these models. The modified adsorbents WCS-CA, WCS-AM, and WCS-Si exhibited a maximum adsorption capacity of 52.08, 40.32, and 158.73 mg/g, respectively, while WCS-Raw had a capacity of 29.06 mg/g. The thermodynamic study revealed that the adsorption process was feasible, spontaneous, and endothermic. The desorption study demonstrated that the adsorbents could be reused for multiple cycles with minimal loss of activity. The present work evidenced the potential practical applicability and sustainability of the WCS-based adsorbents as promising adsorbents in treating and removing Ni(II) from wastewater.

Langmuir Adsorption Kinetics in Liquid Media: Interface Reaction Model.

Adsorption kinetic equation has been derived assuming that the process follows the behavior of a heterogeneous chemical reaction at the solid-liquid interface. This equation is converted into the Langmuir isotherm at equilibrium and describes well the unsteady-state adsorption process. Based on that, a working equation has been developed, which gives adsorption-rate-constant independent of operating parameters including concentration. Also, a kinetic model expressed as a sum of first- and second-order systems available in the literature has been applied (modified with the interface reaction concept) to determine the adsorption rate constant. Both methods gave similar results. Three dimensionless numbers have been developed to determine and distinguish pseudo-first-order and pseudo-second-order kinetics justified from the viewpoint of chemical kinetics. It is shown that curve-fitting with a high correlation coefficient could validate an empirical kinetic model, but the fitted model parameters could not automatically be related to chemical kinetic parameters if the model itself is not grounded on well-defined chemical kinetics. Finally, it is concluded that the currently applied empirical approach could not provide reliable data for comparison among similar systems, while the Langmuir kinetic equation developed based on the concept of heterogeneous reaction would be a good basis for standardization of the method for adsorption system characterization.

A novel highly selective electrochemical chlorobenzene sensor based on ternary oxide RuO2/ZnO/TiO2 nanocomposites.

A novel electrochemical (EC) chlorobenzene (CBZ) sensor was fabricated using a ternary oxide RuO2/ZnO/TiO2 nanocomposite (NC)-decorated glassy carbon electrode (GCE). The nanoparticles (NPs) were synthesized by a wet-chemical method and characterized by X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), and ultraviolet-visible (UV-vis) spectroscopy. The synthesized RuO2/ZnO/TiO2 NC was layered as thin film on a GCE with Nafion (5% suspension in ethanol) adhesive, and the as-prepared sensor was subjected to CBZ analysis using an electrochemical approach. The calibration of the proposed CBZ sensor was executed with a linear relation of current versus concentration of CBZs known as the calibration curve. The sensitivity (32.02 µA µM-1 cm-2) of the CBZ sensor was calculated from the slope of the calibration curve by considering the active surface area of the GCE (0.0316 cm2). The lower detection limit (LD; 98.70 ± 4.90 pM) was also calculated at a signal-to-noise ratio of 3. Besides these, the response current followed a linear relationship with the concentration of chlorobenzene and the linear dynamic range (LDR) was denoted in the range of 0.1 nM to 1.0 µM. Moreover, the CBZ sensor was found to exhibit good reproducibility, reliability, stability, and fast response time. Finally, the sensing mechanism was also discussed with the energy-band theory of ternary doped semiconductor materials. The sensing activity of the proposed sensor was significantly enhanced due to the combined result of depletion layer formation at the heterojunction of RuO2/ZnO/TiO2 NCs as well as the activity of RuO2 NPs as oxidation catalysts. The proposed CBZ sensor probe based on ternary oxide RuO2/ZnO/TiO2 NCs was developed with significant analytical parameters for practical application in monitoring the environmental pollutants of CBZs for the safety of environmental fields on a large scale.

Facile one-pot synthesis of heterostructure SnO2/ZnO photocatalyst for enhanced photocatalytic degradation of organic dye.

In this work, heterostructure SnO2/ZnO nanocomposite photocatalyst was prepared by a straightforward one step polyol method. The resulting photocatalysts were characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption analyses, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The results showed that the synthesized SnO2/ZnO nanocomposites possessed mesoporous wurtzite ZnO and cassiterite SnO2 nanocrystallites. The photocatalytic activity of the prepared SnO2/ZnO photocatalyst was investigated by the degradation of methylene blue dye under UV light irradiation. The heterostructure SnO2/ZnO photocatalyst showed much higher photocatalytic activities for the degradation of methylene blue dye than individual SnO2, ZnO nanomaterials and reference commercial TiO2 P25. This higher photocatalytic degradation activity was due to enhanced charge separation and subsequently the suppression of charge recombination in the SnO2/ZnO photocatalyst resulting from band offsets between SnO2 and ZnO. Finally, these heterostructure SnO2/ZnO nanocatalysts were stable and could be recycled several times without any appreciable change in degradation rate constant which opens new avenues toward potential industrial applications.

Electrochemical detection of 2-nitrophenol using a heterostructure ZnO/RuO2 nanoparticle modified glassy carbon electrode.

A highly selective chemisensor for 2-nitrophenol detection was fabricated using ZnO/RuO2 nanoparticles (NPs) synthesized by impregnation method. The as-synthesized NPs were characterized through UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), Energy dispersive X-ray spectroscopy (EDS), FTIR and X-ray diffraction (XRD). A glassy carbon electrode was modified with as-synthesized ZnO/RuO2 nanoparticles and utilized as a chemical sensor for the detection of 2-nitrophenol. The fabricated sensor exhibited excellent sensitivity (18.20 µA µM-1 cm-2), good reproducibility, short response time (8.0 s.), the lowest detection limit (52.20 ± 2.60 pM) and long-term stability in aqueous phase without interference effects. Finally, the fabricated sensor was validated as a 2-NP probe in various environmental water samples at room conditions.

Improved photocatalytic activity in RuO2-ZnO nanoparticulate heterostructures due to inhomogeneous space charge effects.

New 2-6 wt% RuO2-ZnO heterojunction nanocatalysts were synthesized by a straightforward two-step procedure. They were composed of a porous network of aggregated 25 nm wurtzite ZnO nanocrystallites modified with RuO2 and showed enhanced light absorption in the visible region due to surface plasmon resonance. In order to investigate the energetic structure of the photocatalyst XPS core line and valence band spectra of in situ in UHV prepared heterointerfaces were compared to results obtained from the particles. The shift of Zn 2p3/2 and O 1s core level spectra was determined to be at least 0.80 ± 0.05 eV for the in situ prepared heterojunction whereas it was found to be 0.40 ± 0.05 and 0.45 ± 0.05 eV, respectively, in the photocatalysts. The different values were ascribed to the reduced size of the particles and the different measurability of band bending at the interface of the heterojunction RuO2-ZnO compared to the nanoparticles. The RuO2/ZnO photocatalysts showed higher photocatalytic activity and recyclability than pure ZnO for the degradation of various dyes under UV light irradiation due to vectorial charge separation of photogenerated electrons and holes resulting from internal electric field, the ruthenium oxide acting as a quasi-metallic contact.

Nanostructured SnO2-ZnO heterojunction photocatalysts showing enhanced photocatalytic activity for the degradation of organic dyes.

Nanoporous SnO(2)-ZnO heterojunction nanocatalyst was prepared by a straightforward two-step procedure involving, first, the synthesis of nanosized SnO(2) particles by homogeneous precipitation combined with a hydrothermal treatment and, second, the reaction of the as-prepared SnO(2) particles with zinc acetate followed by calcination at 500 °C. The resulting nanocatalysts were characterized by X-ray diffraction (XRD), FTIR, Raman, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption analyses, transmission electron microscopy (TEM), and UV-vis diffuse reflectance spectroscopy. The SnO(2)-ZnO photocatalyst was made of a mesoporous network of aggregated wurtzite ZnO and cassiterite SnO(2) nanocrystallites, the size of which was estimated to be 27 and 4.5 nm, respectively, after calcination. According to UV-visible diffuse reflectance spectroscopy, the evident energy band gap value of the SnO(2)-ZnO photocatalyst was estimated to be 3.23 eV to be compared with those of pure SnO(2), that is, 3.7 eV, and ZnO, that is, 3.2 eV, analogues. The energy band diagram of the SnO(2)-ZnO heterostructure was directly determined by combining XPS and the energy band gap values. The valence band and conduction band offsets were calculated to be 0.70 ± 0.05 eV and 0.20 ± 0.05 eV, respectively, which revealed a type-II band alignment. Moreover, the heterostructure SnO(2)-ZnO photocatalyst showed much higher photocatalytic activities for the degradation of methylene blue than those of individual SnO(2) and ZnO nanomaterials. This behavior was rationalized in terms of better charge separation and the suppression of charge recombination in the SnO(2)-ZnO photocatalyst because of the energy difference between the conduction band edges of SnO(2) and ZnO as evidenced by the band alignment determination. Finally, this mesoporous SnO(2)-ZnO heterojunction nanocatalyst was stable and could be easily recycled several times opening new avenues for potential industrial applications.

Adsorption of methylene blue from aqueous solution by jackfruit (Artocarpus heteropyllus) leaf powder: A fixed-bed column study.

Continuous fixed-bed studies were undertaken to evaluate the efficiency of jackfruit leaf powder (JLP) as an adsorbent for the removal of methylene blue (MB) from aqueous solution under the effect of various process parameters like bed depth (5-10cm), flow rate (30-50mL/min) and initial MB concentrations (100-300mg/L). The pH at point of zero charge (pH(PZC)) of the adsorbent was determined by the titration method and a value of 3.9 was obtained. A FTIR of the adsorbent was done before and after the adsorption to find the potential adsorption sites for interaction with methylene blue molecules. The results showed that the total adsorbed quantities and equilibrium uptake decreased with increasing flow rate and increased with increasing initial MB concentration. The longest breakthrough time and maximum MB adsorption were obtained at pH 10. The results showed that the column performed well at low flow rate. Also, breakthrough time and exhaustion time increased with increasing bed depth. The bed-depth service time (BDST) model and the Thomas model were applied to the adsorption of MB at different bed depths, flow rates, influent concentrations and pH to predict the breakthrough curves and to determine the characteristic parameters of the column that are useful for process design. The two model predictions were in very good agreement with the experimental results at all the process parameters studied indicating that they were very suitable for JLP column design.

Adsorptive removal of methylene blue by tea waste.

The potentiality of tea waste for the adsorptive removal of methylene blue, a cationic dye, from aqueous solution was studied. Batch kinetics and isotherm studies were carried out under varying experimental conditions of contact time, initial methylene blue concentration, adsorbent dosage and pH. The nature of the possible adsorbent and methylene blue interactions was examined by the FTIR technique. The pH(pzc) of the adsorbent was estimated by titration method and a value of 4.3+/-0.2 was obtained. An adsorption-desorption study was carried out resulting the mechanism of adsorption was reversible and ion-exchange. Adsorption equilibrium of tea waste reached within 5h for methylene blue concentrations of 20-50mg/L. The sorption was analyzed using pseudo-first-order and pseudo-second order kinetic models and the sorption kinetics was found to follow a pseudo-second order kinetic model. The extent of the dye removal increased with increasing initial dye concentration. The equilibrium data in aqueous solutions were well represented by the Langmuir isotherm model. The adsorption capacity of methylene blue onto tea waste was found to be as high as 85.16mg/g, which is several folds higher than the adsorption capacity of a number of recently studied in the literature potential adsorbents. Tea waste appears as a very prospective adsorbent for the removal of methylene blue from aqueous solution.