Reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were prepared by chemical deposition method and were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N2-sorption and X-ray photoelectron spectroscopy (XPS). Operating parameters for the removal process of Pb(II) ions, such as temperature (20–40 °C), pH (3–5), initial concentration (400–600 mg/L) and contact time (20–60 min), were optimized using a quadratic model. The coefficient of determination (R2 > 0.99) obtained for the mathematical model indicates a high correlation between the experimental and predicted values. The optimal temperature, pH, initial concentration and contact time for Pb(II) ions removal in the present experiment were 21.30 °C, 5.00, 400.00 mg/L and 60.00 min, respectively. In addition, the Pb(II) removal by nZVI/rGO composites was quantitatively evaluated by using adsorption isotherms, such as Langmuir and Freundlich isotherm models, of which Langmuir isotherm gave a better correlation, and the calculated maximum adsorption capacity was 910 mg/g. The removal process of Pb(II) ions could be completed within 50 min, which was well described by the pseudo-second order kinetic model. Therefore, the nZVI/rGO composites are suitable as efficient materials for the advanced treatment of Pb(II)-containing wastewater.

Engineered nanoscale zero-valent metals (NZVMs) representing the forefront of technologies have been considered as promising materials for environmental remediation and antimicrobial effect, due to their high reducibility and strong adsorption capability. This review is focused on the methodology for synthesis of bare NZVMs, supported NZVMs, modified NZVMs, and bimetallic systems with both traditional and green methods. Recent studies have demonstrated that self-assembly methods can play an important role for obtaining ordered, controllable, and tunable NZVMs. In addition to common characterization methods, the state-of-the-art methods have been developed to obtain the properties of NZVMs (e.g., granularity, size distribution, specific surface area, shape, crystal form, and chemical bond) with the resolution down to subnanometer scale. These methods include spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), electron energy-loss spectroscopy (EELS), and near edge X-ray absorption fine structure (NEXAFS). A growing body of experimental data has proven that nanoscale zero-valent iron (NZVI) is highly effective and versatile. This article discusses the applications of NZVMs to treatment of heavy metals, halogenated organic compounds, polycyclic aromatic hydrocarbons, nutrients, radioelements, and microorganisms, using both ex situ and in situ methods. Furthermore, this paper briefly describes the ecotoxicological effects for NZVMs and the research prospects related to their synthesis, modification, characterization, and applications.

Reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized in the present study by chemical deposition method and were then characterized by various methods, such as Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The nZVI/rGO composites prepared were utilized for Cd(II) removal from aqueous solutions in batch mode at different initial Cd(II) concentrations, initial pH values, contact times, and operating temperatures. Response surface methodology (RSM) and artificial neural network hybridized with genetic algorithm (ANN-GA) were used for modeling the removal efficiency of Cd(II) and optimizing the four removal process variables. The average values of prediction errors for the RSM and ANN-GA models were 6.47% and 1.08%. Although both models were proven to be reliable in terms of predicting the removal efficiency of Cd(II), the ANN-GA model was found to be more accurate than the RSM model. In addition, experimental data were fitted to the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherms. It was found that the Cd(II) adsorption was best fitted to the Langmuir isotherm. Examination on thermodynamic parameters revealed that the removal process was spontaneous and exothermic in nature. Furthermore, the pseudo-second-order model can better describe the kinetics of Cd(II) removal with a good R2 value than the pseudo-first-order model.

Rhodamine B (Rh B) is a toxic dye that is harmful to the environment, humans, and animals, and thus the discharge of Rh B wastewater has become a critical concern. In the present study, reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) was used to treat Rh B aqueous solutions. The nZVI/rGO composites were synthesized with the chemical deposition method and were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, N2-sorption, and X-ray photoelectron spectroscopy (XPS) analysis. The effects of several important parameters (initial pH, initial concentration, temperature, and contact time) on the removal of Rh B by nZVI/rGO were optimized by response surface methodology (RSM) and artificial neural network hybridized with genetic algorithm (ANN-GA). The results suggest that the ANN-GA model was more accurate than the RSM model. The predicted optimum value of Rh B removal efficiency (90.0%) was determined using the ANN-GA model, which was compatible with the experimental value (86.4%). Moreover, the Langmuir, Freundlich, and Temkin isotherm equations were applied to fit the adsorption equilibrium data, and the Freundlich isotherm was the most suitable model for describing the process for sorption of Rh B onto the nZVI/rGO composites. The maximum adsorption capacity based on the Langmuir isotherm was 87.72 mg/g. The removal process of Rh B could be completed within 20 min, which was well described by the pseudo-second order kinetic model.

The B3LYP/6-311+G(d)-SDD method, which considers the relativistic effect of bromine, was adopted for the calculations of the selected polybrominated diphenyl ethers (PBDEs) in the present study, in which the B3LYP/6-311+G(d) method was also applied. The calculated values and experimental data for structural parameters of the selected PBDEs were compared to find the suitable theoretical methods for their structural optimization. The results show that the B3LYP/6-311+G(d) method can give the better results (with the root mean square errors (RMSEs) of 0.0268 for the C–Br bond and 0.0161 for the C–O bond) than the B3LYP/6-311+G(d)-SDD method. Then, the B3LYP/6-311+G(d) method was applied to predict the structures for the other selected PBDEs (both neutral and anionic species). The lowest unoccupied molecular orbital (LUMO) and the electron affinity are of a close relationship. The electron affinities (vertical electron affinity and adiabatic electron affinity) were discussed to study their electron capture abilities. To better estimate the conversion of configuration for PBDEs, the configuration transition states for BDE-5, BDE-22 and BDE-47 were calculated at the B3LYP/ 6-311+G(d) level in both gas phase and solution. The possible debromination pathway for BDE-22 were also studied, which have bromine substituents on two phenyl rings and the bromine on meta-position prefers to depart from the phenyl ring. The reaction profile of the electron-induced reductive debromination for BDE-22 were also shown in order to study its degradation mechanism.

Abstract:The commercially available nanoscale zerovalent zinc (nZVZ) was used as an adsorbent for the removal of malachite green (MG) from aqueous solutions. This material was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The advanced experimental design tools were adopted to study the effect of process parameters (viz. initial pH, temperature, contact time and initial concentration) and to reduce number of trials and cost. Response surface methodology and rapidly developing artificial intelligence technologies, i.e., artificial neural network coupled with particle swarm optimization (ANN-PSO) and artificial neural network coupled with genetic algorithm (ANN-GA) were employed for predicting the optimum process variables and obtaining the maximum removal efficiency of MG. The results showed that the removal efficiency predicted by ANN-GA (94.12%) was compatible with the experimental value (90.72%). Furthermore, the Langmuir isotherm was found to be the best model to describe the adsorption of MG onto nZVZ, while the maximum adsorption capacity was calculated to be 1000.00 mg/g. The kinetics for adsorption of MG onto nZVZ was found to follow the pseudo-second-order kinetic model. Thermodynamic parameters (∆G 0 , ∆H 0 and ∆S 0 ) were calculated from the Van't Hoff plot of lnKc vs. 1/T in order to discuss the removal mechanism of MG.

The authors wish to make the following addendum to their paper [1]:[...]

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