Boosted micropollutant removal over urchin-like structured hydroxyapatite-incorporated nickel magnetite catalyst via peroxydisulfate activation.

In this work, urchin-like structured hydroxyapatite-incorporated nickel magnetite (NiFe3O4/UHdA) microspheres were developed for the efficient removal of micropollutants (MPs) via peroxydisulfate (PDS) activation. The prepared NiFe3O4/UHdA degraded 99.0 % of sulfamethoxazole (SMX) after 15 min in 2 mM PDS, having a first-order kinetic rate constant of 0.210 min-1. In addition, NiFe3O4/UHdA outperformed its counterparts, i.e., Fe3O4/UHdA and Ni/UHdA, by giving rise to corresponding 3.6-fold and 8.6-fold enhancements in the SMX removal rate. The outstanding catalytic performance can be ascribed to (1) the urchin-like mesoporous structure with a large specific surface area and (2) the remarkable synergistic effect caused by the redox cycle of Ni3+/Ni2+ and Fe2+/Fe3+ that enhances multipath electron transfers on the surface of NiFe3O4/UHdA to produce more reactive oxygen species. Moreover, the effects of several reaction parameters, in this case the initial solution pH, PDS dosage, SMX concentration, catalyst loading, co-existing MPs and humic acid level on the catalytic performance of the NiFe3O4/UHdA + PDS system were systematically investigated and discussed in detail. The plausible catalytic mechanisms in the NiFe3O4/UHdA + PDS system were revealed via scavenging experiments and electron paramagnetic resonance analysis, which indicated a radical (•OH and SO4•-) as the major pathway and a nonradical (1O2) as the minor pathway for SMX degradation. Furthermore, NiFe3O4/UHdA exhibited fantastic magnetically separation and retained good catalytic activity with a low leached ion concentration during the performance of four cycles. Overall, the prepared NiFe3O4/UHdA with outstanding PDS activation could be a promising choice for the degradation of persistent organic pollutants from wastewater.

Catalytic ozonation with vanadium oxide-doped TiO2 nanoparticles for the removal of di-2-ethylhexyl phthalate.

Among various plastic additives, di-2-ethylhexyl phthalate (DEHP) has been a great concern due to its high leaching potential and harmful effects on both human and the ecosystem. For the effective oxidation and mineralization of DEHP by ozone in the existing TiO2 catalytic processes, the heterogeneous catalyst, vanadium oxide (V2O5)-incorporated TiO2 (V2O5/TiO2), was synthesized. The generation of hydroxyl radicals was promoted by cyclic redox reactions of vanadium atoms in V2O5/TiO2 via the increase of surface oxygen vacancies by the replacement of V5+ species in the lattice of TiO2. The catalytic ozonation in the presence of V2O5/TiO2 exhibited the significantly higher degradation of DEHP with the pseudo-second-order kinetic constant of 1.7 × 105 mM-1min-1 and the removal efficiency of 58.7% after 60 s in 2 mg/L of ozone. The degradation of DEHP was initiated by the shortening of the alkyl-side chain followed by the opening of esterified benzene moieties.

Urchin-like structured magnetic hydroxyapatite for the selective separation of cerium ions from aqueous solutions.

In this study, bio-inspired urchin-like structured hydroxyapatite (UHdA) and its magnetic composite (UHdA@Fe3O4) were developed for efficient and easy separation of cerium ions (Ce3+) from aquatic waste streams. UHdA and UHdA@Fe3O4 exhibited superior Ce3+ adsorption capacities of 248.39 and 230.01 mg/g-UHdA respectively, compared to a commercial HdA (141.71 mg/g-HdA) due to their hierarchical mesoporous structure and large specific surface area. The adsorption of Ce3+ to UHdA and UHdA@Fe3O4 were heterogeneous, pseudo-second-order-kinetic, and the rate-limiting step was external mass transfer and intra-particle diffusion. Moreover, thermodynamic studies revealed that the adsorption process was spontaneous and endothermic nature. The high selectivity towards Ce3+ in multi-ionic systems is attributed to the strong affinity between strong Lewis acid (Ce3+) and base (PO43- and OH-) interactions. XRD, FTIR, and XPS analysis demonstrated that the adsorption was mainly attributable to the ion exchange of Ce3+ with Ca2+ and to surface complexation. The desorption of Ce3+ was efficiently accomplished using 0.1 M HNO3. The results suggest that UHdA and UHdA@Fe3O4 could be promising choices for the adsorption and recovery of rare earth elements.

Incorporation of iron (oxyhydr)oxide nanoparticles with expanded graphite for phosphorus removal and recovery from aqueous solutions.

In this work, iron (oxyhydr)oxide nanoparticle-doped expanded graphite (IO/EG-1 and IO/EG-2) was prepared via a hydrothermal reaction and applied for the phosphorus adsorption in the aqueous solutions. The analysis of scanning electron microscopy (SEM) and X-ray diffraction (XRD) verified the successful fabrication of IO/EGs, and iron (oxyhydr)oxide nanoparticles became more crystalized according to the calcination at high temperature (IO/EG-2). The maximum adsorption capacity of IO/EG-1 was considerably higher (7.30 mg/g) than that of IO/EG-2 (0.70 mg/g) mainly due to the electrostatic interaction between the negatively charged phosphate ions with iron (oxyhydr)oxides. At the neutral pH, IO/EG-1 exhibited more positively charged than IO/EG-2, which the iso-electric points (IEP) were pH of 9.1 and 6.0, respectively. The thermodynamic study also suggested that the phosphorus adsorption energy of IO/EG-1was considerably favorable (-12.13 kJ/mol) than that of IO/EG-2 (-7.43 kJ/mol). The regeneration of IO/EG-1 were efficiently achieved by a simple extraction using an alkaline solution such as NaOH. Overall, our study suggested that the prepared IO/EGs could be used as good adsorbents for the phosphorus recovery from aqueous solutions.

Selective removal of color substances by carbon-based adsorbents in livestock wastewater effluents.

Livestock wastewater effluent generated after the anaerobic treatment process contains the considerable amount of color-causing organic matter. In this study, a quantitative comparison of three carbon-based adsorbents included granular activated carbon (GAC), expanded graphite (EG), and multi-walled carbon nanotubes (MWNTs) was carried out for the potential application to the removal of color substances, and their mechanism was proposed. Although GAC showed the highest specific dissolved organic carbon (DOC) adsorption capacity, the color removal efficiency was the smallest among three adsorbents. The selective color removal ratios of EG and MWNTs reached 22.7 ± 0.1 PtCo/mg-DOC-removed and 21.2 ± 0.1 PtCo/mg-DOC-removed, respectively, while that of GAC was only 12.3 ± 0.1 PtCo/mg-DOC-removed. The selective adsorption of color substances by graphene-based carbon materials was due to the aromatic π-π interaction between organic matter and the hexagonal carbon lattice of graphene. The analysis of molecular weight distribution also confirmed that the exposed surface area and macro-pores were responsible for the adsorption of high molecular weight color substances. The chemical regeneration of three adsorbents was examined using 1% NaOCl solution and MWNTs showed almost complete recovery of the initial color removal capacity. In conclusion, MWNTs were the most suitable carbon nanomaterial for the selective color removal from livestock wastewater effluent.

Controlled formation of magnetic yolk-shell structures with enhanced catalytic activity for removal of acetaminophen in a heterogeneous fenton-like system.

Encapsulating magnetic nanoparticles in a silica shell is a promising approach in many research fields. We recently demonstrated that the magnetic yolk-shell structure of Fe3O4@SiO2, which consists of an inner magnetite core and outer silica shell separated by a hollow void space, and its modified counterparts can be used as an effective catalyst for removal of acetaminophen in a heterogeneous Fenton-like reaction. The present study develops this approach further in an effort to design an effective procedure for preparing an optimum yolk-shell structure capable of greater catalytic performance. We investigated the use of a controlled synthesis strategy to fabricate an Fe3O4@SiO2 yolk-shell structure under varying conditions. Our focus was a single-step process that examines the effects of Stöber solution temperature, tetraethyl orthosilicate (TEOS) and hexadecyltrimethylammonium bromide (CTAB) concentrations, ethanol and water volume ratio, incubation time, and temperature on Fe3O4@SiO2 textural morphologies. The catalytic performance of the prepared materials was evaluated through oxidative degradation of acetaminophen in a heterogeneous Fenton-like reaction. Field emission transmission electron microscopy observation showed that magnetic yolk-shell structures with appropriate diameter, shell thickness, and hollow void space could be generated through tight control of synthesis conditions. Particle size and hollow void space increased when TEOS concentration increased from 22.10 to 88.50 mM. Hollow void space also increased as incubation time increased from 24 h to 72 h or incubation temperature increased from 50 to 90 °C. However, a yolk-shell structure did not form at a TEOS concentration of 11.10 mM, an incubation time of 3 h, or with an inappropriate ratio of ethyl alcohol and deionized water. Catalytic activity for degradation of acetaminophen increased with increasing hollow void space and thinning silica shell. In addition, the selected appropriate materials exhibited effective catalytic performance over five cycles of regeneration. This study demonstrates the significance of controlling the formation of yolk-shell structures, which enabled us to produce Fe3O4@SiO2 yolk-shell structures of desired and predictable size, hollow void space volume, and shell thickness for higher catalytic performance in degradation of pharmaceuticals in heterogeneous Fenton-like systems.

Nonsacrificial Template Synthesis of Magnetic-Based Yolk-Shell Nanostructures for the Removal of Acetaminophen in Fenton-like Systems.

Recently, yolk-shell structured materials with active metal cores have received considerable attention in heterogeneous Fenton-like systems, which have excellent catalytic performance. In this study, we initially attempted the nonsacrificial template synthesis of yolk-shell structured nanoparticles with magnetite cores encapsulated in a mesoporous silica shell (Fe3O4@SiO2) via a modified sol-gel process and then evaluated their catalytic activity for acetaminophen degradation in Fenton-like systems. Second, copper nanoparticles were decorated on the surface of the Fe3O4@SiO2 microspheres (Fe3O4@SiO2@Cu) to enhance the catalytic activity. The morphological, structural, and physicochemical properties of the prepared materials were characterized via X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, field emission transmission electron microscopy, nitrogen adsorption-desorption isotherms, specific surface area, ζ-potential, magnetic properties, and Fourier transform infrared spectroscopy. The results demonstrated a successful fabrication of the targeted materials. The yolk-shell structured materials possess a spherical morphology with an active core, protective shell, and hollow void. The Fe3O4@SiO2 and Fe3O4@SiO2@Cu variants showed acetaminophen removal rates significantly higher compared to those of their counterparts, i.e., the Fe3O4 and Fe3O4@Cu core-shell structures. Fe3O4@SiO2@Cu showed that the copper nanoparticles were firmly immobilized on the mesoporous silica shell, dramatically improving the catalytic performance. Both the yolk-shell structured Fe3O4@SiO2 and Fe3O4@SiO2@Cu exhibited good separation and satisfactory regeneration properties, which could be recycled six times without any obvious decline in catalytic activity. Overall, the results of this study suggested that Fe3O4@SiO2 and Fe3O4@SiO2@Cu yolk-shell nanostructures could be promising catalysts for a heterogeneous Fenton-like system by which the removal of emerging contaminants can be greatly improved.

Thermodynamic analysis of fatty acid harvesting by novel carbon-based adsorbent.

In this study, separation and concentration of fatty acids (FA) from the synthetic food processing wastewater containing low concentration of FA (250 mg/L) were investigated using expanded graphite (EG) as a novel adsorbent at different temperatures (298~318 K). The adsorption results were further analyzed to verify adsorption mechanisms and thermodynamics of FA onto EG. Results show that the adsorption of FA onto EG was explained well by the Langmuir model with the maximum adsorption capacity up to 8.01 g FA/g EG at 298 K, and considerably affected by temperature. The adsorption kinetics fitted with pseudo-second-order kinetic model and the adsorption mechanism analysis showed that the intraparticle diffusion was not the rate-limiting step, but the coalescence of FA droplets played the significant role for novel adsorption of FA onto EG. The calculated activation energy and thermodynamic parameters such as Gibbs free energy change (ΔG(0)), enthalpy change (ΔH(0)), and entropy change (ΔS(0)) indicated that the adsorption of FA onto EG was very feasible, was highly spontaneous, occurred physically, was exothermic in nature, and was stable in aquatic environmental changes. Overall, FA can be effectively harvested and concentrated from the food processing wastewater by EG even at low concentration.