A review of the present methods used to remediate soil and water contaminated with organophosphate esters and developmental directions.

Organophosphate esters (OPEs) are widely used commercial additives, but their environmental persistence and toxicity raise serious concerns necessitating associated remediation strategies. Although there are various existing technologies for OPE removal, comprehensive screening for them is urgently needed to guide further research. This review provides a comprehensive overview of the techniques used to remove OPEs from soil and water, including their related influencing factors, removal mechanisms/degradation pathways, and practical applications. Based on an analysis of the latest literature, we concluded that (1) methods used to decontaminate OPEs include adsorption, hydrolysis, photolysis, advanced oxidation processes (AOPs), activated sludge processes, and microbial degradation; (2) factors such as the quantity/characteristics of the catalysts/additives, pH value, inorganic ion concentration, and natural organic matter (NOM) affect OPE removal; (3) primary degradation mechanisms involve oxidation induced by reactive oxygen species (ROS) (including •OH and SO4•-) and degradation pathways include hydrolysis, hydroxylation, oxidation, dechlorination, and dealkylation; (5) interference from the pH value, inorganic ion and the presence of NOM may limit complete mineralization during the treatment, impacting practical application of OPE removal techniques. This review provides guidance on existing and potential OPE removal methods, providing a theoretical basis and innovative ideas for developing more efficient and environmentally friendly techniques to treat OPEs in soil and water.

Effect of synthesis conditions on the porous texture of activated carbons obtained from Tara Rubber by FeCl3 activation.

This paper presents the results of an unique analysis of the influence of the mass ratio of activator FeCl3 to precursor and the temperature of the activation process on the formation of the porous structure of activated carbons obtained from Tara Rubber by FeCl3 activation. The study used the new numerical clustering based adsorption analysis method and the quenched solid density functional theory, taking into account, among other things, the heterogeneity of the analysed surface which is a new approach rarely used in the analysis of the porous structure of adsorbents. On the basis of the calculation results, it was concluded that the activated carbon with the most developed porous texture was obtained at a mass ratio (FeCl3:Tara Rubber) of 2, at an activation process temperature of 800 °C. This activated carbon is also characterised by the lowest degree of surface heterogeneity and at the same time, however, the widest range of micropores compared to activated carbons obtained at other mass ratios. The analyses carried out further demonstrated the valuable and complementary information obtained from the structure analysis methods and their high utility in practical applications, especially in the development of new industrial technologies for the production of adsorbents and the selection of optimal conditions for their production.

Azaindole grafted titanium dioxide for the photodegradation of pharmaceuticals under solar irradiation.

The application of metal-free organic molecules grafted titanium dioxide (TiO2) as photocatalysts for the degradation of pharmaceuticals under solar light has been scarcely studied. Herein, a novel photocatalyst was synthesized anchoring a bipolar electron-donor and -acceptor molecule based on azaindole derivative (AZA4) onto TiO2 aiming to improve the photoactivity under simulated solar irradiation. The TiO2-azaindole (TiO2-AZA4) was fully characterized, confirming that AZA4 was successfully grafted onto TiO2 and improving the light absorption. The grafted TiO2 was applied in the photodegradation of acetaminophen in water, showing a significantly better photocatalytic performance compared to that of pure TiO2 under both solar and visible irradiations. AZA4 grafting leads to the TiO2 band gap narrowing and favors the charge separation, thus improving the TiO2 photoactivity. The photocatalytic performance of TiO2-AZA4 was evaluated using different conditions such as photocatalyst dose or initial pH of the solution, and the radical species involved in the process were investigated. The high activity of TiO2-AZA4 was confirmed in the photodegradation of a mixture of pharmaceuticals, namely acetaminophen, ibuprofen, and antipyrine, further demonstrating its stability and catalytic performance in a novel continuous flow test under simulated solar irradiation, thus finding a new strategy to design solar-light driven photocatalysts for the degradation of pollutants in water.

Synthesis of zero-valent iron supported with graphite and plastic based carbon from recycling spent lithium ion batteries and its reaction mechanism with 4-chlorophenol in water.

Graphite and plastic recycled from spent lithium ion batteries were used to synthesize zero-valent iron/graphite (ZVI/G), zero-valent iron/plastic-based carbon (ZVI/P), and zero-valent iron/graphite and plastic-based carbon (ZVI/GP) with iron oxide through carbothermic reduction. The aim of preparing these catalysts is to improve the performance of ZVI in the removal of 4-chlorophenol (4-CP) in water through heterogeneous Fenton reactions. The structural and textural properties of materials were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption/desorption, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The synthesis procedure successfully disperses ZVI particles on the synthesized materials. The combination of graphite and plastic-based carbon in ZVI/GP resulted in the best 4-CP removal performance. The degradation data fitted pseudo-first-order kinetic well. The Increase in the ZVI/GP dosage and the hydrogen peroxide concentration enhanced the 4-CP removal due to the increase in the amount of Fe2+ ions and reactive sites. Acidic pH increased the 4-CP removal percentage due to the high H+ concentration. The increase in the temperature favored the •OH formation and facilitated the 4-CP removal. The reaction energy of ZVI/GP reaches 53.54 kJ mol-1, which is competitive among the iron catalysts reported in literatures, and showing the 4-CP removal is reaction-controlled process. This study shows a promising way of recycling graphite and plastic in spent LIBs to prepare ZVI materials for wastewater treatment with the advantages of improved conductivity by graphite and added functional groups by plastic based carbon.

Removal of emerging pollutants in aqueous phase by heterogeneous Fenton and photo-Fenton with Fe2O3-TiO2-clay heterostructures.

Fe2O3-TiO2-clay heterostructures have been prepared using an organo-bentonite as support, which organophilic character favored the fixation of TiO2. Furthermore, Fe2O3 was successfully anchored by wet impregnation. The resulting materials are characterized by a disordered layered structure and a mesoporous texture. The heterostructures were employed as catalysts for the removal of two pharmaceuticals, acetaminophen (ACE) and antipyrine (ANT), by heterogeneous Fenton and photo-Fenton processes. ACE removal under different operation conditions was studied in detail to establish structure-performance relationships, being the TiO2 formation and the developed texture the main factors controlling the activity. ANT showed a higher refractory behavior in oxidation by Fenton. Among the technologies studied, heterogeneous photo-Fenton achieved the best catalytic performance and higher kinetic rate and mineralization degree. Iron leaching was very low, lower than 5% of the initial iron load in all cases. This work demonstrates the potential application of these heterostructures for the removal of emerging pollutants of different nature.

Comparison of the behavior of ZVI/carbon composites from both commercial origin and from spent Li-ion batteries and mill scale for the removal of ibuprofen in water.

Zero valent iron/carbon composites were successfully synthesized from commercial iron oxide and graphite (ZVI/C) and also by using graphite obtained from spent Li-ion batteries and iron oxide from mill scale (ZVI/C-X) as a new approach for the valorization of these waste. The composites were synthesized through carbothermic reactions and tested as catalysts for the degradation of ibuprofen from water by Fenton reaction. The optimal conditions for synthesizing ZVI/C composites were a temperature of 1000 °C maintained for 2 h. The structural, and textural features of ZVI/C with different ZVI mass ratios were characterized by different techniques. ZVI/C composites with higher ZVI mass ratios showed higher degradation rates for the removal of ibuprofen both in presence and absence of H2O2. Moreover, ZVI/C-X composite, obtained from industrial waste, showed activity even after four consecutive cycles of use with very low concentration of iron ions in solution after reaction (4.8 mg L-1 after 4 h), which supports the high stability and low Fe-lixiviation of ZVI/C-X composite. The results of this study prove the possibility of synthesizing composites using graphite from spent Li-ion batteries and iron oxide from mill scale, and their potential for the degradation of ibuprofen in water, with comparable activities to those obtained from commercial feedstocks.

Removal of phenol and phosphate from aqueous solutions using activated carbons prepared from oily sludge through physical and chemical activation.

Preparation and characterization of activated carbons (ACs) from oily sludge by physical and chemical activation using steam, ZnCl2 and FeCl3 were investigated. The characteristics of produced adsorbents were determined by iodine number, Brunauer-Emmett-Teller (BET) equation, Fourier transform infrared spectrometry and scanning electron microscopy analyses. Batch adsorption experiments for phenol and phosphate were performed to evaluate the efficiency of adsorbents. The optimum porous structure of adsorbents with a BET surface area of 1,259 m2 g-1, total pore volume of 1.22 cm3 g-1 and iodine number of 994 mg g-1 was achieved by ZnCl2 activation at 500 °C and impregnation ratio of 1:1. The adsorption data were well fitted to the pseudo-second-order kinetic model (R2>0.99) and Freundlich isotherm (R2>0.99). The maximum adsorption capacity of phenol (238 mg g-1) and phosphate (102 mg g-1) based on the Langmuir model was achieved at pH of 6.0 and adsorbent dose of 1 g L-1. Thermodynamic parameters were negative and showed that adsorption of phenol and phosphate onto the AC was feasible, spontaneous and exothermic. The results suggested that prepared AC was an effective adsorbent for removal of phenol and phosphate ions from the polluted water.

Effect of Activating Agent on the Properties of TiO2/Activated Carbon Heterostructures for Solar Photocatalytic Degradation of Acetaminophen.

Several activated carbons (ACs) were prepared by chemical activation of lignin with different activating agents (FeCl3, ZnCl2, H3PO4 and KOH) and used for synthesizing TiO2/activated carbon heterostructures. These heterostructures were obtained by the combination of the activated carbons with a titania precursor using a solvothermal treatment. The synthesized materials were fully characterized (Wavelength-dispersive X-ray fluorescence (WDXRF), X-ray diffraction (XRD), Scanning electron microscopy (SEM), N2 adsorption-desorption, Fourier transform infrared (FTIR) and UV-visible diffuse reflectance spectra (UV-Vis DRS) and further used in the photodegradation of a target pharmaceutical compound (acetaminophen). All heterostructures were composed of anatase phase regardless of the activated carbon used, while the porous texture and surface chemistry depended on the chemical compound used to activate the lignin. Among all heterostructures studied, that obtained by FeCl3-activation yielded complete conversion of acetaminophen after 6 h of reaction under solar-simulated irradiation, also showing high conversion after successive cycles. Although the reaction rate was lower than the observed with bare TiO2, the heterostructure showed higher settling velocity, thus being considerably easier to recover from the reaction medium.

Photostability and photocatalytic degradation of ionic liquids in water under solar light.

The aim of this work is to study, (i) the photostability of different imidazolium and pyridinium ionic liquids (ILs) in water under solar light; and (ii) the photocatalytic degradation of those ILs in water with TiO2 under solar light. The effects of the type of cation and anion as well as the length of the cationic chain of the imidazolium ILs have been analyzed. These imidazolium-based ILs show high solar stability, slightly decreasing as the length of the cationic chain increases. The anion plays a main role in the stability of ILs under solar light, decreasing in the case of hydrophobic anions. The kind of head group (pyridinium or imidazolium) or the presence of functional groups (allyl, OH) also influence the solar light stability. DFT calculations on the fundamental and excited electronic states of the ILs were carried out to obtain a deeper insight on their photostability. In the case of the photocatalytic degradation of the ILs, complete conversion was achieved for all the ILS tested but mineralization reached 80% at the most. The rate of degradation increased with the length of the alkyl chain while the anion showed little effect. The pyridinium-based IL tested was the easiest to breakdown.

Effects of pH value and calcium hardness on the removal of 1,1,1-trichloroethane by immobilized nanoscale zero-valent iron on silica based supports.

Immobilizing nanoscale zero-valent iron (NZVI) particles on silica-based supports is an effective way to overcome the NZVI aggregation. The pH value and calcium hardness can change the aggregation kinetics and alter the stability of the suspensions of NZVI-silica based materials, thus change the reactivity of these NZVI-silica based materials to remove chlorinated aliphatic hydrocarbons (CAHs). The removal of CAHs by these NZVI-silica based materials includes adsorption by silica based supports and degradation by NZVI particles. Using 1,1,1-TCA and mesoporous hydrated silica (mHS) as model chlorinated aliphatic hydrocarbon (CAH) and silica based support, the effects of pH value and Ca2+ concentration on both the adsorption and adsorption-degradation processes of CAHs by NZVI-silica based materials were studied. The structural and textural features, suspension stability, particle size distribution, and Zeta potential of the materials under various conditions were characterized by different techniques. Both decreasing initial pH value and increasing Ca2+ concentration can reduce the Zeta potential of mHS and lead to the aggregation of mHS particles, thus inhibiting the removal of 1,1,1-TCA via adsorption by mHS through decreasing the number of sites for adsorption. Low initial pH value can accelerate the corrosion of NZVI core and remove the passivation layer, thus promoting the removal of 1,1,1-TCA via adsorption-degradation by NZVI@mHS. Ca2+ can decrease the sites for adsorption and form precipitates which can block mesoporous channels, thus hinder the 1,1,1-TCA removal via adsorption-degradation by NZVI@mHS.

Ag-Coated Heterostructures of ZnO-TiO2/Delaminated Montmorillonite as Solar Photocatalysts.

Heterostructures based on ZnO-TiO2/delaminated montmorillonite coated with Ag have been prepared by sol-gel and photoreduction procedures, varying the Ag and ZnO contents. They have been thoroughly characterized by XRD, WDXRF, UV-Vis, and XPS spectroscopies, and N2 adsorption, SEM, and TEM. In all cases, the montmorillonite was effectively delaminated with the formation of TiO2 anatase particles anchored on the clay layer's surface, yielding porous materials with high surface areas. The structural and textural properties of the heterostructures synthesized were unaffected by the ZnO incorporated. The photoreduction led to solids with Ag nanoparticles decorating the surface. These materials were tested as photocatalysts for the degradation of several emerging contaminants with different nitrogen-bearing chemical structures under solar light. The catalysts yielded high rates of disappearance of the starting pollutants and showed quite stable performance upon successive applications.

Silica-sepiolite nanoarchitectures.

Silica-sepiolite heterostructured materials have been prepared as novel nanoarchitectures by generation of SiO2 nanoparticles (NPs) on the surface of the sepiolite fibrous clay mineral. The synthetic approach implies the use of organo-sepiolites dispersed in isopropanol to which is incorporated a selected silicon alcoxysilane, such as tetramethoxysilane (TMOS), that then is slowly hydrolyzed to procure the formation of a viscous gel under ultrasound irradiation. Once the sol-gel reaction is achieved the intermediate silica-sepiolite organo-heterostructures can be submitted to a thermal treatment for the removal of the organic matter, which finally gives rise to the silica-sepiolite nanoarchitectures. Influence of different experimental variables, such as nature of both alkoxysilane precursor and organo-sepiolite as well as their relative ratio in the reaction media, in the characteristics of both intermediate silica-sepiolite organo-heterostructures and final nanoarchitectures has been explored. Both type of heterostructured materials have been characterized by means of diverse experimental techniques such as CHN chemical analysis, TG-DTA, XRD, FTIR, 29Si NMR, FE-SEM and TEM. Special attention has been devoted to the analysis of changes in the morphological and textural features of the SiO2-sepiolite samples before and after the thermal treatment carried out for removing the organic matter and consolidation of the silica network. This study describes the resulting nanoarchitectures as sepiolite microfibers covalently assembled to silica nanoparticles exhibiting specific surface areas ca. to 350 m2/g, practically without microporous contribution. Preliminary tests regarding the use of the SiO2-sepiolite nanoarchitectures as nanofillers in polymer nanocomposites have been also investigated in order to show one of their potential fields of application. Mechanical properties of epoxy resin nanocomposites have been determined and discussed considering the different nature of the external surface of the intermediate organo-heterostructures and the final inorganic nanoarchitectures.

Anatase-TiO2 nanomaterials: analysis of key parameters controlling crystallization.

Nanoparticulated TiO2 materials with anatase structure were synthesized by using a microemulsion method. The structural characteristics of the amorphous solid precursors and their evolution during thermal treatments were studied by using X-ray absorption structure (X-ray absorption near edge structure XANES and extended X-ray absorption fine structure EXAFS), XRD-PDF (X-ray diffraction-pair distribution function), and infrared spectroscopy. Concerning the precursor materials, XANES and EXAFS showed a local order closely related to that of the anatase structure but containing defective, undercoordinated Ti5c4+ species in addition to normal Ti6c4+ species. The PDF technique detects differences among samples in the local order (below 1 nm) and showed that primary particle size varies throughout the amorphous precursor series. The physical interpretation of results concerning the amorphous materials and their evolution under thermal treatment gives conclusive evidence that local, intraparticle ordering variations determine the temperature for the onset of the nucleation process and drive the solid behavior through the whole crystallization process. The significance of this result in the context of current crystallization theories of oxide-based nanocrystalline solids is discussed.

Influence of N-doping on the structure and electronic properties of titania nanoparticle photocatalysts.

N-containing TiO(2)-based nanostructured materials (average particle size approximately 10 nm) with an anatase-type structure were investigated using oxygen (O) K-edge and titanium (Ti) K- and L-edge X-ray absorption near-edge spectroscopy (XANES). The Ti K pre-edge features indicate that samples predominantly contain ([6])Ti with some ([5])Ti, and there is no evidence for ([4])Ti. We observed that those samples with a larger fraction of Ti in a fivefold coordination, that is, with a significant number of oxygen vacancies, also present a modified Ti environment at the medium-range scale. The presence of these defects drastically modifies the electronic structure of the conduction band, as evidenced by the O K XANES spectra, but does not result in the presence of reduced Ti(3+) states. We discuss the influence of N-doping on titania nanoparticles and their structure, electronics and photocatalytic activity.

The structural and electronic properties of nanostructured Ce1-x-yZrxTbyO2 ternary oxides: unusual concentration of Tb3+ and metal<-->oxygen<-->metal interactions.

Ceria-based ternary oxides are widely used in many areas of chemistry, physics, and materials science. Synchrotron-based time-resolved x-ray diffraction, x-ray absorption near-edge spectroscopy (XANES), Raman spectroscopy, and density-functional calculations were used to study the structural and electronic properties of Ce-Zr-Tb oxide nanoparticles. The nanoparticles were synthesized following a novel microemulsion method and had sizes in the range of 4-7 nm. The Ce1-x-yZrxTbyO2 ternary systems exhibit a complex behavior that cannot be predicted as a simple extrapolation of the properties of Ce1-xZrxO2, Ce1-xTbxO2, or the individual oxides (CeO2, ZrO2, and TbO2). The doping of ceria with Zr and Tb induces a decrease in the unit cell, but there are large positive deviations with respect to the cell parameters predicted by Vegard's rule for ideal solid solutions. The presence of Zr and Tb generates strain in the ceria lattice through the creation of crystal imperfections and O vacancies. The O K-edge and Tb LIII-edge XANES spectra for the Ce1-x-yZrxTbyO2 nanoparticles point to the existence of distinctive electronic properties. In Ce1-x-yZrxTbyO2 there is an unexpected high concentration of Tb3+, which is not seen in TbO2 or Ce1-xTbxO2 and enhances the chemical reactivity of the ternary oxide. Tb<-->O<-->Zr interactions produce a stabilization of the Tb(4f,5d) states that is responsible for the high concentration of Tb(3+) cations. The behavior of Ce1-x-yZrxTbyO2 illustrates how important can be metal<-->oxygen<-->metal interactions for determining the structural, electronic, and chemical properties of a ternary oxide.

A variable-temperature diffuse reflectance infrared fourier transform spectroscopy study of the binding of water and pyridine to the surface of acid-activated metakaolin.

Four metakaolins were prepared by heating a Spanish kaolin at 600, 700, 800, and 900 degrees C for 10 h. Following preliminary optimization, these metakaolins were acid activated in 6 M hydrochloric acid at 90 degrees C for 6 h; the samples calcined at 600, 700, and 800 degrees C produced the highest surface area solids and were selected for further study. Variable-temperature diffuse reflectance infrared Fourier transform spectroscopy analysis of the resulting acid-activated metakaolins (AAMKs) identified a wide range of hydrogen bond strengths in adsorbed water at room temperature. Above 300 degrees C it was possible to fit the broad hydroxyl stretching band to seven contributing components at 3730, 3700, 3655, 3615, 3583, 3424, and 3325 cm(-1). As the sample temperature was increased, the 3730 cm(-1) band increased in intensity as the water hydrogen bonded to AlOHAl was thermally desorbed. The other six bands decreased in intensity. The spectra of adsorbed pyridine indicated the presence of both Brönsted and Lewis acid sites on the surface of the air-dried AAMKs. Preheating the AAMK at 200 degrees C prior to pyridine sorption reduced the number of Brönsted acid sites and increased the number of thermally stable Lewis acid sites. A reduction in the amount of adsorbed pyridine after pretreating the AAMK at 400 degrees C was tentatively attributed to a reduction in surface area. This was reflected in fewer thermally stable Lewis acid sites in the AAMK pretreated at 400 degrees C compared to the number present in the sample pretreated at 200 degrees C.