Enhanced Visible-Light-Responsive Photocatalytic Degradation of Ciprofloxacin by the CuxO/Metal-Organic Framework Hybrid Nanocomposite.

Ciprofloxacin (CIP) is a commonly used antibiotic, however, once in the environment, it is highly toxic with a poor biodegradability. Given these attributes, an effective strategy for the removal of CIP is urgently needed for the protection of water resources. Herein, a novel copper metal-organic framework (CuxO/MOF) multifunctional material has been produced, in this work, by the calcination of Cu-MOF urea at 300 °C, in the presence of a 5% H2 atmosphere. The morphological, structural, and thermal properties of the prepared CuxO/MOF were determined through various techniques, and its photocatalytic behavior was investigated for the degradation of CIP under visible-light irradiation. The prepared CuxO/MOF bifunctional material is presented as a graphitic carbon-layered structure with a particle size of 9.2 ± 2.1 nm. The existence of CuO-Cu2O-C, which was found on the CuxO/MOF surface, enhanced the adsorption efficiency and increased the photosensitivity of CuxO/MOF, towards the degradation of CIP in aqueous solutions. The tailored CuxO/MOF, not only shows an excellent CIP degradation efficiency of up to 92% with a constant kinetic rate (kobs) of 0.048 min−1 under visible light, but it can also retain the stable photodegradation efficiency of >85%, for at least six cycles. In addition, CuxO/MOF has an excellent adsorption capacity at pH 6.0 of the maximum Langmuir adsorption capacity of 34.5 mg g−1 for CIP. The results obtained in this study demonstrate that CuxO/MOF is a reliable integrated material and serves as an adsorbent and photocatalyst, which can open a new pathway for the preparation of visible-light-responsive photocatalysts, for the removal of antibiotics and other emerging pollutants.

Sustainable Recovery of Valuable Nanoporous Materials from High-Chlorine MSWI Fly Ash by Ultrasound with Organic Acids.

The new technology development for municipal solid waste incineration fly ash treatment and reuse is urgent due to landfill shortage and environmental effect of leached hazardous substances. Chlorine (Cl) is worth considering due to its high levels in fly ash. In this study, a treatment process of ultrasound combined with organic acid was used to eliminate Cl from fly ash to enhance its properties for reuse. Taguchi methodology was implemented to design the experiments by controlling four impact factors and the contribution of each factor was evaluated by the ANOVA analysis of variance. Following two treatment steps within 5 min with a solid/liquid ratio of 1:10 at 165 kHz, 98.8% of Cl was eliminated. Solid/liquid ratio was the most prominent factor that contributed to the Cl removal with more than 90%, according to the ANOVA analysis of variance. Tert-butyl alcohol (tBuOH), an •OH radical scavenger, was utilized to examine different effects of ultrasonic cavitation on Cl removal efficiency. A 20 kHz ultrasound was used to explore the influence of multi-frequency ultrasound with different mechanical and sonochemical effects on the fly ash dechlorination. This ultrasonic-assisted organic acid treatment was found to be a time and cost-effective pathway for fly ash Cl removal.

Levofloxacin degradation under visible-LED photo-catalyzing by a novel ternary Fe-ZnO/WO3 nanocomposite.

As semiconductor photocatalysts showing their efficient redox ability upon illumination, new development of materials to enhance the pollution degradation is gaining popularity, especially on their oxidation ability. In this study, a highly stable ternary Fe-ZnO/WO3 nanocomposite photocatalyst has been synthesized in order to improve charge transfer of photocatalytic oxidation under 30W LED light (425-470 nm) to efficiency degrade the Levofloxacin (LVF) in the solution. This catalyst was characterized and analyzed by XRD, FE-SEM, HR-TEM, X-ray XPS, UPS, PL, TRPL, LSV, EIS, and Photocurrent. Various important factors for the photodegradation were investigated, including Fe content, initial LVF concentration, catalyst dosage, and solution pH. The optimal conditions were Fe 1.0 wt%, LVF 10 mg L-1, Fe-ZnO/WO3 dosage 0.5 g L-1, and pH 7 for LVF photodegradation up to 96% with a kinetic rate constant of 0.0342 min-1 and were stable in photodegradation efficiency (90%) after five test cycles. In the visible LED light, the activation bandgap was estimated to be 2.75 eV with high electron-hole pair separation and charge transfer from Fe-ZnO to WO3 that could enhance the generation of active species of •OH. Moreover, the more effective charge separation of Fe-ZnO/WO3 were confirmed by lower PL intensity and longer charge carrier lifetime. Fe-ZnO/WO3 also demonstrated the excellent electrochemical properties with high photocurrent and small resistance. For the LVF degradation, 3 possible pathways were proposed with 12 intermediate products. This study demonstrated that the synthesized Fe-ZnO/WO3 could serve as a reliable visible-light responsive photocatalysts with the potential for degrading antibiotics in solution.

Fe/Ni Bimetallic Organic Framework Deposited on TiO2 Nanotube Array for Enhancing Higher and Stable Photoelectrochemical Activity of Oxygen Evaluation Reaction.

Photoelectrochemical (PEC) water splitting is a promising strategy to improve the efficiency of oxygen evolution reactions (OERs). However, the efficient adsorption of visible light as well as long-term stability of light-harvesting electrocatalysis is the crucial issue in PEC cells. Metal-organic framework (MOF)-derived bimetallic electrocatalysis with its superior performance has wide application prospects in OER and PEC applications. Herein, we have fabricated a nickel and iron bimetallic organic framework (FeNi-MOF) deposited on top of anodized TiO2 nanotube arrays (TNTA) for PEC and OER applications. The FeNi-MOF/TNTA was incorporated through the electrochemical deposition of Ni2+ and Fe3+ onto the surface of TNTA and then connected with organic ligands by the hydrothermal transformation. Therefore, FeNi-MOF/TNTA demonstrates abundant photoelectrocatalytic active sites that can enhance the photocurrent up to 1.91 mA/cm2 under 100 mW/cm2 and a negligible loss in activity after 180 min of photoreaction. The FeNi-MOF-doped photoanode shows predominant photoelectrochemical performance due to the boosted excellent light-harvesting ability, rapid photoresponse, and stimulated interfacial energy of charge separation under the UV-visible light irradiation conditions. The results of this study give deep insight into MOF-derived bimetallic nanomaterial synthesis for photoelectrochemical OER and provide guidance on future electrocatalysis design.

Simultaneous Recovery of Display Panel Waste Glass and Wastewater Boron by Chemical Oxo-precipitation with Fluidized-Bed Heterogeneous Crystallization.

Silica-based carrier is a promising material for recovery of metal and nonmetal contaminants in chemical oxo-precipitation-fluidized bed crystallization (COP-FBC) system. Boron species are an essential element for plant growth and can cause health concerns in human beings at high concentrations in water environments. The composition of thin-film transistor liquid crystal display (TFT-LCD) contains a wide variety of metal oxides and can be tailored as promising functional mesoporous carriers for boron crystallization recovery in the presence of barium ions and hydrogen peroxide. In this study, waste-derived mesoporous aluminosilicate (MAS) nanomaterial in the presence of barium ions and hydrogen peroxide was used as a carrier for sustainable recovery of crystallized boron, a priority wastewaters pollutant. The MAS shows the hierarchically homogeneous distribution of nanostructured aluminosilicate particles with an average size of 12.8 ± 3.6 nm on the surface after the activation with Na2CO3 at 1000 °C. Moreover, the negatively charged surface and the mesoporous structure of MAS enhance the adsorption of Ba2+ onto MAS, and the Langmuir adsorption capacity of 105 mg/g is achieved, which is conducive to the enhancement of the recovery of boron species. Moreover, the recovery efficiency and crystallization ratio of boron by MAS can be up to 84.5 and 93.4%, respectively. The cross-sectional scanning electron microscopy images and the high-temperature X-ray diffraction results confirm the boron recovery mechanism that the negatively charged functional group as well as the mesoporosity of MAS triggers the rapid formation of needle-shaped precipitates of barium peroxoborate, and then converted to barium borate after calcination at 1050 °C. Results obtained in this study clearly demonstrate the possibility of fabricating environmentally benign mesoporous aluminosilicate adsorbents from TFT-LCD waste to sustainably recover and crystallize boron species from water and wastewater in COP-FBC.

Sustainable valorization of mesoporous aluminosilicate composite from display panel glasses waste for adsorption of heavy metal ions.

The recycling of the huge amount of thin film transistor liquid crystal display (TFT-LCD) glass wastes has become one of the worldwide environmental issues. Herein, a novel and cost-effective synthesis method for the fabrication of mesoporous aluminosilicate composite (M-ANC) from the TFT-LCD waste has been developed to serve as the environmentally benign adsorbent for the removal of metal ions including Cu2+, Zn2+ and Ni2+. After melting at 1000 °C in the presence of Na2CO3 for phase separation, nanoparticles with average particle size of 12 nm appear on the surface of M-ANC, and subsequently results in the production of mesoporous structure with a surface area of 175 m2 g-1. The tailored M-ANC shows negatively charged and functional groups, which exhibits an excellent adsorption capacity toward metal ion removal in the pH range of 1.5-7.0. The maximum Langmuir adsorption capacity of Cu2+, Zn2+ and Ni2+ are determined to be 64.5, 34.0 and 23.1 mg g-1, respectively, at pH 3.5. Moreover, the environmental applicability of M-ANC is evaluated by column experiment in the presence of real electroplating wastewater. M-ANC can effectively remove Ni2+ in the electroplating wastewater with the adsorption capacity of 18.7 mg g-1. Results obtained in this study clearly indicate that M-ANC recycled from TFT-LCD is a novel environmentally friendly adsorbent toward metal ion removal, which can open a gateway to fabricate mesoporous aluminosilicate materials through the recycling of other electronic wastes for real environmental application to remove metal ions and other emerging pollutants in the contaminated water and wastewater.