Dr. Valdes-Morales, Hector

Antibiotic overuse and indiscriminate disposal ultimately lead to overexploitation of the ecosystems expanding requirements, producing significant environmental and biological consequences. Advanced oxidation processes (AOPs) have kindled the interest of many researchers in targeting the destruction of antimicrobial and waterborne pollutants. As a result, an improvement of low-cost, high-efficiency photocatalysts for the successful decomposition of antibiotics is critical for the cleaning of harmful contaminants in rivers and lakes. In the current work, a simple hydrothermal approach was used to create the bismuth vanadate nanoballs (BiVO4) anchored to the exterior of the ultrathin g-C3N4.It was named g-C3N4/BiVO4(X) (X = 5, 10, 15, and 20%) nanocomposites, and the photocatalytic removal of ciprofloxacin (CPX) and amoxicillin (AMX) was investigated using synthesized composites. According to the advanced characterization techniques, the synthesized composites exhibit superior purity and crystalline nature. The electron transfer occurring within the g-C3N4, in conjunction with the extension of BiVO4 nanoballs, enhances the generation of photoexcited electron−hole (e−/h+) pairs. This phenomenon contributes significantly to the improved photocatalytic activity observed in the g-C3N4/BiVO4 system. Furthermore, the photocatalytic efficiency exhibited by g-C3N4/BiVO4(10%) nanocomposites in antibiotic removal surpasses that of both bare materials and other composite counterparts. The elimination of antibiotics was aided by reactive oxygen species (ROS)such as O2•−, h+, and OH. Finally, g-C3N4/BiVO4(10%), the intermediate byproduct of CPX and AMX decomposition, was discovered, and a probable CPX and AMX removal route was postulated. The g-C3N4/BiVO4(10%) composite exhibits long-term stability after five cycles. This study applies a green and ecologically responsive technique to the development of high-performance photocatalysts for wastewater remediation.

Benzothiazoles are emerging chemical pollutants mainly coming from leather, paper and rubber industries; due to their use as: herbicides, corrosion inhibitors, anti-freezers, and vulcanisation accelerators. This article presents experimental data on ozone treatment of benzothiazole contaminated waters. The effect of the initial concentration of benzothiazole, ozone dosage, temperature (10-30 °C), and pH (2-9), on ozonation removal rate were assessed at bench scale. Experimental results show that reaction between ozone and benzothiazole could be approximated to a second-order kinetic law. Kinetic parameters for direct and indirect ozone reactions are estimated and temperature dependence of rate parameters is evaluated. Moreover, an initial degradation pathway of benzothiazole ozonation is proposed.

Fluoroquinolones are extensively used in medicine due to their antimicrobial activity. Their presence in water inhibits microorganism activity in conventional wastewater treatment plants. This study aims to evaluate the technical feasibility of applying heterogeneous catalytic ozonation to eliminate ciprofloxacin (CIP) as a representative of fluoroquinolone antibiotics normally present in municipal wastewater discharges. Experiments were conducted in a semi-batch stirred slurry reactor, using 0.7 L of 100 mg L−1 CIP aqueous solution, at pH 3 and 30 °C. Experimental results show that single ozonation can easily oxidise CIP molecules (68%) within the first 5 min, leading to the generation of refractory oxidation by-products. However, when heterogeneous catalytic ozonation is applied using iron oxide supported on MFI synthetic zeolite, total degradation of CIP is observed at 5 min and a higher mineralisation rate is obtained. A novel sequential process is developed for CIP mineralisation. In a first step, a flash single ozonation is applied and CIP molecules are broken down. Then, a catalytic ozonation step is conducted by adding the Fe/MFI catalyst into the reactor. As a result of catalyst addition, 44% of Total Organic Carbon (TOC) is eliminated within the first 15 min, compared to single ozonation where only 13% of TOC removal is reached in the same time. The application of this sequential process to a real wastewater effluent spiked with CIP leads to 52% of TOC removal.

This study describes theoretical and experimental considerations to optimize the photocatalytic degradation of caffeic acid in water using 3D-BiOBr based materials under visible light irradiation. Three BiOBr materials were synthesized through the solvothermal method using different bromide sources, namely potassium bromide (KBr) and the ionic liquid (IL) 1-butyl-3-methylimidazolium bromide. Morphological and chemical changes were observed in IL based 3D-BiOBr materials. The theoretical optimization of the experimental conditions in heterogeneous photocatalysis tests (pH and dose of catalyst) were simulated using the MODDE 12.0.1 software. A central composite design (CCD) was applied to obtain a response surface to elucidate the optimal conditions. This model predicted that the maximum photocatalytic degradation can be achieved at pH of 6.7 and a photocatalyst dose of 344 mg L−1. The optimal experimental conditions were tested using the three synthesized 3D-BiOBr materials. The results showed that the highest degradation efficiency and mineralization yield were obtained using the BiOBr microspheres synthesized with the IL at 145 °C.

For renewable energy, it is crucial to create effective photocatalysts with enhanced photo charge separation and transfer to produce photocatalytic hydrogen (H2) efficiently utilizing light energy. Due to their distinct qualities and features, carbonaceous materials have so far been shown to be high-performance co-catalysts to substitute some conventionally costly metal materials in photocatalytic water splitting. Here, a novel ternary nanocomposite, simple hydrothermal process ball milling assisted and wet impregnation approach, a promising ternary nanocomposite is created as an efficient solar light driven photocatalyst. Utilizing a variety of analytical techniques, 3 % Cu3P/ZnS/g-C3N4 nanocomposites as catalysts were characterized in order to check the hydrogen production and investigate their structural properties. The hydrogen production capability of the catalyst is studied by irradiating Na2SO3 + Na2S solutes using a halogen bulb (250 W). The results demonstrated that in terms of photocatalytic activity towards H2 production, 3 % Cu3P/ZnS/g-C3N4 catalyst performed better than 3 % Cu3P/ZnS, Cu3P, ZnS, and g-C3N4. A composite containing 7.5 wt% g-C3N4 demonstrated exceptional durability during photocatalytic hydrogen production, resulting in a 23,086 mol h− 1 g− 1 rate. Higher stability in electron-hole pairs created a higher absorption level of solar light could be responsible for this remarkable performance.

Natural and synthetic zeolites with different properties (porous structure, SiO2/Al2O3 ratio, acidity and Fe-loading) were evaluated as adsorbents/catalysts for octamethylcyclotetrasiloxane (D4) removal in dynamic adsorption tests. BEA type zeolites, with high content of Lewis and Brønsted sites, promoted the catalytic D4 ring-opening leading on the formation of smaller a-x-silanediols, which are narrower molecules able to diffuse into the channel system. Wet oxidation processes were used for the regeneration of a spent BEA zeolite, including ozonation and Fenton-like treatment. Both treatments were optimized to recover almost completely the D4 uptake of the iron-exchanged Fe-BEA in the first use. Thus, its feasibility to be reused was evaluated in successive adsorption/oxidation cycles, recovering up to 80% in at least three subsequent steps. However, in further cycles the accumulation of D4 and/or by-products led to a successive decline in the catalytic activity of the zeolites, hampering not only the capacity to transform D4 into lineal silanediols, thus reducing the adsorption capacity, but also the catalytic activity towards promoting Fenton-like reactions during regeneration.

In this study, a hydrophobic synthetic zeolite, namely ZSM-5 is chosen as an adsorbent/ catalyst for toluene removal. Experimental results showed that toluene adsorption onto ZSM-5 was favourable, following a Langmuir adsorption isotherm model. ZSM-5 zeolite was regenerated using gaseous ozone at low temperature. Adsorbed toluene was oxidised, releasing mainly CO2 and H2O. Traces of oxidation by-products such as acetic acid and acetaldehyde were formed and remained adsorbed after the oxidativate regeneration with ozone. After four successive cycles of adsorption/ozonation, the adsorption efficiency was not affected (92%–99%). These results showed that volatile organic compound (VOC) removal by adsorption onto ZSM-5 zeolite followed by ozone regeneration could be used as a promising hybrid process for the control of VOC emissions in terms of efficiency.

Anatase nanoparticles containing surface oxygen vacancies (VO) and Ti3+ are of great importance for applications in photocatalysis, batteries, catalysis, sensors among other uses. The properties of VO and their dependence on the size of nanoparticles are of great research interest and could allow obtaining advanced functional materials. In this work, a complete set of oxygen vacancies in an anatase nanoparticle of size 1.1 nm was investigated and compared to those of a twice larger nanoparticle, having the same shape and surface hydroxylation pattern. It turned out that the decrease in the size of the anatase nanoparticle strongly facilitated creation of surface oxygen vacancies and Ti3+. After their creation, oxygen vacancies undergo three transformation paths — (1) small repulsion of surrounding Ti cations with retention of the vacancy, (2) transfer of oxygen anion, leading to the movement of oxygen vacancy to a more stable position, and (3) collapse of oxygen vacancy accompanied by structure deformation towards Magneli-like phase.

This article presents the adsorption of Methylene Blue (MB) onto diatomite, in order to develop a low-cost treatment technology as a process alternative for dye removal. Diatomite used in this work was taken from the Nador area in the northeast of Morocco. Diatomite is characterised by different physical–chemical methods (X-ray diffraction, nitrogen adsorption-desorption isotherm, scanning electron microscopy and Fourier transform infrared). Results showed that the adsorption of MB onto diatomite mineral is affected by various operating parameters like contact time, initial dye concentration, adsorbent dosage, pH and temperature. Adsorption equilibrium is reached after 1.5 h of contact time. Maximum MB removal is obtained at pH = 12. MB removal rate decreases as pH decreases. Adsorption equilibrium data are fitted to Langmuir, Freundlich, Redlich–Peterson and Toth models. Adsorption data are well described by Langmuir isotherm model indicating that a homogeneous adsorption occurs. A maximum adsorption capacity (or monolayer coverage) of 11 mg g–1 is obtained at 45°C. A value of the enthalpy of adsorption of 12.78 kJ mol–1 is found confirming the endothermic nature of adsorption process, while a Gibb’s free energy change (∆G°) falling in the range −30.8 to −35.34 kJ mol–1 confirms the spontaneity of the process. Adsorption kinetics are fitted to a pseudo-second-order kinetic model. Experimental results indicate that the Moroccan diatomite could be used as a potential adsorbent for the removal of cationic dye molecules, at lower cost.

We report the synthesis of a new range of ferrihydrite-graphene oxide (FH-GO) foams using chitosan as cross linker, with varying iron content (5 wt%, 10 wt%, and 20 wt% of FH) as highly efficient adsorbents for the removal of arsenic (III) (As(III)) in an aqueous solution. The sonochemical methods were adopted to synthesize various FH-GO foams and were further characterized by XRD, SEM, TEM, FTIR, Raman, and XPS techniques. The synthesized materials were used for the removal of As(III) in both batch and fixed bed absorbent column methods. The adsorption isotherm results showed that the 10 wt% of FH-GO foams demonstrated a superior adsorbent for the As(III) with high adsorption capacities than that of the other two FH-GO foams (5 wt% and 20 wt% of FH). Moreover, 10 wt% of FH-GO foams was also demonstrated to be nearly a complete (>98.4%) removal of As(III) ions at neutral pH 7. The adsorption isotherm fitted very well with the Langmuir model with the highest accuracy data for all the synthesized adsorbent materials. In addition, the fixed bed absorbent column method was also adopted for the removal of As(III) ions in the water sample, which showed > 99.2% of removal efficiency. The outstanding adsorption capabilities, along with their easy and low-cost synthesis, make these kinds of adsorbents extremely capable for commercial applications in wastewater treatment and drinking water purification.