Fe2O3/TiO2 nanocomposites were fabricated via a facile impregnation/calcination technique employing different amounts iron (III) nitrate onto commercial TiO2 (P25 Aeroxide). The as-prepared Fe2O3/TiO2 nanocomposites were characterized by X-ray diffraction (XRD), Raman spectroscopy (RS), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDXS), X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller analysis (BET), electron impedance spectroscopy (EIS), photoluminescence spectroscopy (PL), and diffuse reflectance spectroscopy (DRS). As a result, 5% (w/w) Fe2O3/TiO2 achieved the highest photocatalytic activity in the slurry system and was successfully immobilized on glass support. Photocatalytic activity under visible-light irradiation was assessed by treating pharmaceutical amoxicillin (AMX) in the presence and absence of additional oxidants: hydrogen peroxide (H2O2) and persulfate salts (PS). The influence of pH and PS concentration on AMX conversion rate was established by means of statistical planning and response surface modeling. Results revealed optimum conditions of [S2O82−] = 1.873 mM and pH = 4.808; these were also utilized in presence of H2O2 instead of PS in long-term tests. The fastest AMX conversion possessing a zero-order rate constant of 1.51 × 10−7 M·min−1 was achieved with the photocatalysis + PS system. The AMX conversion pathway was established, and the evolution/conversion of formed intermediates was correlated with the changes in toxicity toward Vibrio fischeri. Reactive oxygen species (ROS) scavenging was also utilized to investigate the AMX conversion mechanism, revealing the major contribution of photogenerated h+ in all processes.
The advancement of pharmaceutical science has resulted in the development of numerous tailor-made compounds, i.e., pharmaceuticals, tuned for specific drug targets. These compounds are often characterized by their low biodegradability and are commonly excreted to a certain extent unchanged from the human body. Due to their low biodegradability, these compounds represent a significant challenge to wastewater treatment plants. Often, these compounds end up in effluents in the environment. With the advancement of membrane technologies and advanced oxidation processes, photocatalysis in particular, a synergistic approach between the two was recognized and embraced. These hybrid advanced water treatment processes are the focus of this review, specifically the removal of pharmaceuticals from water using a combination of a photocatalyst and pressure membrane process, such as reverse osmosis or nanofiltration employing photocatalytic nanocomposite membranes.
Sustainable hydrogen production is one of the main challenges today in the transition to a green and sustainable economy. Photocatalytic hydrogen production is one of the most promising technologies, amongst which BiVO4-based processes are highly attractive due to their suitable band gap for solar-driven processes. However, the performance of BiVO4 alone in this role is often unsatisfactory. Herein we report the improvement of BiVO4 performance with reduced graphene oxide (rGO) as a co-catalyst for the photoelectrochemical water splitting (PEC-WS) in the presence of simple functionalized benzene derivatives (SFBDs), i.e., phenol (PH), benzoic acid (BA), salicylic acid (SA), and 5-aminosalicylic acid (5-ASA) as potential photogenerated hole scavengers from contaminated wastewaters. Linear sweep voltammetry and chronoamperometry, along with electrochemical impedance spectroscopy were utilized to elucidate PEC-WS performance under illumination. rGO has remarkably improved the performance of BiVO4 in this role by decreasing photogenerated charge recombination. In addition, 5-ASA greatly improved current densities. After 120 min under LED illumination, 0.53 μmol of H2 was produced. The type and concentration of SFBDs can have significant and at times opposite effects on the PEC-WS performance of both BiVO4 and rGO-BiVO4.
Comprehensive profiling of serum proteome provides valuable clues of health status and pathophysiological processes, making it the main strategy in biomarker discovery. However, the high dynamic range significantly decreases the number of detectable proteins, obstructing the insights into the underlying biological processes. To circumvent various serum enrichment methods, obtain high-quality proteome wide information using the next-generation proteomic, and study host response in canine leishmaniosis, we applied data-independent acquisition mass spectrometry (DIA-MS) for deep proteomic profiling of clinical samples. The non-depleted serum samples of healthy and naturally Leishmania-infected dogs were analyzed using the label-free 60-min gradient sequential window acquisition of all theoretical mass spectra (SWATH-MS) method. As a result, we identified 554 proteins, 140 of which differed significantly in abundance. Those were included in lipid metabolism, hematological abnormalities, immune response, and oxidative stress, providing valuable information about the complex molecular basis of the clinical and pathological landscape in canine leishmaniosis. Our results show that DIA-MS is a method of choice for understanding complex pathophysiological processes in serum and serum biomarker development.
Wider application of BiVO4 (BVO) for photocatalytic water treatment is primarily limited by its modest photocatalytic effectiveness, despite its appropriately narrow band gap for low-cost, sunlight-facilitated water treatment processes. In this study, we have photomodified an isotype BVO, consisting of a tetragonal zircon and monoclinic scheelite phase, with Fe (Fe@BVO) and Ag (Ag@BVO) ionic precursors under UV illumination in an aqueous ethanol solution in order to assess their effect on the opto-electronic properties and effectiveness for the removal of ciprofloxacin (CIP). Fe@BVO failed to demonstrate enhanced effectiveness over pristine BVO, whereas all Ag@BVO achieved improved CIP degradation, especially 1% Ag@BVO. At pH 4 and 6, 1% Ag@BVO demonstrated nearly 24% greater removal of CIP than BVO alone. Photomodification with Fe created surface oxygen vacancies, as confirmed by XPS and Mott–Schottky analysis, which facilitated improved electron mobility, although no distinct Fe-containing phase nor Fe-doping was detected. On the other hand, the introduction of mid-band gap states by oxygen vacancies decreased the reducing power of the photogenerated electrons as the flat band potentials were shifted to more positive values, thus likely negatively impacting superoxide formation. In contrast, Ag-photomodification (Ag@BVO) resulted in the formation of Ag2O/AgO and Ag nanoparticles on the surface of BVO, which, under illumination, generated hot electrons by surface plasmon resonance and enhanced the mobility of photogenerated electrons. Our research underscores the pivotal role of photogenerated electrons for CIP degradation by BiVO4-based materials and emphasizes the importance of appropriate band-edge engineering for optimizing contaminant degradation.
Photocatalysis has been shown to be a promising and ecofriendly approach to the removal of contaminants of emerging concern (CECs). However, preventing the recombination of photogenerated charge carriers and achievement of suitable band edge positions are still major challenges to ensuring better performance. Herein, we report the preparation of surface-decorated BiVO4 with both a noble metal (Ag) and transition metal (Fe). The structural, morphological, and semiconducting features of the material were examined employing various techniques (XRD, SEM, UV-DRS, PL, and photoelectrochemical tests). The band gap of surface-modified BiVO4 is slightly narrower compared to pristine material, which is further validated by HOMO-LUMO gaps obtained through theoretical modeling approaches. The recombination of photogenerated charges was successfully reduced in the case of Ag–Fe–BiVO4, as proven by lower PL intensity and increased current density. The comparative photocatalytic degradation of the CECs ciprofloxacin (CIP) and perfluorooctanoic acid (PFOA) was conducted employing pristine BiVO4 and its two surface-modified analogues (Ag–BiVO4, and Ag–Fe–BiVO4) under solar light. Ag–Fe–BiVO4 was shown to be the most efficient; however, its effectiveness differed depending on CEC type. Under the same process conditions, degradation of CIP reached 93.9%, while PFOA was degraded only partially (22.9%).