Enhanced removal of pesticide micropollutant and bacteria using solar light-assisted Ag-doped TiO2: prospects for environmental and health impacts.

Pesticide micropollutants like 4-chlorophenol (4CP) and E. coli bacteria represent a substantial hazard, impacting both the environment and human health. This study delves into the effectiveness of Ag-doped TiO2 (Ag@TiO2) in removing both 4CP and E. coli. Ag@TiO2 has demonstrated remarkable effectiveness in removing 4CP under both solar and visible light conditions, earning degradation efficiencies of 91.3% and 72.8%, respectively. Additionally, it demonstrates outstanding photodegradation efficiency for 4CP (98.8%) at an initial concentration of 1 mg L-1. Moreover, Ag@TiO2 exhibited substantially higher removal performance for 4CP (81.6%) compared to TiO2 (27.6%) in wastewater. Analysis of the radicals present during the photodegradation process revealed that ·O2- primarily drives the decomposition of 4CP, with h+ and ·OH also playing significant roles in the oxidation reactions of the pollutant. Interestingly, even under dark conditions, Ag@TiO2 exhibited the capability to eliminate approximately 20% of E. coli, a percentage that increased to over 96% under solar light. In addition, the prospects for environmental and health impacts of utilizing Ag@TiO2 for pesticide micropollutant removal and bacteria were discussed.

Graphite-N reinforced sludge biochar electrode: A experimental and DFT theoretical analysis of efficient evolution and in-situ utilization of H2O2.

Rational reuse of municipal sludge to produce electro-Fenton electrode can not only save resources, but also produce superior peroxide and degradation pollutants simultaneously. Herein, a novel electro-Fenton electrode derived from sludge biochar loaded on Ni foam (SBC@Ni) was constructed via high temperature pyrolysis and chemical coating for efficient H2O2 evolution and pollutant degradation. Systematic experiments and density functional theory calculations (DFT calculation) explained that the production of graphite C and graphite N during high-temperature pyrolysis of municipal sludge can greatly enhance the oxygen reduction reaction of SBC@Ni electrode and promote the evolution of H2O2. And the hybrid heterojunctions, such as FeP, also played a key role in electrocatalytic processes. Notably, the electrode still exhibited excellent performance after 1000 linear scans and 12 h of continuous current stimulation, which demonstrated the excellent stability of the electrode. Moreover, SBC@Ni electrode can not only effectively oxidize 4-chlorophenol through the electro-Fenton effect, but also fully mineralize organic matter, indicating promising environmental application. The free radical quenching experiment also revealed that the ·OH is the main active species for 4-CP degradation in SBC@Ni electro-Fenton system.

How halogenated aromatic compounds affect the electron supply and consumption in glucose supported denitrification?

Halogenated aromatic compounds possess bidirectional effects on denitrifying bio-electron behavior, providing electrons and potentially interfering with electron consumption. This study selected the typical 4-chlorophenol (4-CP, 0-100 mg/L) to explore its impact mechanism on glucose-supported denitrification. When COD(glucose)/COD(4-CP)=28.70-3.59, glucose metabolism remained the dominant electron supply process, although its removal efficiency decreased to 73.84-49.66 %. When COD(glucose)/COD(4-CP)=2.39-1.43, 4-CP changed microbial carbon metabolism priority by inhibiting the abundance of glucose metabolizing enzymes, gradually replacing glucose as the dominant electron donor. Moreover, 5-100 mg/L 4-CP reduced adenosine triphosphate (ATP) by 15.52-24.67 % and increased reactive oxygen species (ROS) by 31.13-63.47 %, causing severe lipid peroxidation, thus inhibiting the utilization efficiency of glucose. Activated by glucose, 4-CP dechlorination had stronger electron consumption ability than NO2--N reduction (NO3--N > 4-CP > NO2--N), combined with the decreased nirS and nirK genes abundance, resulting in NO2--N accumulation. Compared with the blank group (0 mg/L 4-CP), 5-40 mg/L and 60-100 mg/L 4-CP reduced the secretion of cytochrome c and flavin adenine dinucleotides (FAD), respectively, further decreasing the electron transfer activity of denitrification system. Micropruina, a genus that participated in denitrification based on glucose, was gradually replaced by Candidatus_Microthrix, a genus that possessed 4-CP degradation and denitrification functions after introducing 60-100 mg/L 4-CP.

Fenton-like system of UV/Glucose-oxidase@Kaolin coupled with organic green rust: UV-enhanced enzyme activity and the mechanism of UV synergistic degradation of photosensitive pollutants.

This study introduces the UV/glucose-oxidase@Kaolin (GOD@Kaolin) coupled organic green rust (OGR) system (UV/OGR/GOD@Kaolin) to investigate the promotion of glucose oxidase activity by UV light and its synergistic degradation mechanism for photosensitive pollutants, specifically targeting the efficient degradation of 4-chlorophenol (4-CP). The enzyme system demonstrates its ability to overcome drawbacks associated with traditional Fenton systems, including a narrow pH range and high localized concentration of H2O2, by gradually releasing hydrogen peroxide in situ within a neutral environment. In the presence of UV radiation under specific conditions, enhanced enzyme activity is observed, resulting in increased efficiency in pollutant removal. The gradual release of hydrogen peroxide plays a crucial role in preventing unwanted reactions among active substances. These unique features facilitate the generation of highly reactive species, such as Fe(IV)O, •OH, and •O2-, tailored to efficiently target the organic components of interest. Additionally, the system establishes a positive iron cycle, ensuring a sustained reactive capability throughout the degradation process. The results highlight the UV/OGR/GOD@Kaolin system as an effective and environmentally friendly approach for the degradation of 4-CP, and the resilience of the enzyme extends the system's applicability to a broader range of scenarios.

Degradation and metagenomic analysis of 4-chlorophenol utilizing multiple metal tolerant bacterial consortium.

Chlorophenols are persistent environmental pollutants used in synthesizing dyes, drugs, pesticides, and other industrial products. The chlorophenols released from these processes seriously threaten the environment and human health. The present study describes 4-chlorophenol (4-CP) degradation activity and metagenome structure of a bacterial consortium enriched in a 4-CP-containing medium. The consortium utilized 4-CP as a single carbon source at a wide pH range, temperature, and in the presence of heavy metals. The immobilized consortium retained its degradation capacity for an extended period. The 4-aminoantipyrine colorimetric analysis revealed complete mineralization of 4-CP up to 200 mg/L concentration and followed the zero-order kinetics. The addition of glycerol and yeast extract enhanced the degradation efficiency. The consortium showed both ortho- and meta-cleavage activity of catechol dioxygenase. Whole genome sequence (WGS) analysis revealed the microbial compositions and functional genes related to xenobiotic degradation pathways. The identified genes were mapped on the KEGG database to construct the 4-CP degradation pathway. The results exhibited the high potential of the consortium for bioremediation of 4-CP contaminated sites. To our knowledge, this is the first report on WGS analysis of a 4-CP degrading bacterial consortium.

A facile synthesis process of GCN/ZnO-Cu nanocomposite and the evaluation of the performance for the photocatalytic degradation of organic pollutants and the disinfection of wastewater under visible light.

In this research, graphitic carbon nitride/zinc oxide-copper denoted as GCN/ZnO-Cu nanocomposite photocatalysts were synthesized using a novel facile synthesis process, the co-exfoliation method involving ultrasonic exfoliation of the mixture of GCN and ZnO-Cu in ethanol and then thermal exfoliation. Different characterization techniques such as X-ray diffraction (XRD), mean crystallite size (MCS), BET surface area, transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), particle size distribution (PSD), Fourier transform-infrared spectroscopy (FT-IR), photoluminescence (PL) spectra, and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS) were conducted to study the crystallinity, morphology, elemental composition, chemical structure, and optoelectronic properties. The band gap was estimated using the UV-Vis DRS results and Tauc plots. The photocatalytic activity of the GCN/ZnO-Cu3% nanocomposites was evaluated in the degradation of 4-chlorophenol (4-CP), and the disinfection of wastewater primary influent under a narrowband visible light source, royal blue LED (λ = 450 nm). GCN/0.1ZnO-Cu3% nanocomposite showed the best performance in the degradation of 4-CP and the disinfection of municipal wastewater primary influent. For 4-CP degradation, GCN/0.1ZnO-Cu3% was 2.2 times better than GCN, 9.4 times better than ZnO-Cu3%, and 1.8 times better than the sum of the individual GCN and ZnO-Cu3%. A 5.5 log reduction was achieved for the disinfection of total coliforms in wastewater primary influent in 360 min. This enhanced photocatalytic activity of GCN/ZnO-Cu3% nanocomposite can be attributed to the synergistic of GCN and the ZnO-Cu3%, resulting in a large surface area and improved bandgap.

Synergistic visible light assisted photocatalytic degradation of p-chlorophenol and rifampicin from aqueous solution using a novel g-C3N4 quantum dots incorporated α-MoO3 nanohybrid - Mechanism, pathway and toxicity studies.

In this work, a simple g-C3N4 quantum dots enriched MoO3 nanohybrid was formulated for the synergistic photocatalytic degradation of an industrially active organic pollutant, p-chlorophenol (PCP) and a widely prescribed antibiotic, rifampicin (RIF). The nanohybrid was synthesised via a facile ultrasonic assisted hydrothermal method and characterized using various characterization analysis. The efficient Z-scheme charge transfer of the nanohybrid resulted in the elimination of 98% PCP and 89% RIF under visible light with a rate constant of 0.012 and 0.006 min-1 respectively. The photocatalysis was attributed to the formation of both hydroxyl (OH•) and superoxide (O2•-) radicals in the resulting nanohybrid. The intermediates formed in the course of reaction were estimated through gas chromatography-mass spectroscopy/mass spectroscopy (GC-MS/MS) analysis and a suitable degradation pathway was constructed. The structural stability and reusability of the nanohybrid was affirmed through X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis to outweigh the industrial potential of the catalyst, with 85% PCP and 80% RIF removal efficiency after six cycles of degradation. In addition, the mineralization of the pollutants was confirmed by total organic carbon analysis. Further, the toxicity of the drug and the formed intermediates was determined using ecological structure activity relationships (ECOSAR) software. On the whole, this work provides an excellent insight for the development of environment-friendly materials in a large scale for the degradation of water-based pollutants.

Mesoporous NiO/Ni2O3 nanoflowers for favorable visible light photocatalytic degradation of 4-chlorophenol.

The present study highlights the treatment of industrial effluent, which is one of the most life-threatening factors. Herein, for the first time, two types of NiO (green and black) photocatalysts were prepared by facile chemical precipitation and thermal decomposition methods separately. The synthesized NiO materials were demonstrated with various instrumental techniques for finding their characteristics. The X-ray diffraction studies (XRD) and X-ray photoelectron spectroscopy (XPS) revealed the presence of Ni2O3 in black NiO material. The transmission electron microscopic (TEM) images engrained the nanospherical shaped green NiO and nanoflower shaped black NiO/Ni2O3 materials. Further, the band gap of black NiO nanoflower was 2.9 eV compared to green NiO having 3.8 eV obtained from UV-vis spectroscopy. Meanwhile, both NiO catalysts were employed for visible light degradation, which yields a 60.3% efficiency of black NiO comparable to a 4.3% efficiency of green NiO within 180 min of exposure. The higher degrading efficiency of black NiO was due to the presence of Ni2O3 and the development of pores, which was evident from the Barrett-Joyner-Halenda (BJH) method. Type IV hysteresis was observed in black NiO nanoflowers with high surface area and pore size measurements. This black NiO/Ni2O3 synthesized from the thermal decomposition method has promoted better photocatalytic degradation of 4-chlorophenol upon exposure to visible light and is applicable for other industrial pollutants.

Effects of salinity on the performance, microbial community, and functional genes among 4-chlorophenol wastewater treatment.

Chlorophenols frequently occur alongside salinity in industrial wastewater; thus, the effects of low concentrations of salinity (NaCl, 100 mg/L) on sludge performance, microbial community, and functional genes were deeply analyzed among 4-chlorophenol (4-CP, 2.4-4.0 mg/L) wastewater treatment. The influent 4-CP was effectively degraded, but the efficiencies for PO43--P, NH4+-N, and organics reduction were slightly inhibited by NaCl stress. Long-term NaCl and 4-CP stress significantly stimulated the secretion of extracellular polymeric substances (EPS). The abundances of predominant microbes at different taxonomic levels were affected by NaCl, and the increased relative abundances of functional genes encoding proteins contributed to resist NaCl and 4-CP stress. The functional genes associated with phosphorus metabolism and nitrogen metabolism in nitrification were unaffected, but the functional genes in denitrification increased in diversity under NaCl stress in 4-CP wastewater treatment. This finding acquires useful insight into the wastewater treatment with low chlorophenols and low salinity.

Metabolic insights into the interaction between nitrogen removal and 4-chlorophenol reduction of anammox consortia.

The response characteristic and performance stabilization of anammox process under the stress of the potential organic pollutants support the application of ammonia-nitrogen wastewater treatment. In the present study, nitrogen removal performance was significantly suppressed with the addition of 4-chlorophenol. The activity of anammox process was inhibited by 14.23% (0.1 mg/L), 20.54% (1 mg/L) and 78.15% (10 mg/L), respectively. Metagenomic analysis revealed a significant decrease in the abundance of KEGG pathways associated with carbohydrate and amino acid metabolism with increasing 4-chlorophenol concentration. Metabolic pathway profiles suggest that putrescine is down-regulated at high 4-chlorophenol stress due to inhibition of nitrogen metabolism processes, while it is up-regulated to reduce oxidative damage. In addition, the presence of 4-chlorophenol induced an enhancement of EPS and bacterial debris decomposition, and a partial conversion of 4-chlorophenol to p-nitrophenol. This study unravels the mechanism of effect on anammox consortia in response to 4-CP, which could provide supplementary to facilitate its full-scale application.

Catalytic Hydrodechlorination of 4-Chlorophenol by Palladium-Based Catalyst Supported on Alumina and Graphene Materials.

Hydrodechlorination (HDC) is a reaction that involves the use of hydrogen to cleave the C-Cl bond in chlorinated organic compounds such as chlorophenols and chlorobenzenes, thus reducing their toxicity. In this study, a palladium (Pd) catalyst, which is widely used for HDC due to its advantageous physical and chemical properties, was immobilized on alumina (Pd/Al) and graphene-based materials (graphene oxide and reduced graphene oxide; Pd/GO and Pd/rGO, respectively) to induce the HDC of 4-chlorophenol (4-CP). The effects of the catalyst dosage, initial 4-CP concentration, and pH on 4-CP removal were evaluated. We observed that 4-CP was removed very rapidly when the HDC reaction was induced by Pd/GO and Pd/rGO. The granulation of Pd/rGO using sand was also investigated as a way to facilitate the separation of the catalyst from the treated aqueous solution after use, which is to improve practicality and effectiveness of the use of Pd catalysts with graphene-based support materials in an HDC system. The granulated catalyst (Pd/rGOSC) was employed in a column to induce HDC in a continuous flow reaction, leading to the successful removal of most 4-CP after 48 h. The reaction mechanisms were also determined based on the oxidation state of Pd, which was observed using X-ray photoelectron spectroscopy. Based on the results as a whole, the proposed granulated catalyst has the potential to greatly enhance the practical applicability of HDC for water purification.

Extended application of defective metal oxide BiO2-x: Liquid phase low-temperature thermal catalysis for the removal of phenolic pollutants.

Bismuth oxide (BiO2-x) with oxygen vacancies was created using a hydrothermal process and was found to exhibit good catalytic oxidation performance under low-temperature heating without the addition of external oxidants. The catalytic activity of BiO2-x was tested using 4-chlorophenol (4-CP) as the target aqueous pollutant. We observed that 10 ppm of 4-CP was completely degraded within 40 min at a reaction temperature of 65 °C. The effective elimination of 4-CP was attributed to active oxygen species produced by the release of lattice oxygen. Furthermore, the low-temperature thermal catalytic activity of BiO2-x was affected by the electron transfer characteristics of pollutants, leading to the rapid degradation of electron-rich pollutants. This study reveals the unique application of BiO2-x as a catalyst for removing phenolic pollutants under low-temperature thermal catalysis, thereby expanding its catalytic application scenarios and offering a new approach for the degradation of phenolic pollutants.

Hydrothermally improved natural manganese-containing catalytic materials to degrade 4-chlorophenol.

Natural manganese-containing mineral (NMM) was used as a catalyst in heterogeneous catalytic ozonation for 4-chlorophenol (4-CP) degradation. The surface and structural properties of NMM were modified by the hydrothermal aging process and called H-NMM. The catalytic activity of NMM and H-NMM were evaluated for the catalytic ozonation process (COP). The synergistic effect of NMM and H-NMM in ozonation processes for 4-CP degradation under optimal conditions (pH of 7, 1 g/L of NMM and H-NMM, 0.85 mg/min of O3, and 15 min of reaction time) was measured by 3.04 and 4.34, respectively. During the hydrothermal process, Mn4+ and Fe2+ were converted to Mn2+ and Fe3+, which caused better performance of the H-NMM than the NMM. During the catalytic ozonation process, Mn2+ is completely oxidized, which increases the production of Hydroxyl radical (•OH). The reactive oxygen species (ROS) generated in the system were identified using radical scavenging experiments. •OH, superoxide radical (•O2-), and singlet oxygen (1O2) represented the dominant reactive species for 4-CP degradation. The O3/H-NMM process indicated a powerful ability in the mineralization of 4-CP (66.31% of TOC degradation). H-NMM exhibited excellent stability and reusability in consecutive catalytic cycles, and the NMM exhibited desirable performance. This study offers NMM and H-NMM as effective, stable, and competitive catalysts for hastening and enhancing the ozonation process to mitigate environmentally related pollutants of high concern.

Green Constant-wavelength Concurrent Selective Fluorescence Method for Assay of Ibuprofen and Chlorzoxazone in Presence of Chlorzoxazone Degradation Product.

Lower back pain is a universal dilemma leaving a negative effect on both health and life quality. It was found that a fixed dose combination of chlorzoxazone and ibuprofen gave a higher efficiency than analgesic alone in treatment of acute lower back pain. Based on the significant benefit of that combination, a green, sensitive, rapid, direct, and cost-effective method is created for concurrent determination of ibuprofen and chlorzoxazone in presence of 2-amino para chlorophenol (a synthetic precursor and potential impurity of chlorzoxazone) adopting the synchronous spectrofluorimetric technique. Synchronous spectrofluorimetric technique is adopted to avoid the highly overlapped native spectra of both drugs. The synchronous spectrofluorometric method was applied at Δλ = 50 nm, ibuprofen was measured at 227 nm while chlorzoxazone was measured at 282 nm with no hindering from one to another. The various experimental variables affecting the performance of the suggested technique were explored and adjusted. The suggested technique showed good linearity from 0.02 to 0.6 and 0.1 to 5.0 µg/mL for ibuprofen and chlorzoxazone, respectively. The produced detection limits were 0.27 × 10-3 and 0.03, while the quantitation limits were 0.82 × 10-3 and 0.09 µg/mL for ibuprofen and chlorzoxazone, respectively. The suggested approach was successfully applied for the analysis of the studied drugs in the synthetic mixture, different pharmaceutical preparations, and spiked human plasma. The suggested technique was validated with respect to the International Council of Harmonization (ICH) recommendations. The suggested technique was found to be simpler and greener with lower cost compared to the earlier reported methods which required complicated techniques, longer time of analysis, and less safe solvents and reagents. Green profile assessment for the developed method compared with the reported spectrofluorometric method was performed using four assessment tools. These tools confirmed that the recommended technique attained the most possible green parameters, so it could be used as a greener option in routine quality control for analyzing the two drugs in genuine form and pharmaceutical preparations.

Photocatalysis-self-Fenton system over edge covalently modified g-C3N4 with high mineralization of persistent organic pollutants.

The Fenton process is a widely used to remedy organic wastewaters, but it has problems of adding H2O2, low utilization efficiency of H2O2 and low mineralization efficiency. Here, a new photocatalysis-self-Fenton process was exploited for the removal of persistent 4-chlorophenol (4-CP) pollutant through coupling the photocatalysis of 4-carboxyphenylboronic acid edge covalently modified g-C3N4 (CPBA-CN) with Fenton. In this process, H2O2 was in situ generated via photocatalysis over CPBA-CN, the photogenerated electrons assisted the accelerated regeneration of Fe2+ to improve the utilization efficiency of H2O2, and the photogenerated holes facilitated the enhancement of 4-CP mineralization. Under the conjugation of CPBA, the electronic structure of CN was optimized and the molecular dipole was enhanced, resulting in the deepening valence band position, accelerated electron-hole pair separation, and improved O2 adsorption-activation. Therefore, the incremental 4-CP degradation rate in the CPBA-CN photocatalysis-self-Fenton process was approaching 0.099 min-1, by a factor of 3.1 times compared with photocatalysis. The parallel mineralization efficiency increased to 74.6% that was 2.1 and 2.6 times than photocatalysis and Fenton, respectively. In addition, this system maintained an excellent stability in the recycle experiment and can be potentially applied in a wide range of pHs and under the coexistence of various ions. This study would provide new insights for improving Fenton process and promote further development of Fenton in organic wastewater purification.

Electrochemical monitoring of 4-chlorophenol as a water pollutant via carbon paste electrode amplified with Fe3O4 incorporated cellulose nanofibers (CNF).

A crucial problem that needs to be resolved is the sensitive and selective monitoring of chlorophenol compounds, especifically 4-chlorophenol (4-CP), one of the most frequently used organic industrial chemicals. In light of this, the goal of this study was to synthesize Fe3O4 incorporated cellulose nanofiber composite (Fe3O4/CNF) as an amplifier in the development of a modified carbon paste electrode (CPE) for 4-CP detection. Transmission electron microscopy (TEM) was used to evaluate the morphology of the synthesized nanocatalyst, while differential pulse voltammetry (DPV), electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV) techniques were implemented to illuminate the electrochemical characteristics of the fabricated sensor. The ultimate electrochemical sensor (Fe3O4/CNF/CPE) was used as a potent electrochemical sensor for monitoring 4-CP in the concentration range of 1.0 nM-170 µM with a limit of detection value of 0.5 nM. As a result of optimization studies, 8.0 mg Fe3O4/CNF was found to be the ideal catalyst concentration, whereas pH = 6.0 was chosen as the ideal pH. The 4-CP's oxidation current was found to be over 1.67 times greater at ideal operating conditions than it was at the surface of bare CPE, and its oxidation potential decreased by about 120 mV. By using the standard addition procedure on samples of drinking water and wastewater, the suggested capability of Fe3O4/CNF/CPE to detect 4-CP was further investigated. The recovery range was found to be 98.52-103.66%. This study paves the way for the customization of advanced nanostructure for the application in electrochemical sensors resulting in beneficial environmental impact and enhancing human health.

Adsorption of chlorophenols on activated pine sawdust-activated carbon from solution in batch mode.

In this work, a novel adsorbent, activated carbon (PSAC) developed by the activation of pine sawdust's pyrolytic carbon (PSPC), is applied to adsorb 2,4-dichlorophenol (2,4-DCP) and 4-chlorophenol (4-CP). The optimized preparation conditions of PSAC were presented. The results revealed that equilibrium adsorption capacity (qe) of PSAC was notably enhanced up to threefold compared with PSPC. The adsorbents were characterized by a variety of techniques such as SEM, XRD, FT-IR, and elemental analysis. The key factors (such as adsorbent dosage, pH, salt concentration, temperature, and contact time) influencing the adsorption process were also studied. The adsorption quantities of PSAC for 2,4-DCP and 4-CP were 135.7 mg·g-1 and 77.3 mg·g-1, respectively. The equilibrium adsorption of 4-DCP and 4-CP was suitable to be predicted by the Freundlich and Koble-Corrigan models, while kinetic process was better described by the pseudo-second-order kinetic model and Elovich equation. The process was spontaneous. After repeated regeneration of PSAC with ethanol, the adsorption capacity of PSAC was not significantly reduced, indicating that PSAC can be recycled by regeneration after adsorption of 4-CP. This work provides a viable method to use activated carbon as an effective adsorbent for pollutant removal.

Efficient NiO/F-TiO2 nanocomposites for 4-chlorophenol photodegradation.

This work aimed to study NiO/F-TiO2 composites in the photocatalytic degradation of 4-chlorophenol. F-TiO2 support was prepared by in-situ fluorination of TiO2 using the sol-gel method. The heterostructured materials were prepared by wet impregnation method, varying NiO content (0.5, 1.0, and 2.0% wt). The solids were characterized by X-ray fluorescence, X-ray diffraction, nitrogen physisorption, diffuse reflectance UV-Vis spectrophotometry, infrared spectroscopy, and X-ray photoelectron spectroscopy. The characterization studies showed that the coupling of TiO2 with fluoride ions promoted the generation of ≡Ti-F surface species that could be responsible for the decrease in the recombination frequency of charge carriers and the increased photoactivity. In addition, it was found that the coupling of NiO/F-TiO2 semiconductors improved the photocatalytic properties of the fluorinated support, obtaining higher percentages of degradation and mineralization of the phenolic contaminant. These results are possibly a consequence of factors such as the formation of larger crystallites, lower band gap energies, and the generation of p-n type interfacial heterojunctions that potentiate the proper separation of electron-hole pairs. An effect of NiO content on photoactivity was observed, being a percentage of 1.0% wt the optimum in this photocatalytic treatment.

WO3/rGO nanocomposite-based sensor for the detection and degradation of 4-Chlorophenol.

Chlorinated organic compounds are useful chemicals or intermediates that are used extensively in both industry and agriculture. The 4-chlorophenol (4CP) in low concentration poses a serious environmental problem and causes many health issues, including cancer and liver disease. In this work, we demonstrated the detection of 4CP at carbon paste electrodes modified using tungsten oxide (WO3) nanorods and reduced graphene oxide (rGO) nanoparticles. The significance of pH on the voltammetric response of 4CP was investigated, and it was discovered that an alkaline pH is an optimal condition for detecting substituted phenols. Moreover, parameters like heterogeneous rate constant, accumulation time, temperature effect, Gibb's free energy, scan rate, enthalpy, activation energy, and entropy were studied. The excellent catalytic and bulk properties of tungsten oxide nanostructures make it an effective modifier in electrochemical sensors. The employment of nanostructured WO3 for the assay of 4CP offers excellent sensitivity, selectivity, and applicability. The WO3 nanostructures are obtained hydrothermally and characterized in detail to understand the crystalline, quantitative and chemical properties. The electrochemical behavior of 4CP was studied utilizing voltammetry techniques. The CV technique was used to optimize and affect many factors in the electrochemical behavior of 4CP. The scan rate investigation helps to examine the physicochemical characteristics of the electrode process, and the electrooxidation of 4CP included 2 electrons and 2 protons. With 4CP, the modified electrode displayed a broad range of linearity. The limit of detection was determined to be 0.102 nM, while the limit of quantification was 0.3433 nM. The concentration of 4CP ranged between 0.1 × 10-7 M and 3.5 × 10-7 M. The fabricated electrode was also used to detect 4CP in soil and water samples. Good recoveries were obtained from the soil and water samples. The proposed electrode was used for analytical applications, including 4CP detection with high selectivity, low detection limit, sensitivity, and rapid response.

Eco-friendly cubic-ZnS coupled Cu7S4 spines on chitosan matrix: Unravelling defect-engineered nanoplatform for the photodegradation of p-chlorophenol.

Novel ZnS-Cu7S4 nanohybrid supported on chitosan matrix, as an ideal photocatalyst, was fabricated by the sonochemical method wherein high-resolution transmission electron microscopy (HRTEM) and X-ray powder diffraction (XRD) analysis confirmed the co-existence of both ZnS and Cu7S4; presence of vacancy sites in ZnS was verified by electron paramagnetic resonance (EPR) analysis and their introduction could promote two-photon excitation facilitated visible light response and charge transport/separation. The type II interface is formed in the ZnS-Cu7S4/Chitosan heterojunction owing to interstitial states that promote charge separation. The ZnS-Cu7S4/Chitosan was used for the photodegradation of a pharmaceutical pollutant, p-chlorophenol (PCP); over 98.8% of PCP photodegradation was achieved under visible-light irradiation where the ensued ·O2- and ·OH serve a key role in the photodegradation of PCP. In vitro cytotoxicity studies substantiated that the ZnS-Cu7S4/Chitosan is nontoxic to the ecosystem and human beings and endowed with promising photodegradation properties and accessibility via an environmentally friendly design, bodes well for its potential remediation applications.