Chlorination of arenes via the degradation of toxic chlorophenols.

Aryl chlorides are among the most versatile synthetic precursors, and yet inexpensive and benign chlorination techniques to produce them are underdeveloped. We propose a process to generate aryl chlorides by chloro-group transfer from chlorophenol pollutants to arenes during their mineralization, catalyzed by Cu(NO3)2/NaNO3 under aerobic conditions. A wide range of arene substrates have been chlorinated using this process. Mechanistic studies show that the Cu catalyst acts in cooperation with NOx species generated from the decomposition of NaNO3 to regulate the formation of chlorine radicals that mediate the chlorination of arenes together with the mineralization of chlorophenol. The selective formation of aryl chlorides with the concomitant degradation of toxic chlorophenol pollutants represents a new approach in environmental pollutant detoxication. A reduction in the use of traditional chlorination reagents provides another (indirect) benefit of this procedure.

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.

The urinary level of 2,4,5-trichlorophenol was positively associated with both all-cause and cause-specific mortalities in general adult residents of United States.

Chlorophenols are widespread environmental organic pollutants with harmful effects on human beings. Although relationships between chlorophenols and various dysfunctions/diseases have been reported, the contribution of chlorophenols exposure to mortalities is underdetermined. In this cohort study, we included 4 types of urinary chlorophenols, aiming to estimate associations of chlorophenols exposure with all-cause and cause-specific mortalities. Urinary chlorophenols were examined at baseline of National Health and Nutrition Examination Survey (NHANES) 2003-2010, and adjusted for the urinary creatinine level. Associations between chlorophenols and mortalities were estimated using COX regression analyses, results were shown as hazard ratio (HR) and 95% confidence interval (95% CI). By dividing participants into four subgroups based on quartiles of urinary levels of chlorophenols, associations between mortalities and categorical variables of chlorophenols were estimated. Furthermore, the quantile g-computation analysis was used to estimate the joint effects of 4 chlorophenols on mortalities. Among 5817 adults (2863 men), 1034 were deceased during the follow-up. After adjusted for confounders, 2,4,5-trichlorophenol (2,4,5-TCP) was found to be positively associated with both all-cause (HR = 1.46; 95% CI: 1.16, 1.84) and cardiovascular disease (CVD) mortalities (HR = 1.60; 95% CI: 1.00, 2.55). Compared to the subgroup of the lowest level of chlorophenols, participants in subgroups of higher 2,4,5-TCP levels showed higher risk of all-cause mortality (P-value for trend = 0.003). For CVD mortality, HRs in subgroups of higher levels of 2,4-dichlorophenol (2,4-DCP) and 2,4,6-trichlorophenol (2,4,6-TCP) were statistically significant (P-values for trend were 0.017 for 2,4-DCP and 0.049 for 2,4,6-TCP). The HRs (95% CI) of joint effects of 4 chlorophenols were 1.11 (1.01, 1.21) and 1.32 (1.10, 1.57) for all-cause and CVD-specific mortalities, and 2,4,5-TCP showed the highest weight in joint effects. All of these findings implied that among 4 urinary chlorophenols we included, 2,4,5-TCP might be a sensitive one in associations with mortalities among general populations.

Oxidation of chromium(â ¢): A potential risk of using chemical oxidation processes for the remediation of 2-chlorophenol contaminated soils.

Chemical oxidation processes are widely used for the remediation of organically contaminated soils, but their potential impact on variable-valence and toxic metals such as chromium (Cr) is often overlooked. In this study, we investigated the risk of Cr(Ⅲ) oxidation in soils during the remediation of 2-chlorophenol (2-CP) contaminated soils using four different processes: Potassium permanganate (KMnO4), Modified Fenton (Fe2+/H2O2), Alkali-activated persulfate (S2O82-/OH-), and Fe2+-activated persulfate (S2O82-/Fe2+). Our results indicated that the KMnO4, Fe2+/H2O2, and S2O82-/Fe2+ processes progressively oxidized Cr(III) to Cr(Ⅵ) during the 2-CP degradation. The KMnO4 process likely involved direct electron transfer, while the Fe2+/H2O2 and S2O82-/Fe2+ processes primarily relied on HO• and/or SO4•- for the Cr(III) oxidation. Notably, after 4 h of 2-CP degradation, the Cr(VI) content in the KMnO4 process surpassed China's 3.0 mg kg-1 risk screening threshold for Class I construction sites, and further exceeded the 5.7 mg kg-1 limit for Class II construction sites after 8 h. Conversely, the S2O82-/OH- process exhibited negligible oxidation of Cr(III), maintaining a low oxidation ratio of 0.13%, as highly alkaline conditions induced Cr(III) precipitation, reducing its exposure to free radicals. Cr(III) oxidation ratio was directly proportional to oxidant dosage, whereas the Fe2+/H2O2 process showed a different trend, influenced by the concentration of reductants. This study provides insights into the selection and optimization of chemical oxidation processes for soil remediation, emphasizing the imperative for thorough risk evaluation of Cr(III) oxidation before their application.

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.

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.

Application of Fe(III)-EDDS complexes and soybean peroxidase in photo-Fenton processes for organic pollutant removal: insights into possible synergistic effects.

Photo-Fenton processes activated by biodegradable Fe(III)-EDDS complexes have attracted huge attention from the scientific community, but the operative mechanism of the photo-activation of H2O2 in the presence of Fe(III)-EDDS has not been fully clarified yet. The application of the Fe(III)-EDDS complex in Fenton and photo-Fenton (mainly under UV-B light) processes, using 4-chlorophenol (4-CP) as a model pollutant was explored to give insights into the operative mechanism. Furthermore, the potential synergistic contribution of soybean peroxidase (SBP) was investigated, since it has been reported that upon irradiation of Fe(III)-EDDS the production of H2O2 can occur. SBP did not boost the 4-CP degradation, suggesting that the possibly produced H2O2 reacts immediately with the Fe(II) ion with a quick kinetics that does not allow the diffusion of H2O2 into the bulk of the solution (i.e., outside the solvent cage of the complex). So, a concerted mechanism in which the photochemically produced H2O2 and Fe(II) react inside the hydration sphere of the Fe(III)-EDDS complex is proposed.

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.

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.

Porous adsorbent derived from acid activation of food waste biochar: A sustainable approach for novel removal chlorophenol in wastewater.

In this study, porous biochar (PBC) was prepared by acid activation of biochar derived from food waste (FWBC) and used as a suitable approach for the removal of 4-chlorophenol (CP) in wastewater. The characterization of PBC and the influent of different experimental conditions are determined. After the acid activation process, the surface area, porosity, and functional groups of PBC were developed. The removal performances of CP (1 mg/L) by PBC and FWBC were archived at 97.8 and 82.1%, respectively. Adsorption kinetics and isotherms of CP were followed by the second-order and Langmuir models, respectively. The maximum capacities of CP uptake onto mono-layer of FWBC and PBC based on the Langmuir model were determined at 79.8 and 108.7 mg/g, respectively. Besides, PBC could remove more than 89% CP from wastewater within 45 min of reaction time and it is suitable to reuse 8 times with over 60% adsorption efficiency of CP. In addition, the adsorption mechanism and environmental impact were discussed in detail. This work could bring a sustainable approach to the treatment of CP in wastewater as well as the management of food waste in Vietnam.

Exploration of the mechanism of 2-CP degradation by Acinetobacter sp. stimulated by Lactobacillus plantarum fermentation waste: A bio-waste reuse.

Green and economical pollution management methods which reusing bio-waste as biostimulant to effectively improve the removal of target pollutants are receiving more and more attention. In this study, Lactobacillus plantarum fermentation waste solution (LPS) was used to investigate its facilitative effect and the stimulation mechanisms on the degradation of 2-chlorophenol (2-CP) by strain Acinetobacter sp. strain ZY1 in terms of both cell physiology and transcriptomics. The degradation efficiency of 2-CP was improved from 60% to > 80% under LPS treatment. The biostimulant maintained the morphology of strain, reduced the level of reactive oxygen species, and recovered the cell membrane permeability from 39% to 22%. It also significantly increased the level of electron transfer activity and extracellular polymeric substances secretion and improved the metabolic activity of the strain. The transcriptome results revealed the stimulation of LPS to promote biological processes such as bacterial proliferation, metabolism, membrane structure composition, and energy conversion. This study provided new insights and references for the reuse of fermentation waste streams in biostimulation methods.

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.

The in-depth revelation of the mechanism by which a downflow Leersia hexandra Swartz constructed wetland-microbial fuel cell synchronously removes Cr(VI) and p-chlorophenol and generates electricity.

The composite pollution by Cr(VI) and p-chlorophenol (4-CP) has high toxicity and harms water safety. However, research on the effective removal of Cr(VI) and 4-CP composite-polluted wastewater (C&P) and efficient synchronous electricity generation with reclaimed resources is limited. In this study, a downflow Leersia hexandra constructed wetland-microbial fuel cell (DLCW-MFC) was builded to treat C&P, as well as wastewater singularly polluted by Cr(VI) (SC) and 4-CP (SP), respectively, to reveal the mechanism by which DLCW-MFC treats C&P and synchronously generates electricity. The results demonstrate that the cathode layer had a stronger removal effect on pollutants than the middle layer and anode zone layer. Moreover, SC and SP had stronger pollutant removal effects than C&P. Cr(VI) had more competitive with electrons than 4-CP, and they had a synergistic effect on efficient electricity generation. The L.hexandra in SC and SP had a better growth state and lower Cr enrichment concentration than that in C&P. Cr existed in the DLCW-MFC mainly in the form of Cr(III). Gas chromatography-mass spectrometry was used to investigate the degradation pathway of 4-CP in C&P, and indicated that Phenol, 2,4-bis(1,1-dimethylethyl)- and benzoic acid compounds were the main intermediates formed at the cathode, and further mineralized to form medium-long-chain organic compounds to form CO2. The microbial community distribution results revealed that Simplicispira, Cloacibacterium, and Rhizobium are associated with Cr(VI) removal and 4-CP degradation, and were found to be rich in the cathode of C&P. The anode of C&P was found to have more Acinetobacter (1.34%) and Spirochaeta (4.83%) than SC and SP, and the total relative abundance of electricigens at the anode of C&P (7.46%) was higher than that at the anodes of SC and SP. This study can provide a theoretical foundation for the DLCW-MFC to treat heavy metal and chlorophenol composite-polluted wastewater and synchronously generate electricity.

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.

Adsorption and catalytic degradation of bisphenol A and p-chlorophenol by magnetic carbon nanotubes.

Phenolic compounds are common industrial pollutants that seriously endangers water ecology and human health. Therefore, the development of efficient and recyclable adsorbents is of importance for wastewater treatment. In this research, HCNTs/Fe3O4 composites were constructed using co-precipitation way by loading magnetic Fe3O4 particles onto hydroxylated multi-walled carbon nanotubes (MWCNTs), showing excellent adsorption capacity for Bisphenol A (BPA) and p-chlorophenol (p-CP), and excellent catalytic ability of activating potassium persulphate (KPS) for degradation of BPA and p-CP. The adsorption capacity and catalytic degradation potential were evaluated for the removal of BPA and p-CP from solutions. The results showed that the adsorption took only 1 h to reach equilibrium and HCNTs/Fe3O4 had maximum adsorption capacities of 113 mg g-1 for BPA and 41.6 mg g-1 for p-CP at 303 K, respectively. The adsorption of BPA fitted well using the Langmuir, Temkin and Freundlich models while the adsorption of p-CP fitted well using the Freundlich and Temkin models. BPA adsorption on HCNTs/Fe3O4 was dominated by π-π stacking and hydrogen bonding forces. The adsorption included both the mono-molecular layer adsorption on the adsorbent surface and the multi-molecular layer adsorption on the non-uniform surface. The adsorption of p-CP on HCNTs/Fe3O4 was a multi-molecular layer adsorption on a dissimilar surface. The adsorption was controlled by forces such as π-π stacking, hydrogen bonding, partition effect and molecular sieve effect. Moreover, KPS was added to the adsorption system to initiate a heterogeneous Fenton-like catalytic degradation. Over a wide pH range (4-10), 90% of the aqueous BPA solution and 88% of the p-CP solution were degraded in 3 and 2 h, respectively. After three adsorption-regeneration or degradation cycles, the removal of BPA and p-CP remained up to 88% and 66%, indicating that HCNTs/Fe3O4 composite is cost-effective, stable and highly efficient to remove BPA and p-CP from solution.

Biochar supported nano core-shell (TiO2/CoFe2O4) for wastewater treatment.

The porous structure of biochar, its large surface area, and its anti-oxidant properties are extensively used for pollutant removal strategies. The literature to date has reported that the biochar assisted metal-oxide core-shells have a dominating degradation ability under solar irradiation. Therefore, this study is significantly focused on cinnamon biochar as an active anti-oxidant agent incorporated in titania-cobalt ferrite nanocore-shell (Biochar/TiO2/CoFe2O4) structures for the first time in wastewater treatment against chlorophenol pollutants. Pure materials, core-shells, and biochar aided composites were synthesized by chemical methods, and their characteristics were analyzed using various instrumentation techniques. The diffraction outcomes of Biochar/TiO2/CoFe2O4 showed the mixed phases containing biochar, TiO2, and CoFe2O4. The morphological characteristics revealed that the biochar creates porosity and a peripheral layer covering the core-shell. Meanwhile, absorption studies of TiO2/CoFe2O4 core-shell and Biochar/TiO2/CoFe2O4 samples achieved 65% and 92% degradation efficiencies when exposed to visible light against chlorophenol pollutants, respectively. All these results confirm the presence of distinct functional groups as well as the combined synergistic effects that activated the charge separation, resulting in the successful destruction of water pollutants. In addition, the highly efficient Biochar/TiO2/CoFe2O4 sample was recycled, and the efficiency was maintained stable for five repeated degradation processes. Thus, Biochar/TiO2/CoFe2O4 will be utilized to expand the possibilities for biofuel generation and energy storage devices.

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.

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.

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.

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.