Defect Engineering Modulated Iron Single Atoms with Assist of Layered Clay for Enhanced Advanced Oxidation Processes.

Single-atom catalysts (SACs) feature maximum atomic utilization efficiency; however, the loading amount, dispersibility, synthesis cost, and regulation of the electronic structure are factors that need to be considered in water treatment. In this study, kaolinite, a natural layered clay mineral, is applied as the support for g-C3 N4 and single Fe atoms (FeSA-NGK). The FeSA-NGK composite exhibits an impressive degradation performance toward the target pollutant (>98% degradation rate in 10 min), and catalytic stability across consecutive runs (90% reactivity maintained after three runs in a fluidized-bed catalytic unit) under peroxymonosulfate (PMS)/visible light (Vis) synergetic system. The introduction of kaolinite promotes the loading amount of single Fe atoms (2.57 wt.%), which is a 14.2% increase compared to using a bare catalyst without kaolinite, and improved the concentration of N vacancies, thereby optimizing the regulation of the electronic structure of the single Fe atoms. It is discovered that the single Fe atoms successfully occupied five coordinated N atoms and combined with a neighboring N vacancy. Consequently, this regulated the local electronic structure of single Fe atoms, which drives the electrons of N atoms to accumulate on the Fe centers. This study opens an avenue for the design of clay-based SACs for water purification.

Chronic exposure to low concentration of MC-LR caused hepatic lipid metabolism disorder.

Microcystin-LR (MC-LR), a potent hepatotoxin can cause liver damages. However, research on hepatic lipid metabolism caused by long-term exposure to environmental concentrations MC-LR is limited. In the current study, mice were exposed to various low concentrations of MC-LR (0, 1, 30, 60, 90, 120 µg/L in the drinking water) for 9 months. The general parameters, serum and liver lipids, liver tissue pathology, lipid metabolism-related genes and proteins of liver were investigated. The results show that chronic MC-LR exposure had increased the levels of triglyceride (TG) and total cholesterol (TC) in serum and liver. In addition, histological observation revealed that hepatic lobules were disordered with obvious inflammatory cell infiltration and lipid droplets. More importantly, the mRNA and proteins expression levels of lipid synthesis-related nuclear sterol regulatory element binding protein-1c (nSREBP-1c), SREBP-1c, cluster of differentiation 36 (CD36), acetyl-CoA-carboxylase1 (ACC1), stearoyl-CoA desaturase1 (SCD1) and fatty acid synthase (FASN) were increased in MC-LR treated groups, the expression levels of fatty acids ß-oxidation related genes peroxisomal acyl-coenzyme A oxidase 1 (ACOX1) was decreased after exposure to 60-120 µg/L MC-LR. Furthermore, the inflammatory factors interleukin 6 (IL-6) and tumor necrosis factor-α (TNF-α) were higher than that in the control group. All the findings indicated that mice were exposed to chronic low concentrations MC-LR caused liver inflammation and hepatic lipid metabolism disorder .

Surface Functionalization of Montmorillonite with Chitosan and the Role of Surface Properties on Its Adsorptive Performance: A Comparative Study on Mycotoxins Adsorption.

Understanding surface and interfacial information, which has a close relationship to the structures and properties of materials, helps guide the design of materials for specific applications. This study focuses on the surface functionalization of montmorillonite (Mt) with chitosan (CTS) and exploring the role of surface properties on its adsorptive performance. Two prototypical products, namely, 180-Htc@Mt and 250-Htc@Mt, were fabricated via the hydrothermal method at 180 and 250 °C, respectively. Field emission scanning electron microscopy revealed that hydrothermal carbon (Htc) derived from CTS anchored on the surface of Mt uniformly with a spherical morphology. The introduction of Htc endowed the surface of Mt with abundant hydroxy, amine, and amide groups; organic carbon; developed porosity; and hydrophobic interfacial property. Hydrothermal temperature has huge impacts on the surface system, and smaller particles (average size of 27 vs 53 nm) with deeper carbonization, higher content of carbonaceous and nitrogenous functional groups, more developed porosity (66.149 vs 39.434 m2/g of specific surface area, 0.115 vs 0.090 cm3/g of pore volume), and slightly decreased hydrophobicity can be readily achieved at a higher temperature. The incoming surface protonated amine and amide functional groups show an ion-dipolar interaction to polar aflatoxin B1 (AFB1), and the increased organic carbon content as well as interfacial hydrophobicity generate a hydrophobic interaction to weak polar zearalenone (ZER). Consequently, the surface functionalization affords Mt enhanced adsorption capacity for AFB1, approximately two times compared with Mt, and superior adsorption ability for ZER (10 mg/g). The present work provides sufficient evidence of "surface directs application" of Mt, which encourages researchers to focus on studies of the surface science of clay minerals.

Circular RNA expression profiles following MC-LR treatment in human normal liver cell line (HL7702) cells using high-throughput sequencing analysis.

Microcystin-LR (MC-LR), a frequently occurring hepatotoxic cyanotoxin produced by cyanobacterial blooms, poses a great threat to human health. However, the precise molecular mechanisms underlying MC-LR-induced hepatotoxicity remain to be determined. Recent investigators found that in many human diseases circular RNAs (circRNAs) a class of endogenous non-coding RNAs played critical roles in disease outcomes. The aim of this study was to investigate whether circRNAs were involved in MC-LR-mediated hepatotoxicity using human normal liver cell line (HL7702). Using high-throughput sequencing analysis data demonstrated that expression levels of 3250, 3111, 3097, 3253 circRNAs were significantly altered at concentrations ranging from 1 to 10 µM MC-LR. Expression levels of hsa_circRNA_0000657 and hsa_circRNA_0000659 were down-regulated while hsa_circRNA_0003247 and hsa_circRNA_0001535 were up-regulated in all MC-LR-exposed groups. The high-throughput sequencing results of selected circRNAs differential expression genes (DEGs) levels were verified by real-time fluorescent quantitative PCR (qRT-PCR). Gene Ontology (GO) enrichment analysis showed that the functions of circRNAs significantly altered in HL7702 cells were predominantly associated with metabolism, systems development, and protein binding. The Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analysis data revealed that the target genes of differentially expressed circRNAs in HL7702 cells were involved in FoxO signaling pathway, protein processing in endoplasmic reticulum, Ras signaling pathway, cell cycle, PI3K-Akt signaling pathway, MAPK signaling pathway and pathways in cancer. In summary, evidence indicates that a correlation may exist between circRNAs and MC-LR-induced hepatotoxicity.

Effects of microcystins-LR on genotoxic responses in human intestinal epithelial cells (NCM460).

Microcystin-LR (MC-LR), a cyclic heptapeptide toxin produced by cyanobacteria, was found to induce genotoxic actions in various types of cells. Some investigators reported that microcystin-LR acted as tumor initiator in the observed genotoxic action mediated by this cyanotoxin. However, the underlying mechanisms underlying MC-induced DNA damage in the human intestine epithelium cell line (NCM460) are not known. The purpose of this study was to examine the influence of 24 hr exposure to 5 or 10 µM MC-LR on intestinal DNA damage using NCM460 intestine cell line as a model. Data showed that MC-LR increased Olive tail moment (OTM) as evidenced by the comet assay, inhibited protein phosphatase 2A (PP2A) activity, elevated reactive oxygen species levels (ROS) and enhanced γ-H2AX and p-p53 protein expression levels. Results indicated that MC-LR produced intestinal DNA damage by inhibiting PP2A activity, activating p53 protein and subsequently initiating excess generation of ROS. These observations suggest that MC-LR-induced intestinal DNA damage involves a complex series of events that include oxidant stress, PP2A enzymic inhibition and activation of p53 protein.

Influence of microcystins-LR (MC-LR) on autophagy in human neuroblastoma SK-N-SH cells.

Microcystin-LR (MC-LR) variant exposure poses a potential health hazard to ecosystem, animals, and humans. Previously investigators showed that autophagy plays a key role in MC-LR induced cytotoxicity immortalized murine ovarian granular KK-1 cells and rat Sertoli cells. Recently exposure to MC-LR via drinking water was reported to accumulate in mouse brain with associated adverse oxidant and inflammatory responses. However, autophagy the physiological mechanism required for cells to degrade their own impaired organelles to maintain their homeostasis has not been determined with respect to MC-LR actions on the central nervous system (CNS). Thus, the aim of this study was to examine the effects of MC-LR on autophagy using human neuroblastoma SK-N-SH cells as CNS model. Data demonstrated that after treatment with 15 or 30 µmol/L MC-LR for 48 hr significantly reduced survival rate was noted in SK-N-SH cells. MC-LR increased the expression levels of autophagy-related proteins light chain 3 (LC3) II/I and p62 in SK-N-SH cells, resulting in the accumulation of LC3 and increased intracellular free calcium ion levels. Data indicated that MC-LR induced adverse effects on the CNS as evidenced by decreased cellular survival associated with inhibition of autophagy flux and consequent enhanced autophagosomes accumulation.

Involvement of MAPK/ERK1/2 pathway in microcystin-induced microfilament reorganization in HL7702 hepatocytes.

Several studies previously demonstrated that microcystin (MC)-LR produced cytoskeletal damage, especially to actin filaments. However, the underlying mechanisms of MC-induced cytoskeletal reorganization remain to be determined. The aim of this study was to examine the effects of 5 or 10 µM MC-LR on microfilament depolarization and expression of microRNA-451a (miR-451a) which plays a crucial role in cellular processes including cell proliferation, apoptosis and tumorigenesis in HL7702 liver cells after 24 hr treatment. Data demonstrated that MC-LR increased microfilament depolarization, elevated phosphorylation levels of mitogen-activated protein kinase (MAPK/ERK1/2) and vasodilator-stimulated phosphoprotein (VASP) but lowered miR-451a RNA expression levels. These molecular processes were associated with no marked changes in total protein ERK1/2. Data demonstrate that transfection with miR-451a may not be effective in the presence of MC-LR as evidenced by the inability of excess microRNA to prevent toxin-induced inhibition of threonine protein phosphatases1 (PP1) and 2A (PP2A) and microfilament reorganization in HL7702 cells.

Analysis of long non-coding RNA profiled following MC-LR-induced hepatotoxicity using high-throughput sequencing.

The occurrence of microcystin-LR(MC-LR) variant a known hepatotoxin constitutes a global public health concern. However, the molecular mechanisms underlying MC-LR-induced hepatotoxicity remain to be determined. The aim of this study was to investigate whether long noncoding RNAs (lncRNA) were involved in MC-LR-mediated hepatotoxicity using human normal liver cell line HL7702 to profile lncRNAs after 24 hr treatment with MC-LR. With the use of high-throughput sequencing techniques, data showed that the expression levels of 37, 33, 34, 35 lncRNA were significantly altered following exposure to 1, 2.5, 5, or 10 µM MC-LR, respectively. In particular, the expression levels of LINC00847, MIR22HG and LNC_00027 were markedly increased in all treatment groups. It is of interest that LNC_00027 was identified as a novel lncRNA. Quantitative real-time PCR (qPCR) was employed to determine the differentially expressed lncRNA levels. Analysis using Gene Ontology (GO) enrichment identified the functions of target genes involved in systems development, metabolism, and protein binding. Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis demonstrated that MC-LR exposure upregulated some important signaling pathways including pathway in cancer, PI3K-AKT signaling and MAPK pathway. In summary, data indicate that the MC-LR-induced alterations in lncRNA may be associated with hepatotoxicity and that upregulation of LINC00847, MIR22HG and LNC_00027 may play important roles in the observed MC-mediated liver damage.

Synthesis of a novel illite@carbon nanocomposite adsorbent for removal of Cr(VI) from wastewater.

A novel illite@carbon (I@C) nanocomposite adsorbent has been synthesized via a facile hydrothermal carbonization process (HTC) using glucose as carbonaceous source and illite as the carrier. The morphology, microstructure and surface properties of the prepared nanocomposite adsorbent were analyzed by FESEM, TGA, XRD, FT-IR and Zeta potential measurements. Batch experiments were carried out on the adsorption of Cr(VI) to determine the adsorption properties of the composite. The adsorption of Cr(VI) onto the I@C nanocomposite was well described by the pseudo-second-order kinetic model and Langmuir isotherm. Compared with the illite and carbon material (SC) separately, the prepared I@C nanocomposite adsorbent exhibited enhanced adsorption performance for Cr(VI) with a maximum adsorption capacity of 149.25mg/g, which was higher than that of most reported adsorbents. In addition, the adsorption process was spontaneous and endothermic based on the adsorption thermodynamics study. The adsorption of Cr(VI) by I@C was highly pH-dependent and the optimum adsorption occurred at pH2.0. The Zeta potential analysis results indicated that the electrostatic interactions between anionic Cr(VI) and the positively charged surface of the adsorbent might be critical to the adsorption mechanism. This study demonstrated that the I@C nanocomposite should be a promising candidate for a low-cost, environmental friendly and highly efficient adsorbent for the removal of toxic Cr(VI) from wastewater.

Synergistic Promotion System of Montmorillonite with Cu2+ and Benzalkonium Chloride for Efficient and Broad-Spectrum Antibacterial Activity.

By intercalating montmorillonite (MMT) with Cu2+ and benzalkonium chloride (BAC), the present work constructed a synergistic promotion system (Cu2+/BAC/MMT). MMT not only enhances the thermal stability of Cu2+ and BAC but also facilitates the controlled release of Cu2+ and BAC. Concurrently, the introduction of BAC improves the material's organic compatibility. In vitro assays show that the "MIC+" of Cu2+/BAC/MMT against Staphylococcus aureus is merely 7.32 mg/L and 55.56 mg/L against Escherichia coli. At concentrations of 10 and 25 mg/L, Cu2+/BAC/MMT inactivates 100% of S. aureus and E. coli within 2 h, respectively. Furthermore, it is confirmed that the prepared Cu2+/BAC/MMT exhibits a long-term antibacterial ability through antibacterial experiments and release tests. Also, the biosafety of this material was also substantiated by in vitro cytotoxicity tests. These comprehensive findings indisputably portend that Cu2+/BAC/MMT holds promise to supplant antibiotics as an efficacious treatment modality for bacterial infections.

Effect of microstructure in mesoporous adsorbents on the adsorption of low concentrations of VOCs: An experimental and simulation study.

This study evaluated the adsorption of five volatile organic compounds (VOCs) on Opoka, precipitated silica, and palygorskite, to elucidate the effect of their pore size on VOCs adsorption. The adsorption capacity of these adsorbents is not only highly correlated with their surface area and pore volume, but also notably improved by the presence of micropores. The variation in adsorption capacity for different VOCs was primarily influenced by their boiling point and polarity. Palygorskite, which had the smallest total pore volume (0.357 cm3/g) but the largest micropore volume (0.043 cm3/g) among the three adsorbents, exhibited the highest adsorption capacity for all tested VOCs. Additionally, the study constructed slit pore models of palygorskite with micropores (0.5 and 1.5 nm) and mesopores (3.0 and 6.0 nm), calculated and discussed the heat of adsorption, concentration distribution, and interaction energy of VOCs adsorbed on different pore models. The results revealed that the adsorption heat, concentration distribution, total interaction energy, and van der Waals energy decrease with increasing pore size. The concentration of VOCs in 0.5 nm pore was nearly three times that in 6.0 nm pore. This work can also provide guidance for further research on using adsorbents with mixed microporous and mesoporous structures to control VOCs.

Lactobacillus fermentum Alleviates the Colorectal Inflammation Induced by Low-Dose Sub-Chronic Microcystin-LR Exposure.

Microcystin-LR (MC-LR) contamination is a worldwide environmental problem that poses a grave threat to the water ecosystem and public health. Exposure to MC-LR has been associated with the development of intestinal injury, but there are no effective treatments for MC-LR-induced intestinal disease. Probiotics are "live microorganisms that are beneficial to the health of the host when administered in sufficient quantities". It has been demonstrated that probiotics can prevent or treat a variety of human diseases; however, their ability to mitigate MC-LR-induced intestinal harm has not yet been investigated. The objective of this study was to determine whether probiotics can mitigate MC-LR-induced intestinal toxicity and its underlying mechanisms. We first evaluated the pathological changes in colorectal tissues using an animal model with sub-chronic exposure to low-dose MC-LR, HE staining to assess colorectal histopathologic changes, qPCR to detect the expression levels of inflammatory factors in colorectal tissues, and WB to detect the alterations on CSF1R signaling pathway proteins in colorectal tissues. Microbial sequencing analysis and screening of fecal microorganisms differential to MC-LR treatment in mice. To investigate the role of microorganisms in MC-LR-induced colorectal injury, an in vitro model of MC-LR co-treatment with microorganisms was developed. Our findings demonstrated that MC-LR treatment induced an inflammatory response in mouse colorectal tissues, promoted the expression of inflammatory factors, activated the CSF1R signaling pathway, and significantly decreased the abundance of Lactobacillus. In a model of co-treatment with MC-LR and Lactobacillus fermentum (L. fermentum), it was discovered that L. fermentum substantially reduced the incidence of the colorectal inflammatory response induced by MC-LR and inhibited the protein expression of the CSF1R signaling pathway. This is the first study to suggest that L. fermentum inhibits the CSF1R signaling pathway to reduce the incidence of MC-LR-induced colorectal inflammation. This research may provide an excellent experimental foundation for the development of strategies for the prevention and treatment of intestinal diseases in MC-LR.

Subchronic Microcystin-LR Aggravates Colorectal Inflammatory Response and Barrier Disruption via Raf/ERK Signaling Pathway in Obese Mice.

Microcystin-LR (MC-LR) is an extremely poisonous cyanotoxin that poses a threat to ecosystems and human health. MC-LR has been reported as an enterotoxin. The objective of this study was to determine the effect and the mechanism of subchronic MC-LR toxicity on preexisting diet-induced colorectal damage. C57BL/6J mice were given either a regular diet or a high-fat diet (HFD) for 8 weeks. After 8 weeks of feeding, animals were supplied with vehicle or 120 µg/L MC-LR via drinking water for another 8 weeks, and their colorectal were stained with H&E to detect microstructural alterations. Compared with the CT group, the HFD and MC-LR + HFD-treatment group induced a significant weight gain in the mice. Histopathological findings showed that the HFD- and MC-LR + HFD-treatment groups caused epithelial barrier disruption and infiltration of inflammatory cells. The HFD- and MC-LR + HFD-treatment groups raised the levels of inflammation mediator factors and decreased the expression of tight junction-related factors compared to the CT group. The expression levels of p-Raf/Raf and p-ERK/ERK in the HFD- and MC-LR + HFD-treatment groups were significantly increased compared with the CT group. Additionally, treated with MC-LR + HFD, the colorectal injury was further aggravated compared with the HFD-treatment group. These findings suggest that by stimulating the Raf/ERK signaling pathway, MC-LR may cause colorectal inflammation and barrier disruption. This study suggests that MC-LR treatment may exacerbate the colorectal toxicity caused by an HFD. These findings offer unique insights into the consequences and harmful mechanisms of MC-LR and provide strategies for preventing and treating intestinal disorders.

High-efficient mineralization of formaldehyde by three-dimensional "PIZZA"-like bismuth molybdate-titania/diatomite composite.

The application of TiO2-based photocatalysts in air pollution control has attracted much attention thanks to their advantageous green and sustainable performance. However, how to improve the degradation efficiency under visible light is still challenging. Herein, we report a ternary three-dimensional "PIZZA"-like Bi2MoO6-TiO2/diatomite (BTD) composite with high-efficient mineralization and recycling performance towards gaseous formaldehyde (HCHO) under visible light. The high-efficient adsorption-photocatalysis collaborative system with intimate interface combination is successfully established among Bi2MoO6 (BMO), TiO2 and diatomite. The HCHO mineralization rate constant of BTD-1:2 composite is up to around 4.03 times and 2.18 times higher than those of bare BMO and binary Bi2MoO6-TiO2 composite, respectively. It is indicated that the introduction of diatomite increases active sites and plays the vital role in the improvement of photocatalysis. In addition, the photogenerated holes (h+) and hydroxyl radical (OH) are proved to be the main active species for HCHO mineralization. Furthermore, there is a competitive adsorption relationship between water (H2O) molecules and HCHO molecules, and both H2O molecules and oxygen (O2) molecules participated in the reaction of HCHO mineralization based on in-situ DRIFTs spectra analysis. Our work would give a new perspective on gaseous HCHO purification.

Protrudent electron transfer channels on kaolinite modified iron oxide QDs/N vacancy graphitic carbon nitride driving superior catalytic oxidation.

Optimizing electron transfer channels and sufficiently exposing active sites to trigger an efficient Fenton-like reaction are vital for manipulating catalytic properties of water treatment. Herein, Fe2O3 quantum dots were prepared and integrated with composites of g-C3N4 and kaolinite with nitrogen (N) vacancies (FONGK-10) for bisphenol A (BPA) removal in a peroxymonosulfate (PMS)/visible light (Vis) system. X-ray absorption near-edge structures and extended X-ray absorption fine structures demonstrated interface's combined properties. In particular, the tight interfacial contact and introduction of N vacancies resulted in the formation of effective electron channels, which caused more effective separation of electron-hole pairs and an extended response time of 1.5 × 10-4 s. Furthermore, the introduction of kaolinite reduced the Fe2O3 particle size and accelerated PMS consumption. The k value in FONGK-10/PMS/Vis system was 4.5 times that of the FONGK-10/PMS and 27.5 times that of the FONGK-10/Vis system, and the synergetic system exhibited superior consecutive catalytic performance in a fluidized-bed catalytic unit, degrading ~100% of BPA in 200 min. The exposed electron channels significantly maintained the Fe(III)/Fe(II) stable dynamic cycle, thereby enhancing the activation of PMS and photocatalysis performance.

Construction of BiOCl/Clinoptilolite Composite Photocatalyst for Boosting Formaldehyde Removal.

Binary composite was synthesized via coupling BiOCl with alkali leached natural clinoptilolite (40B0/CN), which showed retarded recombination of photo-generated carriers. The clinoptilolite was pretreated with alkali leaching, resulting in a larger pore size and high cation exchange capacity. The modified clinoptilolite was more feasible for the growth of BiOCl and to promote the adsorption ability for formaldehyde (HCHO). In addition, the cation exchange capacity was conducive to anchor Bi3+, further leading to the reduction of the particle size of BiOCl. The carrier effect of alkali leached natural clinoptilolite promoted the amorphous transformation of BiOCl at low temperature, which simultaneously produced more distortions and defects in the BiOCl lattice. The 40B0/CN composite exhibited the superior light absorption ability with a narrower band gap. The photocatalytic degradation rate for HCHO of 40B0/CN under solar light reached 87.7%, and the reaction rate constant was 0.0166 min-1, which was 1.6 times higher than that of BiOCl. This paper gave a deep insight into photocatalytic technology to efficiently degrade formaldehyde.

High Removal Efficiency of Diatomite-Based X Zeolite for Cu2+ and Zn2.

Diatomite-based X zeolite was obtained and its crystallinity, morphology, and interface properties were investigated by XRD, BET, SEM, EDS, and XRF. The obtained X zeolite possessed a unique meso-microporous structure and showed good ion exchange properties for Cu2+ and Zn2+. The pseudo-second-order model and Langmuir isotherm model can best describe the adsorption kinetics and isotherms of Cu2+ and Zn2+, respectively. The maximal adsorption capacities of X zeolite for Cu2+ and Zn2+ were 146 and 195 mg/g at 323 K, respectively. Meanwhile, the adsorption process for Cu2+ and Zn2+ were chemical adsorption and ion exchange, respectively. Furthermore, the adsorption data turned out to be an endothermic and spontaneous process. Compared with other reported materials, the adsorption capacity of X zeolite synthesized from diatomite was among the highest. Therefore, it could be a promising adsorbent for the disposal of wastewater that contains metal ions.

A review of clay based photocatalysts: Role of phyllosilicate mineral in interfacial assembly, microstructure control and performance regulation.

Over the past decades, inspired by the outstanding properties of clay minerals such as abundance, low-cost, environmental benignity, high stability, and regularly arranged silica-alumina framework, researchers put much efforts on the interface assembly and surface modification of natural minerals with bare photocatalysts, i.e. TiO2, g-C3N4, ZnO, MoS2, etc. The clay-based hybrid photocatalysts have resulted in a rich database for their tailor-designed microstructures, characterizations, and environmental-related applications. Therefore, in this study, we took a brief introduction of three representative minerals, i.e. kaolinite, montmorillonite and rectorite, and discussed their basic merits in photocatalysis applications. After that, we summarized the recent advances in construction of stable visible-light driven photocatalysts based on these minerals. The structure-activity relationships between the properties of clay types, pore structure, distribution/dispersion and light absorption, carrier separation efficiency as well as redox performance were illustrated in detail. Such representative information would provide theoretical basis and scientific support for the application of clay based photocatalysts. Finally, we pointed out the major challenges and future directions at the end of this review. Undoubtedly, control and preparation of novel photocatalysts based on clays will continue to witness many breakthroughs in the arena of solar-driven technologies.

Synergistic activation of peroxymonosulfate via in situ growth FeCo2O4 nanoparticles on natural rectorite: Role of transition metal ions and hydroxyl groups.

Developing low-cost, high-efficiency catalysts for advanced oxidation processes remain a key issue for the degradation of organic pollutants. In this study, a novel FeCo2O4/rectorite composite was synthesized via a facile combustion process and employed to activate peroxymonosulfate (PMS) for dealing with atrazine (ATZ). The addition of rectorite could result in higher specific surface area, smaller pore size and more hydroxyl groups, which were beneficial to enrich pollutants to the adsorption sites and provide sufficient reactive sites. After meticulous evaluation, the degradation efficiency of FeCo2O4/rectorite composite towards ATZ exhibited improved PMS activation efficiency which was about 2.6 times than that of pure FeCo2O4. Based on the characterization results, the sulfate radicals and hydroxyl radicals were considered to be the main free radicals which were involved into the circulation of Co(II)-Co(III)-Co(II) as well as the oxidation of ≡Fe(II), which was responsible for the remarkable catalytic efficiency. In addition, the chemical stability and superior catalytic performance of FeCo2O4/rectorite should also be attributed to the chemical combination between metal ions and the surface hydroxyl groups of rectorite. Overall, these findings are beneficial for understanding the mechanism of PMS activation by natural mineral-based catalysts and contributing to the practical application of sulfate-based technology for organic wastewater treatment.

Clinoptilolite mediated activation of peroxymonosulfate through spherical dispersion and oriented array of NiFe2O4: Upgrading synergy and performance.

Inspired by the features of both transition metal oxide and natural clinoptilolite (flaky structure with suitable pore diameter and open skeleton structure), we adopted a robust strategy by immobilization of nickel ferrite nanoparticles (NiFe2O4) on the clinoptilolite surface via typical citric acid combustion method. The hybrid catalyst exhibited enhanced peroxymonosulfate (PMS) activation efficiency and bisphenol A (BPA) degradation performance. Calculated by effective equivalent of NiFe2O4, it is found that the reaction rate constant (k) of NiFe2O4/clinoptilolite/PMS system (0.1859 min-1) was 11.9 times higher than that of bare NiFe2O4/PMS system (0.0156 min-1), which demonstrated that catalyst would be conjugated to PMS or contaminant efficiently and renders the rapid degradation and mineralization in the presence of clinoptilolite. After comprehensive characterization analysis and DFT simulations, natural mineral carrier effect (i.e. decreased crystalline size, increased oxygen vacancy content, etc.), abundant surface-bonded and structural hydroxyl groups as well as effective bonding with iron or nickel ions charged for the potential activation mechanism of PMS by NiFe2O4/clinoptilolite composite. And it is indicated that not only •OH and SO4•-, but also 1O2 was involved into series reactions. Overall, this study put forward a green and promising technology for high-toxic wastewater treatment.