Metal-organic frameworks (MOFs) are recognized as important Fenton-like materials for environmental remediation. However, their applications are often hindered by slow cycling between Fe (III) and Fe (II). This study aimed to address the slow Fe (III)/Fe (II) cycling limitation of Fe-MOFs through dual modification strategy: bimetallic modification and amino functionalization. A series of NH2-MOF(Fe, Co) catalysts with varying Fe/Co ratios were synthesized via a hydrothermal method and evaluated for sulfamethoxazole (SMX) degradation. The optimized NH2-MOF(Fe, Co) catalyst (Fe/Co ratio = 7:3) exhibited substantially enhanced catalytic performance, with SMX removal rate and rate constant in the H2O2 system being 3.2 and 43.5 times higher than those of the Fe-MOF/H2O2 system, respectively. The catalyst demonstrated robust performance across a wide pH range (3.05-7.00), addressing a common limitation of Fenton-like systems. Physicochemical characterization revealed that the enhanced performance was attributed to two key factors: the synergistic effect between Co and Fe in the bimetallic active center, and improved electron transfer to the central metal due to -NH2 functionalization. These modifications effectively addressed the Fe (III)/Fe (II) redox cycling limitation. The proposed reaction mechanism provides insights into SMX degradation pathways in the NH2-MOF(Fe, Co)/H2O2 system. This study presents an efficient and stable MOF-based Fenton-like catalyst with potential applications in wastewater treatment and environmental remediation.

Enhancing the velocity of the oxidation-reduction cycle is crucial for improving the catalytic efficiency of Fenton processes. Therefore, the development of an effective strategy for wastewater degradation at low temperatures is essential. In this context, we present the preparation of an NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. Specifically, CuInS2 nanoparticles are introduced onto the Ferro-organic skeleton, resulting in the exposure of a significant number of active surface sites. Furthermore, NH2-MIL-88B (Fe)/CuInS2 demonstrates an extended photoresponse into the long-wavelength region, which contributes to its excellent photothermal properties. Notably, the degradation rate of tetracycline in low-temperature aqueous environments reaches as high as 99.7 %, several times higher than that of the original sample. Additionally, the hydrogen production of NH2-MIL-88B (Fe)/CuInS2 is 2.23 times that of single NH2-MIL-88B (Fe) and 3.46 times that of single CuInS2. Moreover, the system exhibits good H2O2 evolution performance, forming an efficient photo-Fenton system. The charge transfer process in S-scheme heterojunction is confirmed using in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance. Both transient photoluminescence and photo electrochemical tests further validate the enhanced photoelectrochemical properties of the NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. The exceptional performance of this system can be attributed to the synergistic effects of the S-scheme heterojunction and the bimetallic codoped photo-Fenton system. This research presents a novel approach for the breakdown of low-temperature wastewater using an improved photocatalytic Fenton system.

A method is proposed for studying photochemical reactions in solution in real time using aerodynamic/thermal breakup droplet ionization mass spectrometry. Capabilities of the method were demonstrated by analyses of photodegradation processes of three antibiotics (thiamphenicol, ciprofloxacin, and ofloxacin) by means of aqueous solutions. The method rapidly provided information about photochemical changes for understanding the photochemical processes.

In this work, MIL-88A(Fe) was immobilized onto the expanded perlites to fabricate the floating MIL-88A(Fe)@expanded perlites (M@EP) catalyst via high throughput batch synthesis method under room temperature. The as-prepared M@EP could efficiently activate H2O2 to achieve 100% tetracycline antibiotics (TCs) removal under both artificial low power UV light (UVL) and real sunlight (SL) irradiation. The toxicological evaluation, growth experiment of mung beans and antimicrobial estimation revealed the decreasing aquatic toxicity of the TCs intermediates compared to those of the pristine TCs. A self-designed continuous bed reactor was employed to investigate the long-term operation of the M@EP. The findings demonstrated that the antibiotics mixture can be continuously degraded up to 7 days under UVL and 5 daytimes under SL irradiation, respectively. More importantly, ca. 76.9% and 81.6% of total organic carbon (TOC) removal efficiencies were accomplished in continuous bed reactor under UVL and SL irradiation, respectively. This work advances the immobilized MOFs on floating supports for their practical application in large-scale wastewater purification through advanced oxidation processes. ENVIRONMENTAL IMPLICATION: This work presented the high throughput production and photo-Fenton degradation application of floating MIL-88A(Fe)@expanded perlites (M@EP). Three tetracycline antibiotics (TCs) were selected as model pollutants to test the degradation ability of M@EP in batch experiment and continuous operation under artificial light and solar light. The complete TCs degradation could be accomplished in self-designed device up to 7 d under UV light and 5 d under real solar light. This work tapped a new door to push MOFs-based functional materials in the real water purification.

The use of modified clays can play an effective role as an effective adsorbent in removing fluoride (Flu) ions from water and aqueous solutions. In the present research, montmorillonite clay (MMt) was modified using CoFe2O4 magnetic particles and Al-Fe fumarate metal-organic framework (Al-Fe Fum) and was utilized as an efficient adsorbent for removing Flu from aqueous solution. The properties of MMt and MMt/CoFe2O4/Al-Fe Fum samples were investigated using different techniques. The results showed that with the modification of MMt using CoFe2O4 magnetic particles and the metal-organic framework of Al-Fe Fum, the BET surface has increased notably from 13.217 to 365.80 m2/g. To investigate the effect of independent variables and their interaction on the efficiency of the Flu adsorption, response surface method-central compound design (RSM-CCD) was served. Based on the results of ANOVA, the F-value and p-value parameters for the desired model were determined to be 783.09 and < 0.0001, respectively, which confirms the success and high ability of the model. The number of R2, adjusted R2, and Predicted R2 for adsorption of Flu ion was determined to be 0.998, 0.997, and 0.995, respectively, which shows that the proposed regression model can describe the process of adsorption and interaction between variables well. Compared to other kinetic models, the pseudo 2nd order kinetic model has a greater ability to describe the Flu adsorption behavior. The R2 parameter value determined that the Freundlich isotherm model has a suitable ability to investigate the isotherm behavior and confirms the effect of heterogeneous surfaces in the process. Generally, the outcomes signified that the MMt and MMt/CoFe2O4/Al-Fe Fum samples can be reused several times in the process of Flu adsorption, while the efficiency is more than 90%.

The sphere-shaped zinc oxide (ZnO) photocatalyst was synthesized by the homogeneous precipitation method, using Zn(CH3COO)2·2H2O as a zinc precursor and NH4OH as a precipitating agent. The morphology and crystal structure of the prepared ZnO sample were studied by XRD, SEM, FT-IR, XPS, zeta potential measurements, and a low-temperature nitrogen adsorption-desorption technique. The optical characteristics of ZnO were determined by UV - Vis diffuse reflectance spectroscopy. ZnO photocatalyst performance of up to 100% within 210 min was observed in the photodegradation of the ofloxacin antibiotic under ultraviolet (UV) irradiation. The effect of antibiotic concentration, heavy metal ions, and water sources on the photocatalytic activity of ZnO demonstrated both the potential of its application under different conditions, and a good adaptability of this photocatalyst. The photodegradation reaction correlated well with the first-order kinetics model, with a rate constant of 0.0173 min-1. The reusability of the photocatalyst was verified after three cycles of use. Admittedly, photogenerated electrons and holes played a key role in removal of the antibiotic. This work showed the suitability of prepared ZnO for antibiotic removal, and its potential use for environmental protection.

We synthesized Sr-doped spinel CoCr2O4 using the solution combustion method and characterized the structure, morphology, chemical state, and photocatalytic properties through different techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and electrochemical impedance spectroscopy (EIS). 30-50 nm cuboid CoCr2O4 nanocrystals with Sr doping levels ranging from 0 to 0.6% were obtained; the increasing Sr doping deformed the coordination number of Co and Cr, transitioning to octahedral and tetrahedral units, inducing the phase transition from spinel to inverse spinel at 0.6% Sr content. This modification enhanced optical absorption, reduced the energy band gap, increased photoluminescence intensity, and maintained a high-spin state with oxygen vacancies. 0.6% Sr-doped CoCr2O4 demonstrated the highest photocatalytic efficiency at 93%. The XRD structure and photocatalytic activity remained at 87% over 7 cycles after 14 h. Employing degradation pathways and Mott-Schottky curves elucidated the enhancement mechanism.

Mechanochemical (MC) remediation with zero-valent iron (ZVI) as co-milling agent enables the non-combustion and solvent-free disposal of solid halogenated organic pollutants (HOPs) via solid-phase reaction, but suffers from incomplete dechlorination (especially for less chlorinated chemicals). Herein, a reduction-oxidation coupling strategy using ZVI and peroxydisulfate as synergistic (ZVI-PDS) co-milling agents was investigated, with 2,4-dichlorophenol (2,4-DCP) as probe contaminant. By revisiting the MC destruction process of 2,4-DCP by ZVI, the contribution of both reductive and oxidative routes is confirmed, and the inefficient •OH generation is addressed. With ball-to-material and reagent-to-pollutant mass ratios of 30:1 and 13:1, respectively, ZVI-PDS achieves higher dechlorination ratio (86.8%) for 2,4-DCP within 5 h, outcompeting sole ZVI (40.3%) or PDS (33.9%), due to the accumulation of numerous SO4•-. As suggested by a two-compartment kinetic model, the optimal ZVI/PDS molar ratio of 4:1 is determined, which balances the relative contribution of reductive/oxidative routes and leads to a maximum mineralization efficiency of 77.4%. The analysis on product distribution verifies the generation of dechlorinated, ring-opening and minor coupling products (with low acute toxicity). This work validates the necessity to couple reduction with oxidation in MC destruction for solid HOPs, and may provide information on reagent formulation.

Contaminants in water pose a significant challenge as they are harmful and difficult to treat using conventional methods. Therefore, various new methods have been proposed to degrade organic pollutants in water, among which the photo-Fenton process is considered promising. In recent years, Fe-based metal-organic frameworks (Fe-MOFs) have gained attention and found applications in different fields due to their cost-effectiveness, non-toxic nature, and unique porous structure. Many researchers have applied Fe-MOFs to the photo-Fenton process in recent years and achieved good results. This review focuses on describing different strategies for enhancing the performance of Fe-MOFs in the photo-Fenton process. Also, the mechanism of MOF in the photo-Fenton process is described in detail. Finally, prospects for the application of Fe-MOFs in photo-Fenton systems for the treatment of organic pollutants in water are presented. This study provides information and ideas for researchers to use Fe-MOFs to remove organic pollutants from water by photo-Fenton process.

Visible-light-driven heterogeneous photo-Fenton process has emerged as the most promising Fenton-derived technology for wastewater decontamination, owing to its prominent superiorities including the potential utilization of clean energy (solar light), and acceleration of ≡Fe(II)/≡Fe(III) dynamic cycle. As the core constituent, catalysts play a pivotal role in the photocatalytic activation of H₂O₂ to yield reactive oxidative species (ROS). To date, all types of iron-based heterogeneous photo-Fenton catalysts (Fe-HPFCs) have been extensively reported by the scientific community, and exhibited satisfactory catalytic performance towards pollutants decomposition, sometimes even exceeding the homogeneous counterparts (Fe(II)/H₂O₂). However, the relevant reviews on Fe-HPFCs, especially from the viewpoint of catalyst-self design are extremely limited. Therefore, this state-of-the-art review focuses on the available Fe-HPFCs in literatures, and gives their classification based on their self-characteristics and modification strategies for the first time. Two classes of representative Fe-HPFCs, conventional inorganic semiconductors of Fe-containing minerals and newly emerging Fe-based metal-organic frameworks (Fe-MOFs) are comprehensively summarized. Moreover, three universal strategies including (i) transition metal (TMs) doping, (ii) construction of heterojunctions with other semiconductors or plasmonic materials, and (iii) combination with supporters were proposed to tackle their inherent defects, viz., inferior light-harvesting capacity, fast recombination of photogenerated carriers, slow mass transfer and low exposure and uneven dispersion of active sites. Lastly, a critical emphasis was also made on the challenges and prospects of Fe-HPFCs in wastewater treatment, providing valuable guidance to researchers for the reasonable construction of high-performance Fe-HPFCs.

Treatment of recalcitrant and xenobiotic pharmaceutical compounds in polluted waters have gained significant attention of the environmental scientists. Antibiotics are diffused into the environment widely owing to their high usages, very particularly in the last two years due to over consumption during covid 19 pandemic worldwide. Quinolones are very effective antibiotics, but do not get completely metabolized due to which they pose severe health hazards if discharged without proper treatment. The commonly reported treatment methods for quinolones are adsorption and advanced oxidation methods. In both the treatment methods, metal organic frameworks (MOF) have been proved to be promising materials used as stand-alone or combined technique. Many composite MOF materials synthesized from renewable, natural, and harmless materials by eco-friendly techniques have been reported to be effective in the treatment of quinolones. In the present article, special focus is given on the abatement of norfloxacin and ofloxacin contaminated wastewater using MOFs by adsorption, oxidation/ozonation, photocatalytic degradation, electro-fenton methods, etc. However, integration of adsorption with any advanced oxidation methods was found to be best remediation technique. Of various MOFs reported by several researchers, the MIL-101(Cr)-SO₃H composite was able to give 99% removal of norfloxacin by adsorption. The MIL - 88A(Fe) composite and Fe LDH carbon felt cathode were reported to yield 100% degradation of ofloxacin by photo-Fenton and electro-fenton methods respectively. The synthesis methods and mechanism of action of MOFs towards the treatment of norfloxacin and ofloxacin as reported by several investigation reports are also presented.