Recent advancements in modifications of metal-organic frameworks-based materials for enhanced water purification and contaminant detection.

Metal-organic frameworks (MOFs) have emerged as a key focus in water treatment and monitoring due to their unique structural features, including extensive surface area, customizable porosity, reversible adsorption, and high catalytic efficiency. While numerous reviews have discussed MOFs in environmental remediation, this review specifically addresses recent advancements in modifying MOFs to enhance their effectiveness in water purification and monitoring. It underscores their roles as adsorbents, photocatalysts, and in luminescent and electrochemical sensing. Advancements such as pore modification, defect engineering, and functionalization, combined synergistically with advanced materials, have led to the development of recyclable MOF-based nano-adsorbents, Z-scheme photocatalytic systems, nanocomposites, and hybrid materials. These innovations have broadened the spectrum of removable contaminants and improved material recyclability. Additionally, this review delves into the creation of multifunctional MOF materials, the development of robust MOF variants, and the simplification of synthesis methods, marking significant progress in MOF sensor technology. Furthermore, the review addresses current challenges in this field and proposes potential future research directions and practical applications. The growing research interest in MOFs underscores the need for an updated synthesis of knowledge in this area, focusing on both current challenges and future opportunities in water remediation.

Exploring optical descriptors for rapid estimation of coastal sediment organic carbon and nearby land-use classifications via machine learning models.

This study utilizes ultraviolet and fluorescence spectroscopic indices of dissolved organic matter (DOM) from sediments, combined with machine learning (ML) models, to develop an optimized predictive model for estimating sediment total organic carbon (TOC) and identifying adjacent land-use types in coastal sediments from the Yellow and Bohai Seas. Our results indicate that ML models surpass traditional regression techniques in estimating TOC and classifying land-use types. Penalized Least Squares Regression (PLR) and Cubist models show exceptional TOC estimation capabilities, with PLR exhibiting the lowest training error and Cubist achieving a correlation coefficient 0.79. In land-use classification, Support Vector Machines achieved 85.6 % accuracy in training and 92.2 % in testing. Maximum fluorescence intensity and ultraviolet absorbance at 254 nm were crucial factors influencing TOC variations in coastal sediments. This study underscores the efficacy of ML models utilizing DOM optical indices for near real-time estimation of marine sediment TOC and land-use classification.

Smartphone-based paper strip assay for putrescine and spermidine detection using hybrid organic-inorganic perovskite with Eu3+ complex.

A new method utilizing fluorescent ratiometry is proposed for detecting putrescine and spermidine. The method involves the use of a fluorescent probe comprising a 2D halide perovskite synthesized from octadecylamine-iodine and PbI2via a grinding-sonicating technique, along with a Eu3+-complex. Upon excitation at 290 nm, the probe fluoresces at two distinguishable wavelengths. The addition of putrescine and spermidine significantly decreases the emission of the 2D halide perovskite at 496 nm, while the emission of the Eu3+-complex at 618 nm remains stable. The color changes of the probe depend on the concentration of putrescine and spermidine, and the assay offers linearity over a wide concentration range (30-4000 ng mL-1), a low detection limit (4 ng mL-1 for putrescine, and 7 ng mL-1 for spermidine), and a quick response time. Furthermore, a portable device based on a smartphone can be used to record the color change of the paper test strip using the prepared fluorescent materials. The fluorescence quenching mechanism of the probe is explained as dynamic quenching.

Using CuMgFe layered double oxide to replace laccase as a catalyst for abiotic humification.

Humification offers a promising avenue for sequestering dissolved organic carbon while facilitating environmental cleanup. In this study, CuMgFe layered double oxides (LDO) were applied as a catalyst to replace conventional enzymes, such as laccase, thereby enhancing the in vitro polyphenol-Maillard humification reaction. CuMgFe LDO was synthesized through calcination of CuMgFe layered double hydroxides (LDH) at 500 °C for 5 h. A suite of characterization methods confirmed the successful formation into mixed oxides (Cu2O, CuO, MgO, FeO, and Fe2O3) after thermal treatment. A rapid humification reaction was observed with CuMgFe LDO, occurring within a two-week span, likely due to a distinct synergy between copper and iron elements. Subsequent analyses identified that MgO in CuMgFe LDO also played a pivotal role in humification by stabilizing the pH of the reaction. In the absence of magnesium, LDO's humification activity was more pronounced in the early stages of the reaction, but it rapidly diminished as the reaction progressed. The efficiency of CuMgFe LDO was heightened at elevated temperatures (35 °C), while light conditions manifested a discernible effect, with a modest decrease in humification efficacy under indoor light exposure. CuMgFe LDO surpassed both laccase and MgFe LDH in performance, boasting a superior humification efficiency relative to its precursor, CuMgFe LDH. The catalysts' humification activity was modulated by their crystallinity and valence dynamics. Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results suggested that introducing the amino acid, glycine, expedited the CuMgFe LDO-fueled humification, enhancing the formation of C-N and C-C bonds in the resultant products. The humic-like substances derived from the catalyst-enhanced reaction displayed an elevated presence of aromatic configurations and a richer array of oxygen functional groups in comparison to a typical commercial humic material.

Construction of a uniform zeolitic imidazole framework (ZIF-8) nanocrystal through a wet chemical route towards supercapacitor application.

Exploring larger surface area electrode materials is crucial for the development of an efficient supercapacitors (SCs) with superior electrochemical performance. Herein, a cost-effective strategy was adopted to synthesize a series of ZIF8 nanocrystals, and their size effect as a function of surface area was also examined. The resultant ZIF8-4 nanocrystal exhibits a uniform hexagonal structure with a large surface area (2800 m2 g-1) and nanometre size while maintaining a yield as high as 78%. The SCs performance was explored by employing different aqueous electrolytes (0.5 M H2SO4 and 1 M KOH) in a three-electrode set-up. The SC performance using a basic electrolyte (1 M KOH) was superior owing to the high ionic mobility of K+. The optimized ZIF8-4 nanocrystal electrode showed a faradaic reaction with a highest capacitance of 1420 F g-1 at 1 A g-1 of current density compared to other as-prepared electrodes in the three-electrode assembly. In addition, the resultant ZIF8-4 was embedded into a symmetric supercapacitor (SSC), and the device offered 350 F g-1 of capacitance with a maximum energy and power density of 43.7 W h kg-1 and 900 W kg-1 at 1 A g-1 of current density, respectively. To determine the practical viewpoint and real-world applications of the ZIF8-4 SSC device, 7000 GCD cycles were performed at 10 A g-1 of current density. Significantly, the device exhibited a cycling stability around 90% compared to the initial capacitance. Therefore, these findings provide a pathway for constructing large surface area ZIF8-based electrodes for high-value-added energy storage applications, particularly supercapacitors.

Tungsten-based nanocatalysts with different structures for visible light responsive photocatalytic degradation of bisphenol A.

Environmental pollution, such as water contamination, is a critical issue that must be absolutely addressed. Here, three different morphologies of tungsten-based photocatalysts (WO3 nanorods, WO3/WS2 nanobricks, WO3/WS2 nanorods) are made using a simple hydrothermal method by changing the solvents (H2O, DMF, aqueous HCl solution). The as-prepared nanocatalysts have excellent thermal stability, large porosity, and high hydrophilicity. The results show all materials have good photocatalytic activity in aqueous media, with WO3/WS2 nanorods (NRs) having the best activity in the photodegradation of bisphenol A (BPA) under visible-light irradiation. This may originate from increased migration of charge carriers and effective prevention of electron‒hole recombination in WO3/WS2 NRs, whereby this photocatalyst is able to generate more reactive •OH and •O2- species, leading to greater photocatalytic activity. About 99.6% of BPA is photodegraded within 60 min when using 1.5 g/L WO3/WS2 NRs and 5.0 mg/L BPA at pH 7.0. Additionally, the optimal conditions (pH, catalyst dosage, initial BPA concentration) for WO3/WS2 NRs are also elaborately investigated. These rod-like heterostructures are expressed as potential catalysts with excellent photostability, efficient reusability, and highly active effectivity in different types of water. In particular, the removal efficiency of BPA by WO3/WS2 NRs reduces by only 1.5% after five recycling runs and even reaches 89.1% in contaminated lake water. This study provides promising insights for the nearly complete removal of BPA from wastewater or different water resources, which is advantageous to various applications in environmental remediation.

Structural Characterization and Cytotoxic Activity Evaluation of Ulvan Polysaccharides Extracted from the Green Algae Ulva papenfussii.

Ulvan, a sulfated heteropolysaccharide with structural and functional properties of interest for various uses, was extracted from the green seaweed Ulva papenfussii. U. papenfussii is an unexplored Ulva species found in the South China Sea along the central coast of Vietnam. Based on dry weight, the ulvan yield was ~15% (w/w) and the ulvan had a sulfate content of 13.4 wt%. The compositional constitution encompassed L-Rhamnose (Rhap), D-Xylose (Xylp), D-Glucuronic acid (GlcAp), L-Iduronic acid (IdoAp), D-Galactose (Galp), and D-Glucose (Glcp) with a molar ratio of 1:0.19:0.35:0.52:0.05:0.11, respectively. The structure of ulvan was determined using High-Performance Liquid Chromatography (HPLC), Fourier Transform Infrared Spectroscopy (FT-IR), and Nuclear Magnetic Resonance spectroscopy (NMR) methods. The results showed that the extracted ulvan comprised a mixture of two different structural forms, namely ("A3s") with the repeating disaccharide [→4)-ß-D-GlcAp-(1→4)-α-L-Rhap 3S-(1→]n, and ("B3s") with the repeating disaccharide [→4)-α-L-IdoAp-(1→4)-α-L-Rhap 3S(1→]n. The relative abundance of A3s, and B3s was 1:1.5, respectively. The potential anticarcinogenic attributes of ulvan were evaluated against a trilogy of human cancer cell lineages. Concomitantly, Quantitative Structure-Activity Relationship (QSAR) modeling was also conducted to predict potential adverse reactions stemming from pharmacological interactions. The ulvan showed significant antitumor growth activity against hepatocellular carcinoma (IC50 ≈ 90 µg/mL), human breast cancer cells (IC50 ≈ 85 µg/mL), and cervical cancer cells (IC50 ≈ 67 µg/mL). The QSAR models demonstrated acceptable predictive power, and seven toxicity indications confirmed the safety of ulvan, warranting its candidacy for further in vivo testing and applications as a biologically active pharmaceutical source for human disease treatment.

Cu2O/Fe3O4/UiO-66 nanocomposite as an efficient fenton-like catalyst: Performance in organic pollutant degradation and influencing factors based machinelearning.

The persistent presence of organic pollutants like dyes in water environment necessitates innovative approaches for efficient degradation. In this research, we developed an advanced hybrid catalyst by combining metal oxides (Cu2O, Fe3O4) with UiO-66, serving as a heterogeneous Fenton catalyst for for efficient RB19 breakdown in water with H2O2. The control factors to the catalytic behavior were also quantified by machine learning. Experimental results show that the catalytic performance was much better than its individual components (P < 0.05 & non-zero 95% C.I). The improved catalytic efficiency was linked to the occurrence of active metal centers (Fe, Cu, and Zr), with Cu(I) from Cu2O playing a crucial role in promoting increased production of HO•. Also, UiO-66 served as a catalyst support, attracting pollutants to the reaction center, while magnetic Fe3O4 aids catalyst recovery. The optimal experimental parameters for best performance were pH at 7, catalyst loading of 1.6 g/L, H2O2 strength of 0.16 M, and reaction temperature of 25 °C. The catalyst can be magnetically separated and regenerated after five recycling times without significantly reducing catalytic activity. The reaction time and pH were ranked as the most influencing factors on catalytic efficiency via Random Forest and SHapley Additive exPlanations models. The findings show that developed catalyst is a suitable candidate to remove dyes in water by Fenton heterogeneous reaction.

Metal-organic framework-based nanomaterials for CO2 storage: A review.

The increasing recognition of the impact of CO2 emissions as a global concern, directly linked to the rise in global temperature, has raised significant attention. Carbon capture and storage, particularly in association with adsorbents, has occurred as a pivotal approach to address this pressing issue. Large surface area, high porosity, and abundant adsorption sites make metal-organic frameworks (MOFs) promising contenders for CO2 uptake. This review commences by discussing recent advancements in MOFs with diverse adsorption sites, encompassing open metal sites and Lewis basic centers. Next, diverse strategies aimed at enhancing CO2 adsorption capabilities are presented, including pore size manipulation, post-synthetic modifications, and composite formation. Finally, the extant challenges and anticipated prospects pertaining to the development of MOF-based nanomaterials for CO2 storage are described.

Ni, Co, Zn, and Cu metal-organic framework-based nanomaterials for electrochemical reduction of CO2: A review.

The combustion of fossil fuels has resulted in the amplification of the greenhouse effect, primarily through the release of a substantial quantity of carbon dioxide into the atmosphere. The imperative pursuit of converting CO2 into valuable chemicals through electrochemical techniques has garnered significant attention. Metal-organic frameworks (MOFs) have occured as highly prospective materials for the reduction of CO2, owing to their exceptional attributes including extensive surface area, customizable architectures, pronounced porosity, abundant active sites, and well-distributed metallic nodes. This article commences by elucidating the mechanistic aspects of CO2 reduction, followed by a comprehensive exploration of diverse materials encompassing MOFs based on nickel, cobalt, zinc, and copper for efficient CO2 conversion. Finally, a meticulous discourse encompasses the challenges encountered and the prospects envisioned for the advancement of MOF-based nanomaterials in the realm of electrochemical reduction of CO2.

Characterization and Bioactivity of Piper chaudocanum L. Extract-Doped ZnO Nanoparticles Biosynthesized by Co-Precipitation Method.

Green synthesis and nanomaterials have been the current trends in biomedical materials. In this study, Piper chaudocanum L. leaf extract-doped ZnO nanoparticles (PLE-doped ZnO NPs), a novel nanomaterial, were studied including the synthesis process, and the biomedical activity was evaluated. PLE-doped ZnO NPs were synthesized by the co-precipitation method, with differences in the synthesis procedures and dosages of the extract. The X-ray diffraction, Fourier transform infrared, scanning electron microscopy, energy dispersive X-ray spectroscopy, Brunauer-Emmett-Teller, ultraviolet-visible diffuse reflectance spectroscopy, and photoluminescence spectrum analysis results showed that the biosynthesized PLE-doped ZnO NPs were pure and in a hexagonal wurtzite phase. The PLE-doped NPs were synthesized by adding the extract to the zinc acetate solution before adjusting the pH and exhibited the smallest size (ZPS50 was 22 nm), the richest in the surface organic functional groups and the best optical activity. The highest antibacterial activity against P. aeruginosa and S. aureus was observed at 100 µg/mL of ZPS50 NPs, and the inhibition zone reached 42 and 39 nm, respectively. Moreover, ZPS50 NPs showed a moderate effectiveness against KB cancer cells with an IC50 value of 43.53 ± 2.98 µg/mL. This present study's results suggested that ZPS50 NPs could be a promising nanomaterial in developing drugs for treating human epithelial carcinoma cells and infectious illnesses.

Magnetic visible-light activated photocatalyst ZnFe2O4/BiVO4/g-C3N4 for decomposition of antibiotic lomefloxacin: Photocatalytic mechanism, degradation pathway, and toxicity assessment.

Magnetic ZnFe2O4/BiVO4/g-C3N4 (ZBC) composites were prepared via a facile hydrothermal and calcination method for the degradation of a representative antibiotics lomefloxacin (LFX) under visible light irradiation. The optimal photocatalyst ZBC-10 with a ZnFe2O4:BiVO4:g-C3N4 mass ratio of 1:8:10 performed 96.1% removal of LFX after 105 min of illumination. The excellent performance is ascribed to the effective construction of heterojunctions and its capacity to form a double Z-scheme charge transmission pathway among the hosts in ZBC-10. The composite enhanced the separation and migration of photoexcited charge carriers and the effective generation of multiple active radicals including ·OH, ·O2-, and 1O2. The LFX degradation process, identified based on an integrated HPLC-Q-TOF-MS analysis and density functional theory computation of the Fukui indices, comprised of three pathways initiated by the opening of the piperazinyl ring, separation of piperazinyl and quinoline moieties, and cleavage of the pyridine ring on the quinoline moieties. Ecotoxicological evaluation confirmed the reduced toxicity of transformation intermediates over photocatalysis. Convenient magnetic recovery, high performance, and high recyclability made ZBC-10 a promising visible-light-activated photocatalyst for practical implementation in eliminating antibiotics from wastewater.

Advances in application of g-C3N4-based materials for treatment of polluted water and wastewater via activation of oxidants and photoelectrocatalysis: A comprehensive review.

Recently, graphitic carbon nitride (g-C3N4) has received significant attention as a non-metallic, visible-light-activated photocatalyst for treating water and wastewater by degrading contaminants. Accordingly, previous review articles have focused on the photocatalytic properties of g-C3N4-based materials. However, g-C3N4 has several other notable features, such as high adsorption affinity towards aromatic substances and heavy metals, high thermal and chemical resistances, good compatibility with various materials, and easily scalable synthesis; therefore, in addition to simple photocatalysis, it can be widely used in other decontamination systems based on activation of oxidants and electrocatalysis. This critical review provides a comprehensive summary of recent advancements in g-C3N4-based materials and their use in treating polluted water and wastewater via the following routes (1) activation of oxidizing agents (e.g., hydrogen peroxide, ozone, peroxymonosulfate, and persulfate): and (2) photoelectrocatalysis using fabricated g-C3N4-based photocathodes and photoanodes. For each route, we briefly summarize the primary mechanisms, distinctive features, and performances of various water treatment systems using g-C3N4-based catalysts. We also highlight the specific roles of g-C3N4 in improving the efficiencies of these treatment processes. The advantages and limitations of previously reported water treatment systems using g-C3N4-based materials are also described and compared in this review. Finally, we discuss the challenges and prospects of improving g-C3N4-based water purification applications.

Polyethyleneimine modification of activated fly ash and biochar for enhanced removal of natural organic matter from water via adsorption.

In this study, fly ash (FA) and biochar (BC), two common industrial byproducts, were activated and surface-modified with polyethyleneimine (PEI) to enhance their capacities to remove natural organic matter (NOM) from water via adsorption. Different fluorescent components were identified using fluorescence excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) to explore the individual adsorption behaviors of different organic constituents in a bulk NOM. The NOM adsorption was quantitatively examined via adsorption isotherm and kinetics models. Compared to the pristine adsorbents, the functionalized adsorbent with increased surface area and positive surface charge achieved higher NOM adsorption. By evaluating the adsorptive behaviors of UV-absorbing and fluorescent moieties, it was concluded that the operative mechanism of adsorption included electrostatic attraction, hydrogen bonding, and π-π interaction. At the optimal pH of 3, the surface-modified FA and BC (i.e., FA-PEI and BC-PEI) had adsorption capacities for NOM that were ∼3 times higher than the capacities of the pristine materials. Due to its aromatic features, π-π interaction may have enhanced BC and BC-PEI selective adsorption of aromatic NOM components compared to FA and FA-PEI. Kinetic modelling showed that the mesopores of FA-PEI were available for NOM adsorption and diffusion of NOM molecules into the mesoporous structures was rate-limiting. On the other hand, PEI-modification may have further reduced NOM diffusion through the narrow micropores in BC such that external adsorption primarily occurred on BC-PEI. The modified adsorbents showed a faster adsorption kinetics than the pristine counterparts and a high durability in repeated adsorption-desorption cycles.

Visible light-activated degradation of natural organic matter (NOM) using zinc-bismuth oxides-graphitic carbon nitride (ZBO-CN) photocatalyst: Mechanistic insights from EEM-PARAFAC.

In this study, the complex degradation behavior of natural organic matter (NOM) was explored using photocatalytic oxidation systems with a novel catalyst based on a hybrid composite of zinc-bismuth oxides and g-C3N4 (ZBO-CN). The photooxidation system demonstrated the effective removal of NOM under low-intensity visible light irradiation, presenting removal rates of 53-74% and 65-88% on the basis of dissolved organic carbon (DOC) and the UV absorption coefficient (UV254), respectively, at 1.5 g/L of the catalyst. The NOM removal showed an increasing trend with a higher ZBO-CN dose. Comparative experiments with the hole and OH radical scavengers revealed that the direct oxidation occurring on the catalyst's surface might be the governing photocatalytic mechanism. Fluorescence excitation emission matrix-parallel factor analysis (EEM-PARAFAC) revealed the individual removal behavior of the different constituents in bulk NOM. Different tendencies towards preferential adsorption and subsequent oxidative removal were found among dissimilar fluorescent components within a bulk terrestrial NOM, following the order of terrestrial humic-like (C1) > humic-like (C2) > microbial humic-like (C3) components. The result suggests the dominant operation of π-π and/or hydrophobic interactions between the NOM and the catalyst. The discriminative removal behavior was more pronounced in visible light versus UV-activated systems, probably due to the incapability of visible light to excite è - h+ pairs of ZnO and the triplet state of NOM. The high photoactivity and structural stability of ZBO-CN under visible light implies its potential for an effective, low-cost and energy-saving treatment technology to selectively remove large sized humic-like substances from water.

Structure, conformation in aqueous solution and antimicrobial activity of ulvan extracted from green seaweed Ulva reticulata.

The aim of this study is to elucidate the structure and investigate the antimicrobial activity of an ulvan obtained by water extraction from green seaweed Ulva reticulata collected at Nha Trang sea of Vietnam by using IR, NMR, SEC-MALLS and SAXS methods. The ulvan is composed of rhamnose, galactose, xylose, manose and glucose (mole ratio Rha: Gal: Xyl: Man: Glu = 1:0.12:0.1:0.06:0.03), uronic acid (22.5%) and sulphate groups (17.6%). Chemically structural determination showed that the ulvan mainly composed of disaccharide [→4)ß-D-GlcA(1→4)α-L-Rha3S-(1→]. The results from SAXS indicated that ulvan under study has a rod-like bulky chain conformation. Ulvan from U. reticulata showed high antimicrobial activity, with inhibition zone diameter of 20 mm against Enterobacter cloace and 18 mm against Escherichia coli.