Metal Research Articles

Study of heavy metals adsorption using a silicate-based material: Experiments and theoretical insights

Heavy metal toxicity in water is a serious problem with harmful effects on human health and the ecosystem. This research studied a silicate-based material as an adsorbent for removing four heavy metals from aqueous solutions. The target metal pollutants selected include manganese (Mn2+), copper (Cu2+), cobalt (Co2+), and zinc (Zn2+). First, theoretical tools including potential energy surface analysis, Natural Population Analysis, AIM, Wiberg Bond Index, QTAIM, and topological methods offer profound insights into the nature of interactions present in the Mg2O8Si3M (M = Mn2+, Cu2+, Co2+, Zn2+) clusters. Second, the synthesis and characterization of eco-friendly hydrated amorphous magnesium silicate (MgOSiO2nH2O) was developed. Last, a simple kinetic adsorption test was applied to assess the material selectivity towards heavy metals and support theoretical results. The kinetic adsorption study was analyzed through the pseudo-first and second-order kinetics, Elovich, and the intraparticle diffusion models. The theoretical analysis of the adsorption energies indicates that the adsorption of four metal ions on the Mg2O8Si3 surface is energetically favorable in all cases. The material displayed the following adsorption sequence: Cu2+ (59 mg g-1) > Zn2+(25 mg g-1) ≈ Co2+ (23 mg g-1) > Mn2+ (15 mg g-1). This knowledge can then be used to design and optimize low-cost silicate-based materials for effective heavy metal removal, contributing to efforts to address environmental pollution and protect public health.

Polyoxometalate-Ionic Liquids for Mitigating the Effects of Iron Gall Ink Corrosion on Cellulosic Supports.

Iron gall ink (IGI), renowned for its indelibility, was the most important writing ink in the Western world from the 15th to the late 19th century. However, it is now known that IGIs induce acid-catalyzed hydrolysis and iron-catalyzed oxidation of the cellulose in historical paper documents. These mechanisms of deterioration cause significant damage to the writing support materials, including color alteration and burn-through appearance, and in the worst scenarios, physical disintegration of the supports. Minimally invasive, long-term effective conservation treatments that tackle the underlying mechanisms of IGI degradation and their corrosion effects are yet to be developed. This study introduces the deployment of hydrophobic and anticorrosive polyoxometalate-ionic liquids (POM-ILs) as colorless coatings to counteract IGI-corrosion of cellulosic supports. Model IGI-containing papers (mockups) were prepared, coated with POM-ILs, and artificially aged to assess the compatibility of POM-ILs with IGI-containing documents. Comprehensive monitoring using colorimetric and scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM/EDS) analyses showed minimal interference with the aesthetic properties and morphology of the IGI mockups. In addition, polyoxometalates (POMs) with vacant metal atom sites in the cluster shell can be used to coordinate free transition metal ions. The ability of a monolacunary Keggin-type polyoxotungstate to coordinate free Fe(II) from IGI solution was demonstrated using UV-vis analysis. This led to the formation of a dimeric species, [(SiW11O39Fe)2O]K12·28H2O, which was characterized by single-crystal X-ray diffraction. Altogether, this study points to POM-ILs as promising protective coatings for effectively preserving historical IGI-written heritage.

Highly effective and selective recovery of germanium from coal acid leaching solution by trihydroxyl functionalized titanium dioxide

In this study, a novel trihydroxyl functionalized titanium dioxide (TiO2-NH2-3OH) was successfully synthesized by the Schiff base reaction method. TiO2-NH2-3OH was characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), x-ray Photoelectron Spectroscopy (XPS), x-ray diffraction techniques (XRD), and further applied to recover germanium (Ge(IV)) from coal acid leaching solution. TiO2-NH2-3OH exhibited superior capture performance on Ge(IV) at a pH of 3, and the optimal TiO2-NH2-3OH dosages were 0.8 g L−1. The distribution coefficients of germanium for coexisting metal ions (Zn2+, Co2+, Mn2+, Ni2+ and Al3+) were all greater than 1, indicating that TiO2-NH2-3OH had good selective adsorption performance for Ge(IV) in complex solution environments. Compared with other kinetic models, pseudo-second-order model was more suitable to reveal the absorption of Ge(IV). Moreover, the experiment data were fitted better with Langmuir model at 298 K than the other isothermal models, and the maximum adsorption capacity was up to 72.94 mg g−1. Thermodynamic data suggesting that the capture of Ge(IV) on TiO2-NH2-3OH was a spontaneous endothermic process, increasing the temperature was beneficial for the adsorption reaction to proceed. TiO2-NH2-3OH with saturated adsorption still maintained a high removal rate of 80.55 % of Ge(IV) after five cycles, indicating good stability and recyclability of TiO2-NH2-3OH. XPS analysis indicated that the capture of germanium by TiO2-NH2-3OH may be due to the ion exchange interaction between -OH and Ge(OH)4 on the adsorbent surface. This work indicated that TiO2-NH2-3OH had great advantages and potential for the recovery of Ge(IV) from coal acid leaching solution.

Development of a colorimetric sensor for selective manganese detection using green-synthesized silver nanoparticles from Withania somnifera

This study reports the green synthesis of silver nanoparticles (AgNPs) using the fruit extract of Withania somnifera and their application as a colorimetric sensor for selective manganese (Mn2+) ion detection. The synthesis of AgNPs was optimized by varying pH, reaction time, and concentrations of fruit extract and AgNO3. UV–visible spectroscopy revealed that the highest absorbance of AgNPs occurred at pH 11, indicating optimal conditions for NPs formation. The absorbance behavior over time demonstrated the nucleation and stabilization processes, with optimal stability achieved after 1800 min. Increasing concentrations of fruit extract and AgNO3 enhanced NPs synthesis, reaching a plateau at 1.0 mL of extract and 1.0 mM AgNO3, respectively. Transmission electron microscopy (TEM) confirmed the formation of spherical AgNPs of 43–85 nm. Fourier-transform infrared spectroscopy (FTIR) indicated the involvement of functional groups such as O-H and C=O in the reduction and stabilization of AgNPs. The green-synthesized AgNPs exhibited notable antioxidant activity, with moderate free radical scavenging abilities compared to ascorbic acid. The colorimetric detection of Mn2+ was achieved through the aggregation of AgNPs, leading to a visible color change. UV–vis absorption spectra showed a prominent peak at 412 nm, with a linear relationship between absorbance change and Mn2+ concentration, demonstrating high sensitivity and selectivity. Comparative studies with other metal ions (Co2+, Cr3+, Ni2+) confirmed the specificity of AgNPs towards Mn2+. In conclusion, the green-synthesized AgNPs from W. somnifera offer a cost-effective and environmentally friendly approach for Mn2+ detection, with significant potential for environmental monitoring and biomedical applications.

Efficient removal of environmentally hazardous heavy metal ions from water by NH2-MIL-101-Fe and MOF-808-EDTA based polyether sulfone adsorbents

The potential of metal–organic frameworks (MOFs) based polymeric composites for heavy metal removal was analyzed in this study. Two mixed matrix composites, along with NH2-MIL-101-Fe and MOF-808-EDTA, were synthesized. The MOFs were synthesized using the solvothermal method, and the mixed matrix spheres (MMSs) were prepared using the facile dropping method. The MMSs were characterized, and batch adsorption studies were performed at different pH and adsorbent dosages. For both MMSs, the optimum pH was between 5–5.5, and the highest removal rates were obtained for MOF-808-EDTA spheres (94 % Hg2+, 86 % As, 80 % Mn). The optimum adsorbent dosage for MOF-808-EDTA was found to be 5.42 g/L, while for NH2-MIL-101-Fe, it was 7.13 g/L, after which the metal ion removal efficiency was reduced. Langmuir adsorption isotherm was fitted with thermodynamic evaluation of Gibbs free energy, enthalpy, and entropy. MOF-808-EDTA demonstrated a greater adsorption capacity of 272.7 mg/g (Hg2+), 151.29 mg/g (As3+), and 125.9 mg/g (Mn2+) than the other MMP. The Gibbs free energy of −20.14 (Hg2+), −12.66 (Mn2+), and −52.61 kJ/mol (As3+) were obtained from the thermodynamic study. The results indicated that the process was exothermic and spontaneous. Breakthrough column studies were performed for MOF-808-EDTA spheres using the pore-surface-diffusion model. The transient column study was conducted for individual heavy metal ion solutions using Addesign™ software to evaluate column exhaustion time, breakthrough time and length of mass transfer zone. Studies with multicomponent solutions of heavy metals also gave potentially promising results in the separation of 92 % of Hg, 84 % As, and 75 % Mn which indicates the prepared adsorbents can be used to remove heavy metal ions from industrial wastewater samples.

Serum protein albumin and chromium: Mechanistic insights into the interaction between ions, nanoparticles, and protein

The interaction of human proteins and metal species, both ions and nanoparticles, is poorly understood despite their growing importance. These materials are the by-products of corrosion processes and are of relevance for food and drug manufacturing, nanomedicine, and biomedical implant corrosion. Here, we study the interaction of Cr(III) ions and chromium oxide nanoparticles with bovine serum albumin in physiological conditions. This study combined electrophoretic mobility measurements, spectroscopy, and time-of-flight secondary ion mass spectrometry with principal component analysis. It was determined that neither metal species resulted in global albumin unfolding. The Cr(III) ions interacted strongly with amino acids found in previously discovered metal binding sites, but also were most strongly implicated in the interaction with negatively charged acid residues, suggesting an electrostatic interaction. Bovine serum albumin (BSA) was found to bind to the Cr2O3 nanoparticles in a preferential orientation, due to electrostatic interactions between the positive amino acid residues and the negative chromium oxide nanoparticle surface. These findings ameliorate our understanding of the interaction between trivalent chromium ions and nanoparticles, and biological macromolecules.

Characteristics of inhibition of Aspergillus flavus growth and degradation of aflatoxin B1 by cell-free fermentation supernatant of Bacillus velezensis 906

Aflatoxin, a harmful secondary metabolite produced by Aspergillus flavus and Aspergillus parasiticus, poses a significant risk to human health and food safety. Therefore, the development of safe and environmentally friendly techniques for controlling A. flavus and its aflatoxin production is imperative. In this study, Bacillus velezensis 906 cell-free fermentation supernatant (CFS) inhibited the germination of A. flavus spores and mycelium growth. Scanning electron microscopy and fluorescence microscopy revealed that CFS altered cell morphology and damaged the cell membrane of A. flavus leading to cell death. Fourier transform infrared spectroscopy indicated changes in the functional groups of A. flavus filaments treated with CFS. The trend in ergosterol content demonstrated that CFS effectively inhibited the normal growth of A. flavus cell membranes. The CFS exhibited remarkable efficacy in degrading aflatoxin B1 (AFB1), achieving a degradation rate of up to 60% after 48 h of interaction. The addition of 0.2 mg/mL Cu2+ or Fe3+ metal ions to CFS significantly increased the degradation rate of AFB1 up to 90%. Furthermore, the analysis indicated that the active components responsible for AFB1 degradation might be heat-resistance and exhibit resistance to protease K. These findings underscore the potential of CFS as a green, safe, and economically viable strategy for controlling aflatoxin production by A. flavus, offering promising prospects for mitigating mold contamination in food and feed applications.

Dual structure cobalt sites on surface hydroxyl and oxygen vacancy of BiOCl for cooperative CO2 reduction and tetracycline oxidation

Metal ion cocatalysts have huge prospect for photocatalytic CO2 reduction coupled with organic decomposition because of their cost effectiveness and abundant active sites. Herein, we exploit a defect−group oriented tactic to induce dual−structured Co sites on BiOCl with rich surface hydroxyls (OHs) and oxygen vacancies (OVs) (labeled as BiO1−xCl−OH), in which the surface OHs and OVs acted as anchoring points to anchor Co2+ ions. Density functional theory calculations manifested that surface OHs anchored Co2+ ions via hydrogen bonding to produce tight OH−Co sites, meanwhile, surface OVs with unsaturated metal sites and unpaired electrons captured Co2+ ions through chemical bonding to form close−knit OV−Co site. The as−generated OV−Co and OH−Co site served as reductive and oxidative cocatalyst for CO2 reduction and tetracycline oxidation, respectively, thereby achieving high−efficiency redox activity. This work provided a novel strategy to devise progressive dual functional metal ions cocatalysts for high−efficiency CO2 reduction and organic pollutants oxidation.

Multi-dimensional signals coupling of simultaneous acquisition stripping current with laser-induced breakdown spectroscopy for accurate analysis of Cd(II) in coexisting Cu(II)

BackgroundDespite significant advancements in detecting Cd(II) using nanomaterials-modified sensitive interfaces, most detection methods rely solely on a single electrochemical stripping current to indicate concentration. This approach often overlooks potential inaccuracies caused by interference from coexisting ions. Therefore, establishing multi-dimensional signals that accurately reflect Cd(II) concentration in solution is crucial. ResultsIn this study, we developed a system integrating concentration, electrochemical stripping current, and laser-induced breakdown spectroscopy (LIBS) characteristic peak intensity through in-situ laser-induced breakdown spectroscopy and electrochemical integrated devices. By simultaneously acquiring multi-dimensional signals to dynamically track the electrochemical deposition and stripping processes, we observed that replacement reactions occur between Cu(II) and Cd(II) on the surface of Ru-doped MoS2 modified carbon paper electrodes (Ru-MoS2/CP). These reactions facilitate the oxidation of Cd(0) to Cd(II) during the stripping process, significantly increasing the currents of Cd(II). Remarkably, the ingenious design of the Ru-MoS2 sensitive interface allowed for the undisturbed deposition of Cu(II) and Cd(II) during the electrochemical deposition process. Consequently, our in-situ integrated device achieved accurate detection of Cd(II) in complex environments, boasting a detection sensitivity of 8606.5 counts μM⁻1. SignificanceBy coupling multi-dimensional signals from stripping current and LIBS spectra, we revealed the interference process between Cu(II) and Cd(II), providing valuable insights for accurate electrochemical analysis of heavy metal ions in complex water environments.

Solar driven kaolin-based hydrogels for efficient interfacial evaporation and heavy metal ion adsorption from wastewater

Solar evaporation technology holds great promise for desalination and wastewater treatment due to its low energy consumption and sustainability. However, simultaneously removing contaminants from bulk water during the evaporation process remains challenging. In this work, we developed a clay-based hydrogel evaporator which exhibits efficient photothermal evaporation and heavy metal ion adsorption. The prepared Kaolin/CNTs/PAM hydrogel (KCAH) demonstrated approximately 99.8% light absorption in the wavelength range of 250–2,500 nm and achieved an evaporation rate of 2.99 kg m−2 h−1 under one sun illumination. It maintained over 99% desalination efficiency and exhibited good cycling stability in simulated seawater with different salinities, and its performance was verified in heavy metal ion and organic dye wastewater. Additionally, during the photothermal synergistic adsorption tests for Mn2+ ion, the KCAH achieved an evaporation rate of 2.74 kg m−2 h−1 and an adsorption capacity of 94.5 mg g−1. In the outdoor test, it is shown that the KCAH system’s daily water production was 4.85 kg m−2, with Mn2+ adsorption capacity of 265.37 mg g−1. In summary, this solar evaporator boasts high evaporation performance and excellent adsorption capabilities, making it a promising option for solar water purification, especially for heavy metal ion wastewater treatment.

(Ce, Nd) co-doped TiO2 NPs via hydrothermal route:Structural, optical, photocatalytic and thermal behavior

Rare earth (Ce, Nd) doped/co-doped titania (TiO2) nanoparticles were successfully produced by hydrothermal route. Titanium isopropoxide (IV), cerium nitrate hexahydrate and neodymium nitrate hexahydrate were utilized as raw/starting materials. The effect of Ce and Nd doping/co-doping in TiO2 were studied through different complementary tools such as XRD, FTIR, FE-SEM, EDX, XPS, UV–Visible, PL, photocatalytic and thermal analysis. XRD spectra revealed anatase tetragonal phase and cubic phase due to titania and ceria nanoparticles respectively. The crystallite size, lattice constants, volume and no. of unit cell were determined through XRD data. Optical studies revealed the band gap, urbach energy, extinction coefficient, refractive index, optical conductivity and photoluminescence emission wavelength. FTIR spectra investigated the chemical bondings and functional groups present in prepared samples. Optical absorption spectra confirmed that absorption edge is red shifted, indicating a decrease in band gap from 3.5 to 3.0 eV with the incorporation of rare earth ions (Ce, Nd) in TiO2 matrix. The rate of electron-hole pair recombination was reduced through co-doping of (Ce, Nd) in TiO2 lattice as exhibited by reduction in intensity of photo luminescence spectra. The photocatalytic efficiency was enhanced with the integration of rare earth metal ions in TiO2 matrix for different dyes such as rhodamine B (RhB) and malachite green (MG) with visible light irradiation. The degradation efficiency of (Ce, Nd) co-doped TiO2 NPs against RhB and MG dyes was found to be 89 and 95 % respectively. TGA analysis was carried out to find weight loss during different thermodynamic phases such as dehydration, decomposition and combustion, and crystallization. Various thermodynamic parameters such as activation energy, entropy and enthalpy were estimated by thermal analysis.

N-Doped Carbon Dots for Selective Detection of Fe3+ and Degradation of Fe3+/Basic Red 9 Complexes in Water Samples.

In this work, the eco-friendly N-doped carbon dots KF-CDs and A-CDs were derived from kiwifruit by a simple one-step hydrothermal strategy at 180°C for 6h. KF-CDs have a high fluorescence quantum yield (27.85%), it is obviously rapid quenched by Fe3+, and have a good linear relationship from 1 to 8.26 µM (the detection limit was 0.077 µM). Basic red 9 is extensively used in biological, environmental and industry. Although it makes a great contribution to the economy, its toxicity should be taken seriously, especially with harmful metal ions. Within 2h, A-CDs could degrade basic red 9 with degradation efficiency 89.6%, even though there was a stable compound formed with Fe3+ that the degradation efficiency was up to 88.3%. The results complement the research blank of carbon dots in catalytic degradation of basic red 9.

The conversion of metal ions to metals particles contributes the photoaging of microplastics in aquatic environments

Metals ions enriched on the surface of Microplastics (MPs) may undergo redox reactions under UV irradiation to promote its photoaging. However, there is a paucity of information on studies of the aging behavior of MPs mediated by different metal ions. This study aims to investigate the effects of three different metal ions (Ag+, Cu2+ and Al3+) on the photoaging properties of polypropylene (PP) to enhance our comprehension of their aging in water contaminated by heavy metals. Physicochemical analyses, like the ratio of O/C and carbonyl index (CI), suggested that metal ions accelerated the aging of PP. The correlation model was established between CI and aging time to confirm that the aging sequence of PP in three metal ions solution was Ag+-PP>Cu2+-PP>Al3+-PP. Electron Paramagnetic Resonance (EPR) results showed metal ions enhanced the generation of reactive oxygen species (•O2–, HO• and 1O2) to accelerate aging through free radical pathways. Electronic exchange capability (EEC) and X-Ray Photoelectron Spectroscopy (XPS) confirmed metal particles were on PP, leading to the e-bridge for electronic relays that altered the EEC of PP and accelerated its protonation process. It needs to note the surface plasmon resonance (SPR) effect of metal nanoparticles may also accelerated the photoaging of MPs in UV–vis illumination. For the first time, the study establishes a connection between different valence states metal ion and PP aging, shedding light on interfacial and free radical aging process of MPs. The finding also proposes the potential e-bridge or SPR effect of metal particles may exist in accelerating photoaging reaction of PP in special water bodies contaminated with heavy metals. The environmental implications and ecological risks of this phenomenon warrant greater consideration.

Characterization of metal-binding behavior of DOM component structure in biochar: Analysis of binding sites, binding sequences and impact pathways

The binding of biochar-derived dissolved organic matter (BDOM) to heavy metals is a complex and dynamic process, with potentially different impact pathways. The outer electrons of various heavy metals can also affect their binding ability. This study comprehensively investigated the binding sites, sequences, constants, and influencing pathways of each component structure in BDOM through modern spectroscopic methods and multidimensional chemometrics. Here, the dominance of carboxyl and phenolic groups in the interaction of chromogenic dissolved organic matter (CDOM) with metal ions, which complex with BDOM, leads to an increase in the size of the BDOM molecule. In addition, Cu and Zn primarily bound to humic acids fluorophore, while Pb and Ni preferentially bound to protein-like fluorophore, likely due to the varying affinities of nitrogen- and carbon-based functional groups for different metals. Significant differences were observed in the interactions between different metal ions and fluorophores, involving both direct and indirect effects. Molecular perspectives and pathways suggested that the binding of BDOM to Zn was notably intricate, involving multiple conformational changes and impact pathways. These findings offer a crucial scientific foundation for a comprehensive comprehension of the interaction mechanisms between various metal ions and BDOM components.

Multifunctional Chitosan Nanofiber-Based Sponge Materials Using Freeze-Thaw and Post-Cross-Linking Method.

The fabrication of porous sponge materials with stable structures via cross-linking diverse polymers presents significant challenges due to the simultaneous requirements for phase separation as a pore-forming step and cross-linking reactions during the fabrication process. To address these challenges, we developed a sponge material solely from natural-based polymers, specifically chitosan nanofibers (CSNFs) and dialdehyde carboxymethyl cellulose (DACMC), employing a straightforward, eco-friendly technique. This technique integrates a facile freeze-thaw method with subsequent cross-linking between CSNFs and DACMC. This method effectively addresses the difficulties associated with pore formation in materials, which typically arise from the rapid formation and precipitation of polyionic complexes during the mixing of anionic and cationic polymers, using ice crystals as a rigid template. The resultant sponge materials exhibit remarkable shape recoverability in their wet state and maintain light, stable porosity in the dry state. Furthermore, in comparison to commonly used commercial foams, this composite porous material demonstrates superior fire retardancy and thermal insulation properties in its dry state. Additionally, it shows effective adsorption capacities for both cationic and anionic dyes and metal ions. This method of using biobased polymers to produce porous composites offers a promising avenue for creating multifunctional materials, with potential applications across various industries.

Surface- modified preparation of CuFe2O4/sodium alginate hydrogel catalysts for the long-lasting degradation of tetracycline

Copper ferrate spinel (CuFe2O4) catalysts are widely used in advanced oxidation processes for environmental wastewater treatment due to their advantages of low price, mild reaction conditions and ease of operation. Therefore, it is crucial to investigate the factors influence the surface properties of catalysts on their catalytic activity. In this research, the effects of process parameters on the surface properties of CuFe2O4 were investigated, and the relationship between the surface properties of CuFe2O4 and its catalytic activity was clarified. The optimised CuFe2O4 exhibited 92.4 % degradation of tetracycline (TC) and 55 % mineralisation of total organic carbon (TOC) within 30 min, the pseudo-first-order reaction rate was 0.0315 min−1, which was 2.2 times higher than that of the unoptimised CuFe2O4. The mechanism of action for enhancing catalyst performance and the degradation mechanism of tetracycline were clarified through a combination of characterization analysis. To further solve the problems of secondary pollution caused by ion leaching and the difficulty of practical application of powder catalysts, novel hydrogel microspheres composed of sodium alginate and CuFe2O4 were prepared by using the property of metal ions and sodium alginate to form a solid gel (SA/Ort-6). SA/Ort-6 was characterized by low ion leaching, excellent performance and excellent stability. The mass ratio of catalyst to treated water could be up to 1:22,000, and the mass ratio of catalyst to treated water can reach up to 1:22000, the removal rate of TOC was stable above 35 %. This study provides valuable insights into the relationship between surface properties and catalytic performance of CuFe2O4, offers a new approach to effectively solve leaching of metal ions, and opens up a new avenue for practical application of powder catalysts.

An efficient voltammetric sensing platform for trace determination of Norfloxacin based on nanoplate-like α-zirconium phosphate/carboxylated multiwalled carbon nanotube nanocomposites

Norfloxacin (NOR) residues pose a potential threat to our health and ecosystem, so it is highly urgent to develop a simple but accurate method for NOR determination. Therefore, an efficient voltammetric sensing platform was constructed for trace detection of NOR based on nanoplate-like α-zirconium phosphate/carboxylated multiwalled carbon nanotubes (α-ZrP/CMWCNT). The physiochemical characteristics of α-ZrP/CMWCNT were scrutinized using various microscopic, spectroscopic, and electrochemical means. In order to pursuit higher voltammetric responses, detection conditions of NOR such as accumulation potential, accumulation time and buffer pH, were explored comprehensibly. The α-ZrP/CMWCNT enlarged the electrochemically active surface area and lowered the charge transfer resistance. Owing to the synergistic interactions between nanoplate-like α-ZrP NPs and CMWCNTs, the α-ZrP/CMWCNT boosted the voltammetric response signals and reduced the over-potential of NOR. Consequently, the α-ZrP/CMWCNT demonstrated remarkably catalytic activity for NOR electrooxidation, with two broad linear detection ranges (0.01–0.1 μM; 0.1–10.0 μM) and a low detection limit (2.8 nM). The α-ZrP/CMWCNT modified glassy carbon electrode (GCE) exhibited strong anti-interfering ability even in excess of other antibiotics and common metal ions, and maintained robust response peaks up to two weeks. The α-ZrP/CMWCNT/GCE realized accurate determination of NOR from complicated matrices at trace levels with good recoveries (99.00–104.40 %).

Ultra-sensitive detection of cadmium and lead in water using crown ether gel electromembrane extraction coupled with miniaturized electrochemical system

This study presents the development of an electrochemical technique combined with gel electromembrane extraction (G-EME) for the simultaneous detection of cadmium and lead in environmental water samples. Crown ether (18C6) was added to the gel as a complexing agent and cationic carrier. The electrochemical responses were evaluated using differential pulse anodic stripping voltammetry (DPASV) across various pH levels and deposition times. The most sensitive response (acetate buffer pH 4, deposition time 90 s) was selected for the development of the G-EME process. By applying a 30 V electrical potential across the gel membrane containing 1 % (w/v) of 18C6 for 10 min, positively charged Cd2+ and Pb2+ ions migrated from the donor phase (pH 5.0) through the 18C6@gel membrane (pH 5.0) into the acceptor phase (pH 5.0). This resulted in a linear range from 0.3 to 5 µg/L for Cd2+ and 0.5 to 5 µg/L for Pb2+, with detection limits of 0.10 µg/L and 0.19 µg/L, respectively— up to 120 times more sensitive than direct electrochemical measurements. Furthermore, the proposed technique maintained selectivity for cadmium and lead, despite the presence of other potential heavy metal ions in the environment.

Synthesis of a dual-response signal sensor and naked-eye recognition of hypochlorite in real water samples

An innovative dual-modal colorimetric and fluorometric probe MDXM is synthesized based on the dihydro-1H-xanthene motif via Knoevenagel reaction. The incorporation of a malononitrile group into the dihydro-1H-xanthene motif via a double bond results in an extensive macroconjugated π-system, which endows MDXM with a pronounced molar absorptivity and effectively quenches the intramolecular charge transfer (ICT) effect. Upon exposure to hypochlorite, the C = C bond in MDXM undergoes cleavage, resulting in the formation of an aldehyde group. This process restores the ICT effect and manifests as a clear fluorescent ''turn-on'' signal at 530 nm, with a remarkably linear response across the ClO− concentration range of 0–60 μM. The probe achieves a notably low detection limit of 7.14 nM, reflecting its exceptional sensitivity. In the presence of 15 common metal ions and oxidizing agents, MDXM can specifically identify hypochlorite with excellent anti-interference ability. The response mechanism of MDXM to hypochlorite was confirmed through Nuclear Magnetic Resonance (NMR) spectroscopy and computational Density Functional Theory (DFT) calculations. The practical applicability of MDXM is underscored by its successful implementation in analyzing hypochlorite in 5 varied real water samples. This showcases MDXM's promise for environmental and analytical chemistry, providing a robust tool for hypochlorite detection in diverse settings.

In-depth insights into transformation mechanism of synthetic saponite to amorphous silica under acid attack

Amorphous mesoporous materials derived from synthetic saponite (Sap) by acid treatment have been used in catalysis for several decades. Uncovering the transformation process of Sap from layered to amorphous structure under acid attack is beneficial to optimize the structure of Sap-derived mesoporous materials, yet such transformation process remains unclear. Herein, a magnesium-Sap was synthesized by hydrothermal method and then treated with sulfuric acid. By studying the changes in phase composition, morphology, chemical state of elements and surface area of the synthetic Sap after acid attack, a specified transformation mechanism of synthetic Sap to amorphous silica is clarified. The experimental results indicate that after leaching of Mg and Al cations from the Mg/AlO6 octahedral sheets of Sap during acid attack, the retained SiO4 tetrahedral sheets of Sap were transformed into amorphous short-range ordered silica phases and nanoscrolls with pseudohexagonal side pores. The transformation process of synthetic Sap under acid attack can be divided into leaching of metal ions from octahedral sheets of Sap to form layered silica particles, splitting and crimping of surface nano-silica layers from the formed silica particles, and completely amorphous transformation. The distortion of SiO bonds in SiO4 tetrahedral sheets during acid attack might be the driving force for such transformation. This work provides specific transformation process of synthetic Sap under acid attack which is conductive to the controllable preparation of acid-treated Sap derivates, and has certain significance for understanding of structural transformation of clay minerals with MgO6 octahedral structure.