Search Results (2,665)

To address the low selectivity in the electrocatalytic conversion of furfural (FFR) to furfuryl alcohol (FFA) under alkaline conditions, a Zn-based metal–organic framework (MBON-2) featuring a 3D hierarchical flower-like architecture self-assembled from nanosheets was synthesized via a simple hydrothermal method. Under optimal conditions, MBON-2 exhibited an extremely high selectivity of FFA (100%) and a high Faradaic efficiency (FE) of 93.19% at −0.2 V vs. RHE. Electrochemical impedance spectroscopy (EIS) revealed the excellent electron transfer and mass transport properties of MBON-2. In addition, in situ Fourier transform infrared (FTIR) spectroscopy studies confirmed the adsorption of FFR molecules onto the Zn and B sites of MBON-2 during the ECH of FFR, providing key insights into the hydrogenation mechanism. The numerous exposed B and Zn sites of the MBON-2, as well as its robust structural stability contributed to its outstanding catalytic performance in the electrochemical hydrogenation (ECH) of FFR. This work provides valuable guidelines for developing efficient Zn-based catalysts for the ECH of FFR. Full article

Metal–organic frameworks (MOFs), particularly ZIF-8, have emerged as promising materials due to their high porosity, tunability, and chemical stability. In this study, we report the synthesis of ZnFe₂O₃-doped ZIF-8 composites with 10 wt% loading via a solvothermal method to enhance their optical and photocatalytic performance. Structural analyses confirmed the successful incorporation of ZnFe₂O₃ without disrupting the ZIF-8 framework. Optical studies revealed enhanced absorption in the visible range, a narrowed bandgap (4.26 eV vs. 4.37 eV for pristine ZIF-8), and an increased extinction coefficient, indicating superior light-harvesting potential. The photocatalytic activity was evaluated by methylene blue (MB) degradation under visible light, where the 10 wt% ZnFe₂O₃-ZIF-8 composite achieved 90% degradation efficiency, outperforming pristine ZIF-8 (67.8%). The catalyst also demonstrated excellent recyclability over five cycles and a proposed degradation mechanism involving ·OH and ·O₂⁻ radical formation. These findings demonstrate the potential of highly doped ZnFe₂O₃@ZIF-8 composites for environmental remediation and photonic applications. Full article

The gastrointestinal tract mediates the absorption of nutrients from the diet, which is increasingly contaminated with toxic metal(loid) species (TMs) and thus threatens food safety. Evidence in support of the influx of TMs into the bloodstream of the general and vulnerable populations (babies, children, pregnant women, and industrial workers) has been obtained by accurately quantifying their blood concentrations. The interpretation of these TM blood concentrations, however, is problematic, as we cannot distinguish between those that are tolerable from those that may cause the onset of environmental diseases. Since TMs that have invaded the bloodstream may perturb biochemical processes therein that will eventually cause organ damage it is crucial to better understand their bioinorganic chemistry as these processes collectively determine their organ availability. Thus, bioinorganic processes of TMs in the bloodstream represent selectivity filters which protect organs from their influx and ultimately determine the corresponding exposure-response relationships. The need to better understand selectivity filters prompted us to mechanistically disentangle them into the major bioinorganic chemistry processes. It is argued that the detoxification of TMs in the bloodstream and the biomolecular mechanisms, which mediate their uptake into target organs, represent critical knowledge gaps to revise regulatory frameworks to reduce the disease burden. Full article

This study assesses sediment toxicity in the historically contaminated Orbetello Lagoon (southern Tuscany) using Paracentrotus lividus embryo development bioassays. Elutriates from 15 sites were analysed for trace metals, organic matter, and ammonium. Despite elevated mercury concentrations, toxicity did not consistently correlate with metal levels. Instead, Principal Component Analysis (PCA) identified ammonium as a key driver of developmental toxicity, suggesting that it significantly influences both biological effects and metal bioavailability. These results demonstrate that ammonium, often overlooked, can confound sediment toxicity assessments and should be integrated into risk evaluation frameworks for coastal systems affected by legacy pollution. Full article

Direct air capture (DAC), as a complementary strategy to carbon capture and storage (CCS), offers a scalable and sustainable pathway to remove CO₂ directly from the ambient air. This study presents a detailed evaluation of the amine-functionalised metal-organic framework (MOF) sorbent, mmen-Mg₂(dobpdc), for DAC using a temperature–vacuum swing adsorption (TVSA) process. While this sorbent has demonstrated promising performance in point-source CO₂ capture, this is the first dynamic simulation-based study to rigorously assess its effectiveness for low-concentration atmospheric CO₂ removal. A transient one-dimensional TVSA model was developed in Aspen Adsorption and validated against experimental breakthrough data to ensure accuracy in capturing both the sharp and gradual adsorption kinetics. To enhance process efficiency and sustainability, this work provides a comprehensive parametric analysis of key operational factors, including air flow rate, temperature, adsorption/desorption durations, vacuum pressure, and heat exchanger temperature, on process performance, including CO₂ purity, recovery, productivity, and specific energy consumption. Under optimal conditions for this sorbent (vacuum pressure lower than 0.15 bar and feed temperature below 15 °C), the TVSA process achieved ~98% CO₂ purity, recovery over 70%, and specific energy consumption of about 3.5 MJ/KgCO₂. These findings demonstrate that mmen-Mg₂(dobpdc) can achieve performance comparable to benchmark DAC sorbents in terms of CO₂ purity and recovery, underscoring its potential for scalable DAC applications. This work advances the development of energy-efficient carbon removal technologies and highlights the value of step-shape isotherm adsorbents in supporting global carbon-neutrality goals. Full article

Luminescent metal–organic frameworks (MOFs) are used for the detection of organophosphorus pesticides (OPs) due to their large surface area and pore volume as well as their special optical properties. However, most self-luminescent MOFs are not only complex to synthesize and unstable in water but also feature a “turn-off” sensing system, which has highly restricted their practical applications in OP detection. Herein, a “turn-on” fluorescence sensor based on the guest-induced luminescence MOF Ru(bpy)₃²⁺@UiO-66 was constructed, which realized the sensitive detection of OPs through a dual-enzyme system for the first time. Compared with self-luminescent MOFs, Ru(bpy)₃²⁺@UiO-66 was not only more easily synthesized but also had higher chemical and photostability in water. In this strategy, by means of the hydrolysis of AChE and ChOx, H₂O₂ will be produced, which can oxidize Fe²⁺ to Fe³⁺, thereby quenching the fluorescence of Ru(bpy)₃²⁺@UiO-66. In the presence of OPs, the activity of AChE can be inhibited, resulting in the inability to generate H₂O₂ and Fe³⁺, which will turn on the fluorescence signal of Ru(bpy)₃²⁺@UiO-66. As a result, the Ru(bpy)₃²⁺@UiO-66 sensing system not only had high sensitivity for OPs detection but also possessed a satisfactory detection recovery rate for parathion-methyl in real samples, which provides a new approach for OP detection in food safety as well as environmental monitoring. Full article

Water scarcity poses a formidable challenge around the world, especially in arid regions where limited availability of freshwater resources threatens both human well-being and ecosystem sustainability. Membrane-based desalination technologies offer a viable solution to address this issue by providing access to clean water. This work ultimately aims to develop a novel permselective polymeric membrane material to be employed in an electrochemical desalination system. This part of the study addresses the optimization, preparation, and characterization of a polyvinylidene difluoride (PVDF) polymeric membrane using the electrospinning technique. The membranes produced in this work were fabricated under specific operational, environmental, and material parameters. Five different additives and nano-additives, i.e., graphene oxide (GO), carbon nanotubes (CNTs), zinc oxide (ZnO), activated carbon (AC), and a zeolitic imidazolate metal–organic framework (ZIF-8), were used to modify the functionality and selectivity of the prepared PVDF membranes. Each membrane was synthesized at two different levels of additive composition, i.e., 0.18 wt.% and 0.45 wt.% of the entire PVDF polymeric solution. The physiochemical properties of the prepared membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), zeta potential, contact angle, conductivity, porosity, and pore size distribution. Based on findings of this study, PVDF/GO membrane exhibited superior results, with an electrical conductivity of 5.611 mS/cm, an average pore size of 2.086 µm, and a surface charge of −38.33 mV. Full article

Recently, it has been found that electrochemical sensing technology is one of the significant approaches for the monitoring of toxic and hazardous substances in food and the environment. Nitrofurazone (NFZ) and nitrofurantoin (NFT) possess a hazardous influence on the environment, aquatic life, and human health. Thus, various advanced materials such as graphene, carbon nanotubes, metal oxides, MXenes, layered double hydroxides (LDHs), polymers, metal–organic frameworks (MOFs), metal-based composites, etc. are widely used for the development of nitrofurazone and nitrofurantoin sensors. This review article summarizes the progress in the fabrication of electrode materials for nitrofurazone and nitrofurantoin sensing applications. The performance of the various electrode materials for nitrofurazone and nitrofurantoin monitoring are discussed. Various electrochemical sensing techniques such as square wave voltammetry (SWV), differential pulse voltammetry (DPV), linear sweep voltammetry (LSV), amperometry (AMP), cyclic voltammetry (CV), and chronoamperometry (CA) are discussed for the determination of NFZ and NFT. It is observed that DPV, SWV, and AMP/CA are more sensitive techniques compared to LSV and CV. The challenges, future perspectives, and limitations of NFZ and NFT sensors are also discussed. It is believed that present article may be useful for electrochemists as well materials scientists who are working to design electrode materials for electrochemical sensing applications. Full article

The prosperity of enzyme-mimicking catalysis has promoted the development of nanozymes with diversified activities, mainly including catalase-like, oxidase-like, peroxidase-like, and superoxide dismutase-like characteristics. Thus far, the reported nanozymes can be roughly divided into five categories, comprising noble metals, metal oxides, carbon-based nanostructures, metal–organic frameworks, and covalent organic frameworks. This review systematically summarizes the research progress of nanozymes for improving catalytic activity toward sensing applications in food safety monitoring. Specifically, we highlight the unique advantages of nanozymes in enhancing the performance of colorimetric, fluorescence, and electrochemical sensors, which are crucial for detecting various food contaminants. Moreover, this review addresses the challenges faced in food safety detection, such as the need for high sensitivity, selectivity, and stability under complex food matrices. Nanozymes offer promising solutions by providing robust catalytic activity, adjustable enzyme-like properties, and excellent stability, even in harsh environments. However, practical implementation challenges remain, including the need for a deeper understanding of nanozyme catalytic mechanisms, improving substrate selectivity, and ensuring long-term stability and large-scale production. By focusing on these aspects, this review aims to provide a comprehensive overview of the current state of nanozyme-based sensors for food safety detection and to inspire future research directions. Full article

Aerogel sponges of bio-based polymers loaded with metal–organic frameworks (MOFs) are highly promising for environmental applications, but a central challenge is to improve their stability and efficiency for removal processes. Here, the effective incorporation of the MOFs MIL-100(Fe) and ZIF-8 in composite aerogels of chitosan–pectin–lactic acid is reported. The presence of pectin was critical to loading the MOFs efficiently and homogeneously, while the incorporation of lactic acid induced a large increase in the Young’s modulus and provided structural preservation in aqueous solutions. The presence of MOFs enhanced the removal of two dyes, methyl orange (MO) and methylene blue (MB), under batch and flow conditions, with removal efficiencies of methyl orange of about 85% and 90% when loaded with ZIF-8 and MIL-100(Fe), respectively. Bentonite, celite 545, and two ionenes were loaded for comparison. Factors beyond charge-to-charge electrostatic interactions influenced the removal, since no correlations were obtained between the electrical charges of dyes, fillers, and polymers. The kinetic data were analyzed by adapting the Langmuir kinetic model, incorporating absorption and desorption processes, which allowed the recovery of the respective rate constants. Full article

In this study, we systematically investigated the adsorption behavior of a titanium-based metal–organic framework (MOF) sensing layer on five primary alcohol homologs using the quartz crystal microbalance (QCM) technique. Unexpectedly, response signals were significantly enhanced for molecules exceeding the framework’s pore dimensions, contradicting conventional molecular sieving models. Further investigations revealed that the adsorption time constant (${\tau }_a$) is linearly proportional to the molecular diameter ($R^2=0.952$) and the integral response (AUC) increases almost exponentially with the molecular weight ($R^2=0.891$). Although the effective diffusion coefficient ($D_{\mathrm{eff}}$) decreases with increasing molecular size ($D_{\mathrm{eff}}\propto d^{-5.96}$, $R^2=0.981$), the normalized diffusion hindrance ratio ($D_{\mathrm{eff}}/D_{\mathrm{gas}}$) decreases logarithmically with an increasing diameter. Larger responses result from stronger host–guest interactions with the framework despite significant diffusion limitations for larger molecules. These findings demonstrate the synergistic regulation of adsorption and diffusion in MOF-QCM systems. Our investigation experimentally elucidates the ’size-selectivity paradox’ in microporous sensing interfaces and establishes a quantitative framework for optimizing sensor performance through balanced control of diffusion kinetics and interfacial interactions in similar materials. Full article

The rapid recombination of photoinduced charge carriers in semiconductors remains a significant challenge for their practical application in photocatalysis. This study presents the design of a step-scheme (S-scheme) heterojunction composed of carbon nitride (g-C₃N₄) and nickel-based metal–organic framework (Ni-MOF) to achieve enhanced charge separation. The establishment of an S-scheme charge transfer configuration at the interface of the Ni-MOF/g-C₃N₄ heterostructure plays a pivotal role in enabling efficient charge carrier separation, and hence, high CO₂ photoreduction efficiency with a CO evolution rate of 1014.6 µmol g⁻¹ h⁻¹ and selectivity of 95% under simulated solar illumination. CO evolution represents an approximately 3.7-fold enhancement compared to pristine Ni-MOF. Density functional theory (DFT) calculations, supported by in situ irradiated X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) experimental results, confirmed the establishment of a well-defined and strongly bonded interface, which improves the charge transfer and separation following the S-scheme mechanism. This study sheds light on MOF-based S-scheme heterojunctions as fruitful and selective alternatives for practical CO₂ photoreduction. Full article

Direct Air Capture (DAC) is emerging as a critical climate change mitigation strategy, offering a pathway to actively remove atmospheric CO₂. This comprehensive review synthesizes advancements in DAC technologies, with a particular emphasis on the pivotal role of nanostructured solid sorbent materials. The work critically evaluates the characteristics, performance, and limitations of key nanomaterial classes, including metal–organic frameworks (MOFs), covalent organic frameworks (COFs), zeolites, amine-functionalized polymers, porous carbons, and layered double hydroxides (LDHs), alongside solid-supported ionic liquids, highlighting their varied CO₂ uptake capacities, regeneration energy requirements, and crucial water sensitivities. Beyond traditional temperature/pressure swing adsorption, the review delves into innovative DAC methodologies such as Moisture Swing Adsorption (MSA), Electro Swing Adsorption (ESA), Passive DAC, and CO₂-Binding Organic Liquids (CO₂ BOLs), detailing their unique mechanisms and potential for reduced energy footprints. Despite significant progress, the widespread deployment of DAC faces formidable challenges, notably high capital and operational costs (currently USD 300–USD 1000/tCO₂), substantial energy demands (1500–2400 kWh/tCO₂), water interference, scalability hurdles, and sorbent degradation. Furthermore, this review comprehensively examines the burgeoning global DAC market, its diverse applications, and the critical socio-economic barriers to adoption, particularly in developing countries. A comparative analysis of DAC within the broader carbon removal landscape (e.g., CCS, BECCS, afforestation) is also provided, alongside an address to the essential, often overlooked, environmental considerations for the sustainable production, regeneration, and disposal of spent nanomaterials, including insights from Life Cycle Assessments. The nuanced techno-economic landscape has been thoroughly summarized, highlighting that commercial viability is a multi-faceted challenge involving material performance, synthesis cost, regeneration energy, scalability, and long-term stability. It has been reiterated that no single ‘best’ material exists, but rather a portfolio of technologies will be necessary, with the ultimate success dependent on system-level integration and the availability of low-carbon energy. The review paper contributes to a holistic understanding of cutting-edge DAC technologies, bridging material science innovations with real-world implementation challenges and opportunities, thereby identifying critical knowledge gaps and pathways toward a net-zero carbon future. Full article

The electrocatalytic CO₂ reduction reaction (CO₂RR) offers an energy-saving and environmentally friendly approach to producing hydrocarbon fuels. The use of a gas diffusion electrode (GDE) flow cell has generally improved the rate of CO₂RR, while the gas diffusion layer (GDL) remains a significant challenge. In this study, we successfully engineered a novel metal–organic framework (MOF) heterojunction through the controlled coating of zeolitic imidazolate framework (ZIF-L) on ultrathin nickel—metal–organic framework (Ni-MOF) nanosheets. This innovative architecture simultaneously integrates GDL functionality and exposes abundant solid–liquid–gas triple-phase boundaries. The resulting Ni-MOF@ZIF-L heterostructure demonstrates exceptional performance, achieving a formate Faradaic efficiency of 92.4% while suppressing the hydrogen evolution reaction (HER) to 6.7%. Through computational modeling of the optimized heterojunction configuration, we further elucidated its competitive adsorption behavior and electronic modulation effects. The experimental and theoretical results demonstrate an improvement in electrochemical CO₂ reduction activity with suppressed hydrogen evolution for the heterojunction because of its hydrophobic interface, good electron transfer capability, and high CO₂ adsorption at the catalyst interface. This work provides a new insight into the rational design of porous crystalline materials in electrocatalytic CO₂RR. Full article

The electrocatalytic decomposition of ammonia represents a promising route for sustainable hydrogen production, yet current systems rely heavily on noble metal catalysts with prohibitive costs and limited durability. A critical challenge lies in developing non-noble electrocatalysts that simultaneously achieve high active site exposure, optimized electronic configurations, and robust structural stability. Addressing these requirements, this study strategically engineered Cu-doped ZIF-8 architectures via in situ growth on nickel foam (NF) substrates through a facile room-temperature hydrothermal synthesis approach. Systematic optimization of the Cu/Zn molar ratio revealed that Cu_0.7Zn_0.3-ZIF/NF achieved optimal performance, exhibiting a distinctive nanoflower-like architecture that substantially increased accessible active sites. The hybrid catalyst demonstrated superior electrocatalytic performance with a current density of 124 mA cm⁻² at 1.6 V vs. RHE and a notably low Tafel slope of 30.94 mV dec⁻¹, outperforming both Zn-ZIF/NF (39.45 mV dec⁻¹) and Cu-ZIF/NF (31.39 mV dec⁻¹). Combined XPS and EDS analyses unveiled a synergistic electronic structure modulation between Zn and Cu, which facilitated charge transfer and enhanced catalytic efficiency. A gas chromatography product analysis identified H₂ and N₂ as the primary gaseous products, confirming the predominant occurrence of the ammonia oxidation reaction (AOR). This study not only presents a noble metal-free electrocatalyst with exceptional efficiency and durability for ammonia decomposition but also demonstrates the significant potential of MOF-derived materials in sustainable hydrogen production technologies. Full article