Zirconium-based Metal-organic Framework Research Articles

Portable foodborne pathogen detection via ratiometric fluorescence nanoprobe for adenosine triphosphate quantification based on DNA-functionalized metal-organic framework.

The increasing incidence of foodborne illnesses highlights the need for rapid, sensitive, and portable methods to detect pathogenic bacteria in food. In this work, we develop a portable method that utilizes a ratiometric fluorescence nanoprobe for adenosine triphosphate (ATP) quantification. The nanoprobe is constructed by encapsulating Ru(bpy)32+ within a zirconium-based metal-organic framework, followed by functionalization of double-stranded DNA (dsDNA). This design permits SYBR Green I (SGI) to intercalate into dsDNA, conferring the nanoprobe with dual-emission property. The presence of ATP disrupts dsDNA structure, quenching SGI fluorescence while maintaining Ru(bpy)32+ fluorescence, providing a stable reference signal. This differential response enables the nanoprobe to achieve ratiometric ATP detection with high precision and sensitivity, with a detection limit of 0.63 μM. Since ATP is a reliable biomarker for viable bacterial cells, a portable hydrogel kit was further developed by integrating the ratiometric fluorescence nanoprobe into an agarose hydrogel matrix. The validation of the kit was conducted using a smartphone application for color recognition, enabling the rapid and on-site detection of pathogens in milk samples. The kit exhibits exceptional sensitivity with a detection limit of 10 CFU/mL, making it a promising tool for real-time bacteria detection in food safety monitoring.

Zirconium-based metal–organic framework immobilized subtilisin for anti-biofilm

Biofilm formation contributes significantly to bacterial drug resistance, and employing enzymes to combat biofilms is an effective way. In this study, UiO-66-NH2 was synthesized to immobilize subtilisin, resulting in enzymatic anti-biofilm composite materials. The stability, biofilm inhibition capabilities, and biological safety of the composite materials were investigated. The results demonstrated that the immobilized proteases displayed significantly enhanced thermal and pH stability compared to free subtilisin. After 30 days of storage, the immobilized enzymes maintained around 66.8 % of their activity. Furthermore, it effectively suppressed biofilm formation by Staphylococcus aureus and Escherichia coli. Importantly, it does not induce hemolysis of red blood cells or exhibit cytotoxicity, demonstrating its favorable biocompatibility. This study provides novel light on the development of enzyme-based antibiofilm agents.

Dispersive solid phase extraction of apixaban from human plasma samples prior to capillary electrophoresis determination using zirconium-based metal organic frameworks prepared by different modulator and solvent

Dispersive solid phase extraction of apixaban from human plasma samples prior to capillary electrophoresis determination using zirconium-based metal organic frameworks prepared by different modulator and solvent

A highly efficient and recyclable zirconium-based metal organic framework for the effective removal of nanoplastics from multiple aqueous environments

A highly efficient and recyclable zirconium-based metal organic framework for the effective removal of nanoplastics from multiple aqueous environments

UiO-67 metal-organic framework loaded on hardwood biochar for sustainable management of environmental boron contaminations

Boron contamination in water poses significant potential risks to human health and the environment, necessitating the development of efficient, cost-effective, and sustainable remediation technologies. This study introduces a novel composite material combining a zirconium-based metal-organic framework (UiO-67) and a low-cost carbonaceous material (hardwood biochar, BC) with synergetic efficiency to address boron-polluted waters. The UiO-67-biochar (UBC) composite exhibits effective surface chemistry and a remarkably high specific surface area of approximately 881.9m²/g, substantially increasing from the 19.7m²/g of biochar. Our experimental results demonstrate that UBC removed up to 88.5% of boron from 20 ppm polluted water, achieving levels compliant with the WHO standards. The composite also showed excellent reusability, maintaining 95% efficiency over multiple cycles without loss of crystallinity. Life cycle assessment and cost analysis indicate that an optimal MOF to biochar ratio of approximately 60wt% minimises CO2 emissions and costs while maximising the boron removal efficiency. The UiO-67-biochar composites proposed here offers a promising scalable solution for boron contamination and potentially other environmental pollutants, combining the high functionality of UiO-67 with the practical and economic advantages of biochar.

Enhancing Biocatalysis: Metal-Organic Frameworks as Multifunctional Enzyme Hosts.

ConspectusEnzymes are highly efficient and selective catalysts that operate under mild conditions, making them invaluable for various chemical transformations. However, their limitations, such as instability and high cost, call for advancements in enzyme immobilization and the development of suitable host materials. Metal-organic frameworks (MOFs), characterized by high porosity, crystallinity, and tunability, are promising candidates for enzyme encapsulation. Among these, zirconium-based MOFs (Zr-MOFs) stand out due to their exceptional structural diversity and chemical stability. The physical and chemical properties of Zr-MOFs can be tuned and characterized with atomic precision, and their interactions with enzymes can be analyzed through a range of techniques spanning from chemistry and materials science to biochemistry. This tunable platform provides opportunities to systematically investigate the impact of encapsulation on the stability and activity of enzymes in order to develop design rules for enzyme hosts.In this Account, we discuss experimentally validated concepts for designing MOF hosts based on their structural properties and enzyme encapsulation mechanisms. We present methods to enhance enzyme catalytic performance through encapsulation and strategies for creating multifunctional enzyme@MOF systems via host modifications. We start by highlighting the importance of host structural design that maximizes substrate diffusion and enzyme availability, with particular focus on MOFs containing hierarchical mesoporous structures such as those in the csq topology. We then delve into the encapsulation process and host-guest interactions examined through techniques such as microscopy, calorimetry, and computational methods, which provide guidelines to fine-tune the local pore chemical environment to enhance enzyme stability and catalytic activity. Techniques found in biochemistry, such as isothermal titration calorimetry (ITC) and confocal laser scanning microscopy (CLSM), were developed to investigate enzyme encapsulation mechanisms, revealing high-entropy-driven host-guest affinity. Additionally, we discuss cases in which enzyme@MOF systems demonstrated enhanced catalytic activities and multifunctional capabilities. Encapsulated enzymes have demonstrated improved thermal and chemical stabilities compared to their free counterparts, maintaining activity under conditions that typically lead to denaturation. Additionally, the highly tunable nature of the MOF platforms allows them to support more complex systems such as tandem reactions, enabling applications in biophotocatalysis, bioelectrocatalysis, and targeted therapeutic protein delivery.The versatility of enzyme@MOFs promises extensive applications in both research and industrial processes across fields including biotechnology, pharmaceutical development, and environmental science. We provide an outlook for promising directions for enzyme@MOF research, with the aim of continuing innovation and exploration. We hope that this Account can benefit chemists, biologists, and material scientists toward designing efficient and adaptable next-generation biocatalytic composite materials.

Zr-MOF composites with zipped and unzipped carbon nanotubes for high-performance electrochemical supercapacitors.

Metal-organic frameworks (MOFs) have gained considerable interest as crystalline porous materials with notable characteristics, such as high surface area and excellent electrochemical performance, particularly in supercapacitor applications. The combination of MOFs with various nanocarbon materials further enhances their performance. This study investigated the combination of zirconium-based MOFs (Zr-MOFs) with graphene oxide nanoribbons (GONRs), zipped carbon nanotubes, and functionalized carbon nanotubes (FCNTs) to fabricate composites with elevated electrical conductivity, adjustable surface area, chemical robustness, mechanical strength, and customizable attributes for specific applications. Zr-MOFs exhibit remarkable capacitance, making them promising electrode materials for supercapacitors. GONRs and FCNTs have recently emerged as focal materials owing to their unique properties, which make them promising materials for electrochemical energy storage devices. A thorough investigation of the supercapacitive behavior of GONRs, FCNTs, Zr-MOFs, Zr-MOFs/FCNTs, and Zr-MOFs/GONRs in 1 M H2SO4 using different evaluation systems (three- and two-electrode systems) revealed a significant enhancement in the capacitance of Zr-MOFs after the introduction of GONRs and FCNTs. Employing Zr-MOF/GONR and Zr-MOF/FCNT composites as positive electrodes and GONRs as negative electrodes in two-electrode measurements demonstrated remarkable cycling stability by retaining their specific capacitances (Cs) even after 10 000 consecutive charge/discharge cycles at a high current density of 10 A g-1. Moreover, they feature a broad potential window of 1.7 V in the three-electrode system. This extends to 2 V in the two-electrode system, achieving high Cs. This highlights the remarkable electrochemical performance of the Zr-MOF/GONR and Zr-MOF/FCNT composites, offering a compelling approach for energy storage applications.

Fluoride Product Inhibition: New Insight into the Degradation of Nerve Agents by Zr-MOFs.

Zirconium-based metal-organic frameworks (Zr-MOFs) have shown remarkable efficacy in catalytically degrading neurotoxic agents in recent years. However, the catalytic activity of Zr-MOFs can be inhibited due to the binding of phosphate degradation products to the Zr nodes. Here, we reported the inhibition effect of a nonphosphate substance, fluoride, which can deactivate Zr-MOF nodes for the degradation of GD and VX and simulate DEPPT. The experimental and theoretical calculation results reveal that the fluoride product during GD degradation shows much more significant suppression than phosphate. The phosphate products can depart from the Zr nodes completely by adding H2O molecules on the Zr nodes to reduce the energy barrier. However, the fluoride can replace the bridged μ3-OH groups and terminal -OH groups on Zr-oxo clusters irreversibly, changing the electric density of Zr nodes and eliminating the terminal -OH. Without the terminal -OH, the five-coordinate phosphorus intermediate cannot be formed, resulting in the inactivation of Zr-O-Zr sites. This study provides new insights into Zr-MOF catalyst deactivation mechanisms and may help to develop a new strategy to design MOFs with high anti-inhibition efficiency for the degradation of nerve agents.

Water motifs in zirconium metal-organic frameworks induced by nanoconfinement and hydrophilic adsorption sites

The intricate hydrogen-bonded network of water gives rise to various structures with anomalous properties at different thermodynamic conditions. Nanoconfinement can further modify the water structure and properties, and induce specific water motifs, which are instrumental for technological applications such as atmospheric water harvesting. However, so far, a causal relationship between nanoconfinement and the presence of specific hydrophilic adsorption sites is lacking, hampering the further design of nanostructured materials for water templating. Therefore, this work investigates the organisation of water in zirconium-based metal-organic frameworks (MOFs) with varying topologies, pore sizes, and chemical composition, to extract design rules to shape water. The highly tuneable pores and hydrophilicity of MOFs makes them ideally suited for this purpose. We find that small nanopores favour orderly water clusters that nucleate at hydrophilic adsorption sites. Favourably positioning the secondary adsorption sites, hydrogen-bonded to the primary adsorption sites, allows larger clusters to form at moderate adsorption conditions. To disentangle the importance of nanoconfinement and hydrophilic nucleation sites in this process, we introduce an analytical model with precise control of the adsorption sites. This sheds a new light on design parameters to induce specific water clusters and hydrogen-bonded networks, thus rationalising the application space of water in nanoconfinement.

Synthesis of zirconium-based metal-organic framework under mild conditions and its application to the removal of cationic and anionic dyes from wastewater

Water resources contaminated by industrial dyes can pose a significant threat to the environment and human health. Herein, we conducted a study on the removal of cationic and anionic dyes, such as methylene blue (MB) and methyl orange (MO), using MIL-140A, a zirconium-based metal-organic framework. MIL-140A is synthesized in a Schlenk flask at 120 °C, whereas its conventional synthesis route involves a teflon-sealed autoclave at 220 °C, highlighting the cost reduction and lower equipment requirements of the low-temperature synthesis. The structure of MIL-140A is characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscope (SEM), and nitrogen adsorption techniques. The optimal pH for the adsorption of two dyes by MIL-140A is pH 5–8 for MB and pH 3 for MO. The adsorption equilibrium can be reached within 60 min at room temperature, and the adsorption of both dyes on MIL-140A follows pseudo-second-order kinetics and Langmuir isotherm, and the maximum adsorption capacity of MO and MB by MIL-140A were 163.6 and 89.2 mg/g, respectively. Thermodynamic studies indicate an entropy-driven spontaneous process. The adsorption mechanism of MO and MB on MIL-140A is investigated using FT-IR and X-ray photoelectron spectroscopy. The adsorption of MO involves coordination between Zr and sulfonate, while MB adsorption occurs via π-π interactions. Additionally, MIL-140A exhibits better removal efficiency for MO from lithium battery wastewater compared to MB, primarily due to stronger coordination interactions than π-π interactions. These findings demonstrate that MIL-140A is a promising adsorbent for effectively removing both anionic and cationic dyes from water resources.

Fine-Tuning Porous Structure of Zirconium-Based Metal-Organic Frameworks for Efficient Separation and Purification of Astaxanthin by Defect Engineering.

Efficient separation of bioactive compounds from nature source, particularly that of astaxanthin (AXT), remains challenging due to their low content in complicated matrix and readily degradable structure. Herein, a modulator-induced defect engineering is presented on the stable zirconium-based metal-organic frameworks (Zr-MOFs) to optimize pore size and pore chemistry for the efficient separation and purification of AXT for the first time. High adsorption capacity of 26.21mgg-1 is achieved on the best-performing defect Zr-MOF (d-UiO-67-4), superior over the other reported adsorbent for AXT. Meanwhile, d-UiO-67-4 exhibits the selective adsorption of AXT over other carotenoids analogues with similar structure and properties. This is attributed to the preferential non-covalent interactions between defect framework and AXT revealed by the spectroscopy analysis and density functional theory (DFT) calculations. High purity of AXT with 89.0%±2.3% extraction efficiency can be realized after the purification of AXT by d-UiO-67-4. The practical separation performance of d-UiO-67-4 for AXT extracted from Haematococcus pluvialis is demonstrated by fixed-bed column-based dynamic adsorption and desorption experiments. This work broadens the preparation methods for thermosensitive active substances and provided new research ideas for the controlled adsorption of functional food factors.

Engineering Ion Affinity of Zr-MOF Hybrid PDMS Membranes for the Selective Separation of Na+/Ca2.

Ion-selective separation, especially Na+/Ca2+ separation, is of significant importance in the realms of biomimetic research and the fabrication of biomimetic devices, underscoring the pivotal role that sodium and calcium ions play in cellular metabolism. However, the analogous ionic radii and charge densities shared by sodium and calcium ions significantly impede their effective discrimination, presenting formidable challenges for the precise engineering of ion separation materials, such as separation membranes. In this study, a polydimethylsiloxane (PDMS) separation membrane hybridized with zirconium-based metal-organic frameworks (UiO-66, UiO-66-NO2 and UiO-66-NH2) was constructed. Through the meticulous design of the MOF functional groups, the material's affinity for specific ions was modulated, thereby achieving efficient Na+/Ca2+ separation. Notably, the PDMS integrated with amino-modified Zr-MOF exhibited an efficacious selective separation of Na+ and Ca2+ ions. The interaction between the amino group of UiO-66-NH2 and Ca2+ gave rise to the observed superior selectivity toward Ca2+ cations and enhanced separation efficiencies of up to 64% compared to pristine PDMS for UiO-66-NH2-embedded membranes.

Unexpected Photodriven Linker-to-Node Hole Transfer in a Zirconium-Based Metal-Organic Framework.

Zr6(μ3-O)4(μ3-OH)4 node cores are indispensable building blocks for almost all zirconium-based metal-organic frameworks. Consistent with the insulating nature of zirconia, they are generally considered electronically inert. Contrasting this viewpoint, we present spectral measurements and calculations indicating that emission from photoexcited NU-601, a six-connected Zr-based MOF, comes from both linker-centric locally excited and linker-to-node charge-transfer (CT) states. The CT state originates from a hole transfer process enabled by favorable energy alignment of the HOMOs of the node and linker. This alignment can be manipulated by changing the pH of the medium, which alters the protonation state of multiple oxy groups on the Zr-node. Thus, the acid-base chemistry of the node has a direct effect on the photophysics of the MOF following linker-localized electronic excitation. These new findings open opportunities to understand and exploit, for energy conversion, unconventional mechanisms of exciton formation and transport in MOFs.

Incorporation of Zirconium-Based Metal-Organic Framework on Kaolin for Boosting Rhodamine-B Adsorption

This research was focused on the use of a zirconium-based metal-organic framework (UiO-66) supported kaolin composite (UiO-66@kaolin) for rhodamine-b (RB) adsorption. The proposed composite was prepared via solvothermal method, and the functional groups were characterized by FT-IR analysis. The adsorption performances of kaolin and UiO-66@kaolin were compared by equilibrium experiments and the maximum monolayer adsorption capacities calculated from the Langmuir model were found to be 2.10 mg g⁻¹ and 17.22 mg g⁻¹, respectively. It was observed that the adsorption capacity of pristine kaolin was significantly increased by UiO-66 support. Besides, kaolin mineral was fitted to the monolayer Langmuir isotherm model, while the isotherm character of the composite adsorbent was described by the multilayer model Freundlich. The equilibrium time for UiO-66@kaolin was obtained as 240 min and the adsorption process was identified to occur via chemisorption with pseudo-second-order model fitting. It was observed that RB removal rate decreased with decreasing pH and solution pH had a major effect on adsorption. The parameters gathered from thermodynamic data demonstrated that RB adsorption was exothermic and spontaneous. The effective removal of RB dye from wastewater systems using the prepared UiO-66@kaolin composite adsorbent was confirmed by extensive adsorption studies. The reported findings may inspire further potential investigations.

Sulfonate-Functionalized Metal-Organic Framework as a Porous "Proton Reservoir" for Boosting Electrochemical Reduction of Nitrate to Ammonia.

The electrochemical reduction reaction of nitrate (NO3RR) is an attractive route to produce ammonia at ambient conditions, but the conversion from nitrate to ammonia, which requires nine protons, has to compete with both the two-proton process of nitrite formation and the hydrogen evolution reaction. Extensive research efforts have thus been made in recent studies to develop electrocatalysts for the NO3RR facilitating the production of ammonia. Rather than designing another better electrocatalyst, herein, we synthesize an electrochemically inactive, porous, and chemically robust zirconium-based metal-organic framework (MOF) with enriched intraframework sulfonate groups, SO3-MOF-808, as a coating deposited on top of the catalytically active copper-based electrode. Although both the overall reaction rate and electrochemically active surface area of the electrode are barely affected by the MOF coating, with negatively charged sulfonate groups capable of enriching more protons near the electrode surface, the MOF coating significantly promotes the selectivity of the NO3RR toward the production of ammonia. In contrast, the use of MOF coating with positively charged trimethylammonium groups to repulse protons strongly facilitates the conversion of nitrate to nitrite, with selectivity of more than 90% at all potentials. Under the optimal operating conditions, the copper electrocatalyst with SO3-MOF-808 coating can achieve a Faradaic efficiency of 87.5% for ammonia production, a nitrate-to-ammonia selectivity of 95.6%, and an ammonia production rate of 97 μmol/cm2 h, outperforming all of those achieved by both the pristine copper (75.0%; 93.9%; 87 μmol/cm2 h) and copper with optimized Nafion coating (83.3%; 86.9%; 64 μmol/cm2 h). Findings here suggest the function of MOF as an advanced alternative to the commercially available Nafion to enrich protons near the surface of electrocatalyst for NO3RR, and shed light on the potential of utilizing such electrochemically inactive MOF coatings in a range of proton-coupled electrocatalytic reactions.

Modeling and optimization of adsorption behavior of lactic acid onto zirconium-based metal-organic framework: response surface methodology (RSM)

ABSTRACT Lactic acid is readily generated in bacterial fermentations; however, a significant amount of processing and expenses are required for the purification of lactic acid in the fermentation broth. In this work, the sorption of lactic acid from a simulated broth has been studied by utilizing zirconium-based metal-organic framework (Zr-UiO-66 MOF) that acts as a prominent adsorbent due to its specific geometries and functional groups. The morphological, and structural properties of the prepared MOF are investigated using different characterization techniques such as Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) pattern, Fourier transform infrared (FTIR) analysis, and Brunauer-Emmett-Teller (BET) analysis. The characterization results demonstrate the accuracy of the synthesis procedure. In order to achieve an efficient lactic acid separation process, it is essential to determine the optimal operational conditions. To address this, response surface methodology (RSM) was employed to devise an approach for optimizing five crucial process parameters for achieving the optimal response in lactic acid recovery removal. These parameters include initial LA concentration (ranging from 1 to 36 mg.L−1), pH (3–10), temperature (25 to 55 °C), adsorbent mass (0.25 to 1 g), and contact time (10 to 240 min). The RSM analysis revealed that the quadratic model provided the best fit for the experimental data, with a high coefficient of determination (R2). Three validation trials were carried out to determine the precision of the optimization process, leading to a maximum adsorption efficiency of 97.7% being reached under the optimized conditions (initial concentration = 18.5 mg.L−1, pH = 6.5, adsorbent mass = 0.625 g, contact time = 240 min, and temperature = 40 °C).

Slippery Liquid-Infused Porous Surfaces Containing UiO-66 Incorporated with 8-Hydroxyquinoline for Excellent Corrosion Protection of AZ31 Mg Alloys.

The conventional slippery liquid-infused porous surfaces (SLIPSs) provide relatively limited corrosion protection and self-healing performance for AZ31 Mg alloys. To this end, 8-hydroxyquinoline (8-HQ) was incorporated into a zirconium-based metal-organic framework UiO-66 through coordination (8-HQ@UiO-66), which was then dispersed into silicone oil to fabricate nanoparticle-enhanced-SLIPSs (8-HQ@UiO-66-SLIPSs). Especially, the influences of 8-HQ@UiO-66 concentration on the surface morphology, surface hydrophobicity, and corrosion resistance were studied. It was found that the surface hydrophobicity first increased and then decreased with increasing concentration, showing the highest water contact angle of 121.2° at a concentration of 1 mg mL-1 (8-HQ@UiO-66-SLIPS-1). This was attributed to the development of well-constructed hierarchical micro/nanostructures. Moreover, it also exhibited the best anticorrosion property, with the lowest corrosion current density of 1.24 × 10-10 A cm-2 and the highest impedance modulus of 9.88 × 108 Ω cm2 at 0.01 Hz, primarily associated with the synergistic interaction of 8-HQ and UiO-66. Further, the self-healing performance was evaluated using the scanning vibration electrode technique (SVET), verifying the superior self-healing performance of 8-HQ@UiO-66-SLIPS-1. Hence, the nanoparticle-enhanced-SLIPSs exhibit considerable potential in the corrosion protection of Mg alloys, thereby accelerating their extensive applications in industry.

Computational Analysis of Sarin, Soman, and Their Water Mixtures in NU-1000: Interaction Mechanisms, Distribution Patterns, and Pairing Effects.

Due to their extraordinary structural stability under humid conditions, zirconium-based metal-organic frameworks (Zr-MOFs) have been widely investigated for the hydrolytic degradation of nerve agents. That said, mechanisms of hydrolysis in the solid state and the participation of environmental water are not well understood. This work utilizes computational techniques to evaluate the behavior of water and two organophosphorus nerve agents (sarin and soman) in NU-1000, a Zr-MOF with the characteristic attributes for hydrolytic efficiency under humid conditions. Density functional theory (DFT) calculations reveal that soman binds more favorably to NU-1000 active sites than sarin, resulting in different preferential locations of each nerve agent within the framework. The strength of nerve agent binding is also found to vary depending on the site environment, with more favorable binding of both nerve agents occurring in the c-pores of NU-1000 than in the mesopores. Molecular dynamics (MD) simulation results further illustrate that free water molecules in NU-1000 prioritize interactions with nerve agents. Given the variation in their affinity for active site interactions, the introduction of different nerve agents to the framework results in substantial differences in water distribution and behavior. The results give insight into potential variances in the functionality of NU-1000 toward the hydrolysis of each nerve agent. More importantly, they emphasize the significance of considering the role of environmental water in hydrolysis and the possibility of diverse reaction variables based on the type of nerve agent and the properties of the MOF.

Zr-MOF-based substrate with inherent internal standards facilitates reliable SERS analysis of sulfonamide antibiotics

A multifunctional structure comprising gold nanoparticles immobilized within a zirconium-based metal-organic framework (AuNPs/Zr-MOF) was systematically designed. With the capabilities of analyte enrichment, Raman signal enhancement and internal standard calibration, the as-prepared AuNPs/Zr-MOF substrates demonstrate the outstanding SERS sensing performance toward the representative sulfonamide antibiotics (SAs), sulfadiazine, sulfamerazine, sulfamethazine and sulfaquinoxaline. For the first time, these four SAs are detected by SERS in real honey samples at levels of 2.8 ∼ 5.2 ng·g−1 within 10 min. The extensive π-bond conjugated system of Zr-MOF significantly enhances the concentration of SAs through π-π interactions. The entrapped SAs are adsorbed perpendicularly onto the surface of Au via coordinated interactions between Au and two oxygen atoms, or between Au and the terminal amino group. To achieve reliable quantitative analysis, the inherent vibration of the Zr-MOF structure was used as an internal standard label. Combined with a simple clean-up protocol, the established SERE sensing method is superior to conventional methods in terms of time, while achieving the impressive sensitivity. This study presents a robust SERS-based approach for the rapid detection and monitoring of multiple analytes.

Separation of molybdenum and tungsten using selective adsorption with zirconium based metal organic framework

BackgroundThe separation of tungsten and molybdenum has always been a significant challenge. Metal organic frameworks (MOFs) has potential to solve the problem. In this study, the adsorption and separation performance of UiO-66 for tungsten and molybdenum and adsorption mechanism were investigated. MethodsUiO-66 was synthesized by solvothermal method. The physical and chemical properties of UiO-66 and adsorption mechanism were characterized and analyzed by XRD, SEM-EDS, FT-IR, Zeta-potential, XPS and thermodynamic analysis, the adsorption and separation performance of Mo/W using UiO-66 were evaluated by ICP-OES. Significant findingsUiO-66 with uniform pore size could be obtained under the conditions of crystallization for 24 h at 180 °C. This study revealed superior Mo/W separation performance under acidic conditions, where the adsorption capacity for Mo (QMo) of UiO-66 was 219.4 mg⋅g−1 and the highest separation factor (βMo/W) was 52.3. It was found that the mechanism involved the effect of pore size, electrostatic attraction and the metal point Zr had stronger affinity for Mo. This material was expected to serve as an eco-friendly and reusable adsorbent for separation of tungsten and molybdenum in resource recovery, aiming for high-quality regeneration of both metals.