Search Results (38)

The conversion of alkanes/alkenes into useful intermediates is highly important in the chemical industry. In this study, the physicochemical properties and catalytically active forms of bismuth molybdates (BiMo) were investigated using the selective oxidation of propene to acrolein as a model reaction. The catalysts were prepared by two methods, coprecipitation and spray-drying, with emphasis on spray-drying. The catalysts were characterized using X-ray diffraction, N₂ adsorption/desorption isotherms, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The catalytic properties of the BiMo samples were studied in a conventional fixed-bed reactor operated under different reaction conditions. The one-dimensional (1D) pseudohomogeneous model was applied to describe the obtained experimental results. The experimental kinetic data were correlated with two complex kinetic models based on multiple reactions (parallel and serial reaction systems). The proposed models were verified by comparing computer simulation data with experimental laboratory results. This study aimed to extend the understanding of the relationship between catalyst composition/structure and catalyst activity/selectivity for different BiMo structures, and to propose kinetic models using two approaches based on parallel and series reactions, in line with efforts to improve the valorization of light olefins. Full article

The limited availability of phosphorus (P) in soil poses a critical constraint on agricultural productivity, and sustainable P fertilization practices are of great importance for crop production. In this study, we developed a novel dual-function granular material (RMG) derived from red mud, a waste residue from the aluminum industry. This material is capable of adsorbing P in P-rich soils and releasing P in P-deficient soils, thereby enabling the sustainable use of red mud and P fertilizer. The influences of RMG on the migration and transformation of P in soil were investigated. Application of RMG significantly increased the critical threshold for P leaching, thereby effectively mitigating P loss. In the initial stage of leaching, P in the leachate was present predominantly as particulate phosphorus, whereas molybdate-reactive P became the dominant form in later stages. With increasing RMG dosage, the pH of the leachate rose while the total phosphorus concentration declined, indicating that alkaline components in RMG promoted the adsorption and precipitation of phosphates in soil. The release behavior of P from P-enriched RMG was also examined. The results showed that the total soil P content increased progressively with higher RMG dosage and longer cultivation duration. Elevated temperature and soil moisture content were found to enhance the release and migration of P from RMG into the soil. SEM-EDS analyses revealed that released components (e.g., Ca²⁺ and Fe³⁺) from RMG formed relatively stable complexes with free phosphates. Moreover, adsorption of P onto the RMG surface further facilitated its migration and transformation within the soil. The research findings provide valuable insights for the simultaneous pollution remediation and resource utilization of red mud and phosphorus. Full article

Drying is ubiquitous. However, its influence on surface speciation has been seldom studied. Through an in situ Attenuated Total Reflection–Infrared (ATR-IR) spectroscopy analysis of the drying of molybdate solutions on a lepidocrocite particle film, the change in surface speciation is followed. No formation polymolybdates nor precipitate are observed upon drying at pH 8. An in situ washing of the dried solid/solution interface unveils the existence of surface outer-sphere and inner-sphere complexes. Decreasing the molybdate concentration highlights a saturation effect of the surface upon drying. Moreover, the careful analysis of substrate IR bands showed non-uniform drying which is an important insight to understand dehydration chemistry. The remaining molybdate ions at the surface as inner-sphere complexes are present as binuclear monodentate complexes stabilized by sodium. Full article

With the rapid development of flexible electronic skin materials, the demand for ion-conductive hydrogels is constantly growing. Specifically, these ion-conductive hydrogels are required to simultaneously exhibit excellent mechanical properties, high conductivity, and multifunctionality. Moreover, this performance requirement needs to be met in complex environments. However, the rapid production of hydrogels that combine high conductivity and photochromic properties remains a major challenge. In this study, a simple one-pot method was employed to successfully prepare multifunctional photochromic hydrogels by incorporating ammonium molybdate (Mo₇) and lithium chloride (LiCl) into a dual-network hydrogel composed of polyacrylamide (PAAm) and sodium alginate (SA). PAAm/SA/Mo₇/LiCl (PSML) hydrogels exhibit excellent comprehensive performance, including superior conductivity (average value of 164 S/cm), rapid UV response time (<20 s), good color-changing reversibility, outstanding high stretchability (peak value of 2800%), and high transparency (>70%). The design ingeniously combines two types of synergistic effects: the synergistic effect of the dual-network structure and that of the multifunctional component functional additives (Mo₇, LiCl). Specifically, the PSML hydrogel integrates photochromic properties, excellent mechanical properties, good anti-freezing properties, and 3D printability through this design. Due to these outstanding properties, the PSML hydrogel shows broad application prospects in fields such as flexible strain sensors, information storage, and encryption devices. Full article

Molybdenum (Mo) is a critical industrial metal valued for its corrosion resistance and strength-enhancing properties. However, increasing demand necessitates more efficient and sustainable recovery methods. Bio-recovery of Mo by biosorption is a promising resolution, especially by the use of surface-engineered microbes that express metal binding proteins on its cell surface. This study investigates the potential of Saccharomyces cerevisiae strain ScBp6, which displays a molybdate-binding protein (ModE) on its cell surface, immobilized on porous materials. Our findings reveal that polyurethane sponges (PS) significantly outperform ceramic materials in yeast immobilization, entrapping 1.76 × 10⁷ cells per sponge compared to 1.70 × 10⁶ cells per ceramic cube. Furthermore, the yeast–PS complex demonstrated superior Mo adsorption, reaching 2.16 pg Mo per yeast cell under 10 ppm Mo conditions, comparable to free yeast cells (1.96 pg Mo per yeast cell). These results establish PS as an effective and scalable platform for Mo recovery, offering high biosorption efficiency, reusability, and potential for industrial wastewater treatment applications. Full article

The elimination of absorbance of excess dye by selective oxidation was first proposed for analytical methods using the formation of ion-association complexes (IAs). On this basis, a new sensitive and selective spectrophotometric method for the determination of phosphate in the form of the IA of 11-molybdovanadophosphate with diindodicarbocyanine (DIDC) was developed. Symmetric diindodicarbocyanine and diindotricarbocyanine dyes can be completely oxidized by sufficiently strong oxidizing agents such as permanganate, dichromate, cerium (IV), and vanadate. Of the three dyes investigated (DIDC, N,N’-dipropyldiindodicarbocyanine, and diindotricarbocyanine), the best results were obtained with DIDC. A mixture of molybdate, vanadate, and nitric acid was preferably used as an oxidizing agent. Selective decolorization of only free dye ions, as well as changes in the IA spectrum compared to the dye spectrum, were explained by the isolation of the dye due to the formation of poorly soluble IA nanoparticles and changes in the redox potential of the dye due to its aggregation. The following optimal conditions for phosphate determination were found: 0.3 M nitric acid, 0.43 mM sodium molybdate, 0.041 mM sodium vanadate, 0.015 mM DIDC, and 18 min for the reaction time. The molar absorptivity of the IA was 1.86 × 10⁵ mol⁻¹·L·cm⁻¹ at 600 nm, and the detection limit for phosphate was 0.013 µM. The developed method was applied to the determination of phosphate in natural water samples. Full article

The adoption of chrome-free anodizing and sealing systems for aluminum alloys, particularly AA2024, is gaining prominence due to environmental and health concerns associated with traditional Cr(VI)-based processes. This study evaluates the environmental and economic impacts of sulfuric acid anodizing (SAA) combined with sealing based on fluorozirconate, molybdate, and cerate. Comparative analyses were conducted against conventional Cr(VI) systems and SAA with Cr(III) sealing, focusing on corrosion resistance, energy consumption, washing steps and material flows. The entire anodizing process was examined, including pretreatment, anodization, and sealing. Electrochemical analyses and surface characterization through SEM/EDS, FIB, and XPS were conducted. The results demonstrate that the chromium-free system offers competitive corrosion resistance while significantly reducing environmental and economic costs. Furthermore, fluorozirconate, molybdate, and cerate-based post-treatments broaden its application spectrum in corrosion science and warrant further exploration. However, adopting new sealing technologies in aerospace requires extensive certification involving corrosion resistance, durability assessments, and stringent environmental simulations. Compliance with regulatory standards set by the FAA (Federal Aviation Administration) and EASA (European Union Aviation Safety Agency) necessitates thorough documentation, third-party validation, and testing to ensure safety and performance before industrial implementation. These challenges underscore the complexity of transitioning to more sustainable anodizing and sealing technologies in the aerospace industry. Full article

Lanthanide molybdates are materials known for their mixed proton–ionic conductivity. This study investigates the effects of Pr content and Nb-doping on the crystal structure and electrical properties of the La_5.4−xPr_xMo_1−yNb_yO_12−δ (x = 0, 1.35, 2.7, 4.05, 5.4; y = 0, 0.1) series. The research focuses on two primary objectives: (i) enhancing the electronic conductivity through the use of Pr⁴⁺/Pr³⁺ redox pairs and (ii) increasing the ionic conductivity through Nb⁵⁺ aliovalent doping. The materials were thoroughly characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission and scanning electron microscopy (TEM and SEM), and complex impedance spectroscopy. The average crystal structure of the materials depended significantly on the Pr content. In general, compositions with a higher Pr content crystallize in a cubic fluorite-type structure, whereas those with a lower Pr content stabilize a rhombohedral polymorph. However, detailed TEM studies reveal a more complex local crystal structure characterized by nanodomains and incommensurate modulations. The highest conductivity values were observed in a N₂ atmosphere for compositions with an elevated Pr content, with values of 0.17 and 204.4 mS cm⁻¹ for x = 0 and x = 5.4, respectively, at 700 °C, which is attributed to electronic conduction mediated by the Pr⁴⁺/Pr³⁺ redox pair, as confirmed by XPS. These findings highlight the potential of tailored doping strategies to optimize the conducting properties of lanthanide molybdates for specific high-temperature electrochemical applications. Full article

Functionalized nanomaterials with surface-active groups have garnered significant research interest due to their wide-ranging applications, particularly in water treatment for removing various contaminants. This study focuses on developing a novel, multi-functional nanobiosorbent by synthesizing nanosized biochar from artichoke leaves (NBAL) and molybdic acid (MA). The resulting nanobiosorbent, MA@NBAL, is produced through a microwave-irradiation process, offering a promising material for enhanced environmental remediation. The characteristics of assembled MA@NBAL were evaluated from SEM-EDX, XPS, TGA, FT-IR, and zeta potential detection. The size of particles ranged from 18.7 to 23.7 nm. At the same time, the EDX analysis denoted the existence of several major elements with related percentage values of carbon (52.9%), oxygen (27.6%), molybdenum (8.8%), and nitrogen (4.5%) in the assembled MA@NBAL nanobiosorbent. The effectiveness of MA@NBAL in removing Hg(II) ions was monitored via the batch study method. The optimized maximum removal capacity of Hg(II) ions onto MA@NBAL was established at pH 6.0, 30.0 min equilibrium time, and 20 mg of nanobiosorbent, providing 1444.25 mg/g with a 10.0 mmol/L concentration of Hg(II). Kinetic studies revealed that the adsorption process followed a pseudo-second-order model, with R² values ranging from 0.993 to 0.999 for the two tested Hg(II) concentrations, indicating excellent alignment with the experimental data. This suggests that the chemisorption mechanism involves cation exchange and complex formation. Isotherm model evaluation further confirmed the adsorption mechanism, with the Freundlich model providing the best fit, yielding an R² of 0.962. This result indicates that Hg(II) adsorption onto the surface of MA@NBAL nanobiosorbent occurs on a heterogeneous surface with multilayer formation characteristics. The results of the temperature factor and computation of the thermodynamic parameters referred to endothermic behavior via a nonspontaneous process. Finally, the valid applicability of MA@NBAL nanobiosorbent in the adsorptive recovery of 2.0 and 5.0 µg/mL Hg(II) from contaminated real aquatic matrices was explored in this study, providing 91.2–98.6% removal efficiency. Full article

Efficiently treating wastewater, particularly the elimination of heavy metal ions from water systems, continues to be one of the most pressing and complex challenges in modern environmental management. In this work, reduced graphene oxide coupled silver molybdate binary nanocomposites (RGO-Ag₂MoO₄ NCs) have been prepared via hydrothermal method. The crystalline nature and surface properties of the developed RGO-Ag₂MoO₄ NCs were proved by XRD, FTIR, SEM, and EDS techniques. Adsorption experiments demonstrated that the nanocomposites (NCs) effectively removed Pb(II) ions within 120 min, achieving a maximum removal efficiency ranging from 94.96% to 86.37% for Pb(II) concentrations between 20 and 100 mg/L at pH 6. Kinetic studies showed that the adsorption process followed a pseudo-second order model. Isotherm analysis presented that the Langmuir model provided the greatest fit for the equilibrium data, with a monolayer adsorption capacity of 128.94 mg/g. Thermodynamic analysis revealed that the adsorption process was spontaneous and endothermic. The results of this study highlight RGO-Ag₂MoO₄ NCs as a highly promising and eco-friendly material for the effective elimination of Pb(II) ions from wastewater. Their strong adsorption capacity, coupled with sustainable properties, makes them an efficient solution for addressing lead contamination, offering significant potential for practical applications in water treatment systems. Full article

The global demand for sustainable energy sources has led to extensive research regarding (green) hydrogen production technologies, with water splitting emerging as a promising avenue. In the near future the calculated hydrogen demand is expected to be 2.3 Gt per year. For green hydrogen production, 1.5 ppm of Earth’s freshwater, or 30 ppb of saltwater, is required each year, which is less than that currently consumed by fossil fuel-based energy. Functional ceramics, known for their stability and tunable properties, have garnered attention in the field of water splitting. This review provides an in-depth analysis of recent advancements in functional ceramics for water splitting, addressing key mechanisms, challenges, and prospects. Theoretical aspects, including electronic structure and crystallography, are explored to understand the catalytic behavior of these materials. Hematite photoanodes, vital for solar-driven water splitting, are discussed alongside strategies to enhance their performance, such as heterojunction structures and cocatalyst integration. Compositionally complex perovskite oxides and high-entropy alloys/ceramics are investigated for their potential for use in solar thermochemical water splitting, highlighting innovative approaches and challenges. Further exploration encompasses inorganic materials like metal oxides, molybdates, and rare earth compounds, revealing their catalytic activity and potential for water-splitting applications. Despite progress, challenges persist, indicating the need for continued research in the fields of material design and synthesis to advance sustainable hydrogen production. Full article

From reactions involving sodium molybdate and dianilines [2,2′-(NH₂)C₆H₄]₂(CH₂)_n (n = 0, 1, 2) and amino-functionalized carboxylic acids 1,2-(NH₂)(CO₂H)C₆H₄ or 2-H₂NC₆H₃-1,4-(CO₂H)₂, in the presence of Et₃N and Me₃SiCl, products adopting H-bonded networks have been characterized. In particular, the reaction of 2,2′-diaminobiphenyl, [2,2′-NH₂(C₆H₄)]₂, and 2-aminoterephthalic acid, H₂NC₆H₃-1,4-(CO₂H)₂, led to the isolation of [(MoCl₃[2,2′-N(C₆H₄)]₂}{HNC₆H₃-1-(CO₂),4-(CO₂H)]·2[2,2′-NH₂(C₆H₄)]₂·3.5MeCN (1·3.5MeCN), which contains intra-molecular N–H∙∙∙Cl H-bonds and slipped π∙∙∙π interactions. Similar use of 2,2′-methylenedianiline, [2,2′-(NH₂)C₆H₄]₂CH₂, in combination with 2-aminoterephthalic acid led to the isolation of [MoCl₂(O₂CC₆H₃NHCO₂SiMe₃)(NC₆H₄CH₂C₆H₄NH₂)]·3MeCN (2·3MeCN). Complex 2 contains extensive H-bonds between pairs of centrosymmetrically-related molecules. In the case of 2,2′ethylenedianiline, [2,2′-(NH₂)C₆H₄]₂CH₂CH₂, and anthranilic acid, 1,2-(NH₂)(CO₂H)C₆H₄, reaction with Na₂MoO₄ in the presence of Et₃N and Me₃SiCl in refluxing 1,2-dimethoxyethane afforded the complex [MoCl₃{1,2-(NH)(CO₂)C₆H₄}{NC₆H₄CH₂CH₂C₆H₄NH₃}]·MeCN (3·MeCN). In 3, there are intra-molecular bifurcated H-bonds between NH₃ H atoms and chlorides, whilst pairs of molecules H-bond further via the NH₃ groups to the non-coordinated carboxylate oxygen, resulting in H-bonded chains. Complexes 1 to 3 have been screened for the ring opening polymerization (ROP) of both ε-caprolactone (ε-CL) and δ-valerolactone (δ-VL) using solvent-free conditions under N₂ and air. The products were of moderate to high molecular weight, with wide Ð values, and comprised several types of polymer families, including OH-terminated, OBn-terminated (for PCL only), and cyclic polymers. The results of metal-free ROP using the dianilines [2,2′-(NH₂)C₆H₄]₂(CH₂)_n (n = 0, 1, 2) and the amino-functionalized carboxylic acids 1,2-(NH₂)(CO₂H)C₆H₄ or 2-H₂NC₆H₃-1,4-(CO₂H)₂ under similar conditions (no BnOH) are also reported. The dianilines were found to be capable of the ROP of δ-VL (but not ε-CL), whilst anthranilic acid outperformed 2-aminoterephthalic acid for both ε-Cl and δ-VL. Full article

This paper reviews not the largest, but at the same time quite an interesting, group of natural and synthetic uranyl molybdate compounds. Nowadays, nine minerals of U and Mo are known, but the crystal structures have only been reported for five of them. Almost an order of magnitude more (69) synthetic compounds are known. A significant discrepancy in the topological types for natural and synthetic phases is shown, which is most likely due to elevated temperatures of laboratory experiments (up to 1000 °C), while natural phases apparently grow at significantly lower temperatures. At the same time, the prevalence of dense topologies (with edge-sharing interpolyhedral linkage) among natural phases can be noted, which is fully consistent with other recently considered mineral groups. Uranyl molybdates demonstrate several similarities with compounds of other U-bearing groups; however, even topological matches do not lead to the appearance of completely isotypic compounds. Structural complexity calculations confirm, in general, crystal chemical observations. Considering the prevalence of dense structures in which coordination polyhedra of uranium and molybdenum are connected through common edges as well as framework architectures, one can expect a less significant influence of interlayer species on the formation of the crystal structure than the main U-bearing complexes. The more structural complexity of the uranyl molybdate units, the more complex of the entire crystal structure is. In addition, there is a tendency for complexity to increase with increasing density of the complex; the simplest structures are vertex-shared, while the complexity increases with the appearance of common edges. Full article

This review article deals with the pathways of cellular and global molybdate distribution in plants, especially with a full overview for the model plant Arabidopsis thaliana. In its oxidized state as bioavailable molybdate, molybdenum can be absorbed from the environment. Especially in higher plants, molybdenum is indispensable as part of the molybdenum cofactor (Moco), which is responsible for functionality as a prosthetic group in a variety of essential enzymes like nitrate reductase and sulfite oxidase. Therefore, plants need mechanisms for molybdate import and transport within the organism, which are accomplished via high-affinity molybdate transporter (MOT) localized in different cells and membranes. Two different MOT families were identified. Legumes like Glycine max or Medicago truncatula have an especially increased number of MOT1 family members for supplying their symbionts with molybdate for nitrogenase activity. In Arabidopsis thaliana especially, the complete pathway followed by molybdate through the plant is traceable. Not only the uptake from soil by MOT1.1 and its distribution to leaves, flowers, and seeds by MOT2-family members was identified, but also that inside the cell. the transport trough the cytoplasm and the vacuolar storage mechanisms depending on glutathione were described. Finally, supplying the Moco biosynthesis complex by MOT1.2 and MOT2.1 was demonstrated. Full article

Molybdenum (Mo) is vital for the activity of a small but essential group of enzymes called molybdoenzymes. So far, specifically five molybdoenzymes have been discovered in eukaryotes: nitrate reductase, sulfite oxidase, xanthine dehydrogenase, aldehyde oxidase, and mARC. In order to become biologically active, Mo must be chelated to a pterin, forming the so-called Mo cofactor (Moco). Deficiency or mutation in any of the genes involved in Moco biosynthesis results in the simultaneous loss of activity of all molybdoenzymes, fully or partially preventing the normal development of the affected organism. To prevent this, the different mechanisms involved in Mo homeostasis must be finely regulated. Chlamydomonas reinhardtii is a unicellular, photosynthetic, eukaryotic microalga that has produced fundamental advances in key steps of Mo homeostasis over the last 30 years, which have been extrapolated to higher organisms, both plants and animals. These advances include the identification of the first two molybdate transporters in eukaryotes (MOT1 and MOT2), the characterization of key genes in Moco biosynthesis, the identification of the first enzyme that protects and transfers Moco (MCP1), the first characterization of mARC in plants, and the discovery of the crucial role of the nitrate reductase–mARC complex in plant nitric oxide production. This review aims to provide a comprehensive summary of the progress achieved in using C. reinhardtii as a model organism in Mo homeostasis and to propose how this microalga can continue improving with the advancements in this field in the future. Full article