Search Results (42)

Silver-white, matte, smooth, and durable deposits of silver-rhenium, with thicknesses ranging from 2.0 to 13.7 μm and containing 0.15 to 13.5 wt.% Re, were obtained with a current efficiency of 66–98% from a developed dicyanoargentate–perrhenate bath based on a borate–phosphate–carbonate silver-plating electrolyte. This study was focused on the influence of bath composition, the [Ag(I)]:[ReO₄⁻] ratio, surfactant additives, applied current density, temperature, and stirring, on the alloys’ composition, structure, morphology, microhardness, adhesion, and porosity. A voltammetric analysis was conducted, considering the influence of ethanolamines on electrode processes. In baths with triethanolamine (TEA), coatings similar to a silver matrix with rhenium doped in mass fractions are likely achievable. Monoethanolamine (MEA) is recommended due to its process-activating properties. All coatings were nanocrystalline (τ = 28.5–35 nm). For deposits containing less than 10 wt.% Re, characteristic silver XRD peaks were observed, while for other deposits, additional peaks attributed probably to Re(VII) and Re(VI) oxides. A linear relationship H_v − τ^−1/2, typical for Hall–Petch plots, was obtained, confirming that grain boundaries play a crucial role in mechanical properties of coatings. The conditions for stable electrochemical synthesis of promising functional Ag-Re coatings of predetermined composition (0.7–1.5 wt.% Re) were proposed for practical use in power electronics and energy sectors for manufacturing electrical contacts operating across a wide temperature range. This was realized by deposition from an Ag-rich bath in the area of mixed electrochemical kinetics, at potential values corresponding to the region of half the limiting current: j = 2.5–6 mA cm⁻², t = 19–33 °C. Full article

This study investigates the formation of metallic rhenium through Solution Combustion Synthesis (SCS), focusing on the thermodynamics, kinetics, and phase composition of the process. The impact of the fuel-to-oxidizer ratio (φ) on the synthesis of rhenium was evaluated, demonstrating that the stoichiometric ratio (φ = 1) leads to the highest combustion temperature and the formation of pure metallic rhenium, as confirmed by XRD. Deviation from this stoichiometric condition, either by fuel excess (φ > 1) or oxidizer excess (φ < 1), resulted in incomplete reduction and the formation of rhenium oxides (ReO₂ and ReO₃). Thermodynamic calculations revealed that under reducing conditions, metallic rhenium is the primary product while oxidizing conditions favor the formation of rhenium dioxide. Kinetic analysis of the thermal decomposition of ammonium perrhenate suggested that the process involves a multi-stage reaction, with the reduction of rhenium occurring in a stepwise manner. The findings provide new insights into the role of rhenium as both a metal and an oxidizer in SCS and emphasize the critical influence of the fuel/oxidizer ratio in controlling the phase composition and crystallinity of the final product. Full article

Yearly, thousands of tons of wasted coffee grounds are produced according to high coffee consumption. Still, after the coffee brewing, wasted coffee grounds contain some amounts of caffeine (CAF). CAF, in turn, contains multiple O and N chelating atoms in its structure. These have a potential to be reductors for complexes of metals. In this context, within the present study, a set of CAF extracts derived from coffee beans and coffee grounds were obtained and then used for the one-step reduction of ReO₄⁻ ions with no additional toxic chemicals. Within this approach, CAF was applied as a secondary, green resource for the synthesis of unique rhenium nanoparticles (ReNPs) containing Re species at 0 and +6 oxidation states. The obtained ReNPs were identified and characterized with the use of X-ray powder diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Further, the capping and stabilization of ReNPs by CAF were verified with the aid of Fourier transformation infrared spectroscopy (FT-IR). The so-obtained “green” ReNPs were then used as a homogenous catalyst in the catalytic hydrogenation of 4-nitrophenol (4-NP). This new nanomaterial revealed a superior catalytic activity, leading to the complete reduction of 4-NP to 4-aminophenol within 40–60 min with a first-order rate constant of 0.255 min⁻¹. Full article

Titanium alloys, particularly Ti6Al4V, are widely used in biomedical applications due to their excellent mechanical properties and inherent biocompatibility. However, enhancing their surface characteristics, such as biocompatibility and corrosion resistance, remains a key challenge for their long-term use in medical implants. In this study, we investigate the effects of rhenium–carbon coatings deposited on Ti6Al4V substrates via magnetron sputtering, incorporating a molybdenum anchoring layer. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) analyses confirmed the formation of rhenium carbides, elemental rhenium, and rhenium oxides within the coatings. Despite these successful depositions, scanning electron microscopy (SEM) revealed significant delamination and poor adhesion of the coatings to the Ti6Al4V substrates. Corrosion resistance, evaluated through potentiodynamic polarization tests, showed an increase in corrosion current densities and more negative corrosion potentials, indicating a detrimental effect on the substrate’s corrosion resistance. Biocompatibility assessments using PK15 cells demonstrated a marked decrease in cell viability and metabolic activity, particularly in samples with higher surface roughness. These findings underscore the critical need for the optimization of surface preparation and deposition processes to improve both the adhesion and biocompatibility of rhenium–carbon coatings on Ti6Al4V substrates. Future research should aim to refine coating technique to enhance adhesion, explore the mechanisms of cytotoxicity related to surface roughness, and expand biocompatibility studies across different cell lines and biological environments. Full article

This study outlines findings from an investigation into the development of a hydrometallurgical process for manufacturing various forms of zinc perrhenate, entirely from waste from recycling and from the Zn–Pb industry. Scraps of Re-bearing Ni-based superalloys and acidic waste, circulating zinc solutions generated during the production of Zn by the electrolytic method and which contain >45 g/dm³ of Zn, Na, Mn, and Mg, were used in the research. In the publication, the conditions for the production of three types of zinc perrhenate, i.e., Zn(ReO₄)₂·4H₂O, Zn(ReO₄)_2, and Zn(ReO₄)₂·2H₂O, are presented. As a result of the analysis of the obtained results, it was concluded that to obtain the above-mentioned forms of zinc perrhenate, zinc carbonate can be used, precipitated from acidic, waste, and multi-component solutions after their prior neutralization to pH 4.0 and partial purification from Mn, Mg, and Na using metallurgical zinc oxide. Zinc carbonate should be precipitated using Na₂CO₃ at pH 6.3 and subsequently purified from other impurities, i.e., Mg, Na, and Mn, using aqueous ammonia solutions. As a result, zinc carbonate was obtained, which was used in a reaction with an aqueous solution of HReO₄ to produce zinc perrhenate. The precipitated forms of Zn(ReO₄)₂ were obtained by appropriately drying the crude and hydrated Zn(ReO₄)₂ to obtain its tetrahydrate, dihydrate, and anhydrous forms, respectively, using drying temperatures of 55, 135, and 185 °C. The developed technology has been submitted for a patent and is an example of a technology founded on the principles of sustainable development, with a particular emphasis on the minimalization of loss of rhenium and zinc at all stages of its realization. Full article

4-(2-furyl)-3-buten-2-one (FAc) is obtained by aldol condensation of furfural and acetone and has been used in hydrodeoxygenation reactions to obtain fuel products using noble metal catalysts. The hydrogenation of FAc in the aqueous phase using metallic- and Re oxide-supported catalysts on graphite was studied, within a temperature range of 200–240 °C, in a batch reactor over a 6 h reaction period. The catalysts were characterized using N₂ adsorption–desorption, TPR-H₂, TPD-NH₃, XRD, and XPS analyses. Catalytic reactions revealed that metallic rhenium and rhenium oxide-supported catalysts are active for the hydrogenation and Piancatelli rearrangement of FAc. Notably, metallic rhenium exhibited a fourfold higher initial rate than rhenium oxide, which was attributed to the higher dispersion of Re in the Re/G catalyst over graphite. Re/G and ReOx/G catalysts tended to rearrange and hydrogenate FAc to 2-(2-oxopropyl)cyclopenta-1-one in water. Full article

In contrast to corresponding nitrosyl compounds, thionitrosyl complexes of rhenium and technetium are rare. Synthetic access to the thionitrosyl core is possible by two main approaches: (i) the treatment of corresponding nitrido complexes with S₂Cl₂ and (ii) by reaction of halide complexes with trithiazyl chloride. The first synthetic route was applied for the synthesis of novel rhenium and technetium thionitrosyls with the metals in their oxidation states “+1” and “+2”. [M^VNCl₂(PPh₃)₂], [M^VNCl(PPh₃)(L^OMe)] and [M^VINCl₂(L^OMe)] (M = Re, Tc; {L^OMe}⁻ = (η⁵-cyclopentadienyl)tris(dimethyl phosphito-P)cobaltate(III)) complexes have been used as starting materials for the synthesis of [Re^II(NS)Cl₃(PPh₃)₂] (1), [Re^II(NS)Cl₃(PPh₃)(OPPh₃)] (2), [Re^II(NS)Cl(PPh₃)(L^OMe)]⁺ (4a), [Re^II(NS)Cl₂(L^OMe)] (5a), [Tc^II(NS)Cl(PPh₃)(L^OMe)]⁺ (4b) and [Tc^II(NS)Cl₂(L^OMe)] (5b). The triphenylphosphine complex 1 is partially suitable as a precursor for ongoing ligand exchange reactions and has been used for the synthesis of [Re^I(NS)(PPh₃)(Et₂btu)₂] (3a) (HEt₂btu = N,N-diethyl-N′-benzoyl thiourea) containing two chelating benzoyl thioureato ligands. The novel compounds have been isolated in crystalline form and studied by X-ray diffraction and spectroscopic methods including IR, NMR and EPR spectroscopy and (where possible) mass spectrometry. A comparison of structurally related rhenium and technetium complexes allows for conclusions about similarities and differences in stability, reaction kinetics and redox behavior between these 4d and 5d transition metals. Full article

Rhenium is an extremely rare critical metal element in Earth’s continental crust. Owing to its extremely high melting point and heat-stable crystalline structure, rhenium is an essential component of alloy materials used in high-performance aircraft engines. Demand for rhenium resources is therefore growing. Currently, most rhenium is produced as a byproduct of molybdenum mining in porphyry copper–molybdenum deposits. Research has therefore focused on the enrichment characteristics of rhenium in this type of deposit, with little attention paid to rhenium in other types of deposits. This study reports the occurrence state and enrichment mechanism of rhenium in the Qianjiadian sandstone-type uranium deposit in the Songliao Basin, Northeast China. Sequential extraction revealed that the average proportions of different forms of rhenium are as follows: water-soluble (57.86%) > organic-sulfide-bound (13.11%) > residual (12.26%) > Fe/Mn oxide-bound (10.67%) > carbonate-bound (6.10%). Combining mineralogical analysis techniques such as SEM-EDS, EMPA, and XRD, it has been established that rhenium does not occur as a substitute in sulfides (e.g., molybdenite) or uranium minerals in various types of deposits. Instead, it is mainly adsorbed onto clay minerals and Fe-Ti oxides, and in a small number of other minerals (pyrite, organic matter, and pitchblende). Rhenium is similar to redox-sensitive elements such as uranium and vanadium, and it is transported in a water-soluble form by oxidizing groundwater to the redox transition zone for enrichment. However, unlike uranium, which generally forms as uranium minerals, rhenium is mainly adsorbed and enriched onto clay minerals (kaolinite and interlayered illite–smectite). Most of the rhenium in sandstone-type uranium deposits occurs in an ion-adsorption state, and is easily leached and extracted during in-situ leaching mining of uranium ores. This type of deposit demonstrates excellent production potential and will become a crucial recoverable resource for future rhenium supply. Full article

The production of oxygenated bio-additives for traditional fuels represents a key challenge due to their depletion in the near-future and their positive contribution to the reduction in environmental pollution. The present study considers the synthesis of 1-hexanol/hexyl hexanoate mixtures, two oxygenated Diesel bio-additives produced through the hydrogenation of hexanoic acid, obtainable from the fermentation of a wide variety of waste biomasses. In our case, crude hexanoic acid was produced through the fermentation of grape pomace, an abundant Italian agrifood waste. Commercial 5 wt% Re/γ-Al₂O₃ was adopted for the catalytic hydrogenation of crude hexanoic acid, and the support acidity allowed the tuning of the reaction selectivity toward the formation of hexyl hexanoate, instead of 1-hexanol, reaching yields of 40 and 25 mol%, respectively. The effects of each bio-additive on Diesel engine performance and exhaust emissions (soot, nitrogen oxides, carbon monoxide, unburned hydrocarbons) were evaluated, highlighting noteworthy positive effects especially on the reduction in carbon monoxide and soot emissions, if compared with those of Diesel fuel alone. Similar promising performances were achieved by employing Diesel blend mixtures of 1-hexanol/hexyl hexanoate, mimicking typical compositions of the rhenium-catalyzed post-hydrogenation mixtures. Even in such cases, 1-hexanol/hexyl hexanoate mixtures can be blended with commercial Diesel fuel, up to high loadings currently not yet investigated (20 vol%), without altering the engine performances and, again, significantly lowering soot and carbon monoxide emissions by more than 40%. This work highlights the possibility of obtaining such oxygenated bio-additives starting from waste through to a fully sustainable process and proves their beneficial effects on the reduction in exhaust emissions with no changes in engine performance. Full article

Water–gas shift (WGS) reaction was performed over 5% Ni/CeO₂, 5% Ni/Ce-5% Sm-O, 5% Ni/Ce-5% Gd-O, 1% Re 4% Ni/Ce-5% Sm-O and 1% Re 4% Ni/Ce-5% Gd-O catalysts to reduce CO concentration and produce extra hydrogen. CeO₂ and M-doped ceria (M = Sm and Gd) were prepared using a combustion method, and then nickel and rhenium were added onto the mixed oxide supports using an impregnation method. The influence of rhenium, samarium and gadolinium on the structural and redox properties of materials that have an effect on their water–gas shift activities was investigated. It was found that the addition of samarium and gadolinium into Ni/CeO₂ enhances the surface area, reduces the crystallite size of CeO₂, increases oxygen vacancy concentration and improves Ni dispersion on the CeO₂ surface. Moreover, the addition of rhenium leads to an increase in the WGS activity of Ni/CeMO (M = Sm and Gd) catalysts. The results indicate that 1% Re 4% Ni/Ce-5% Sm-O presents the greatest WGS activity, with the maximum of 97% carbon monoxide conversion at 350 °C. An increase in the dispersion and surface area of metallic nickel in this catalyst results in the facilitation of the reactant CO adsorption. The result of X-ray absorption near-edge structure (XANES) analysis suggests that Sm and Re in 1% Re 4% Ni/Ce-5% Sm-O catalyst donate some electrons to CeO₂, resulting in a decrease in the oxidation state of cerium. The occurrence of more Ce³⁺ at the CeO₂ surface leads to higher oxygen vacancy, which alerts the redox process at the surface, thereby increasing the efficiency of the WGS reaction. Full article

Zwitterionic compounds such as pyridine-containing tellurenyl compounds are interesting building blocks for heterometallic assemblies. They can act as ambiphilic donor/acceptors as is shown by the products of reactions of the zwitterions HpyTeCl₂ or HCF₃pyTeCl₂ with the rhenium(V) complex [ReOCl₃(PPh₃)₂]. The products have a composition of [ReO₂Cl(pyTeCl)(PPh₃)₂] and [ReO₂Cl(CF₃pyTeCl)(PPh₃)₂] with central ${\{\mathrm{O}=\mathrm{R}\overgroup{\mathrm{e}=\mathrm{O}\dots \mathrm{Te}(\mathrm{Cl})\mathrm{p}}y\}}^{+}$ units. The Re-O bonds in the products are elongated by approximately 0.1 Å compared with those to the terminal oxido ligands and establish Te…O contacts. Thus, the normally easily assigned concept of oxidation states established at the two metal ions becomes questionable (Re^V/Te^II vs. Re^III/Te^IV). A simple bond length consideration rather leads to a description with the coordination of a mesityltellurenyl(II) chloride unit to an oxido ligand of the Re(V) center, but the oxidation of the tellurium ion and the formation of a tellurinic acid chloride cannot be ruled out completely from an analysis of the solid-state structures. DFT calculations (QTAIM, NBO analysis) give clear support for the formation of a Re(V) dioxide complex donating into an organotellurium(II) chloride and the alternative description can at most be regarded as a less favored resonance structure. Full article

Rhenium (Re) is widely used in the diagnosis and treatment of cancer due to its unique physical and chemical properties. Re has more valence electrons in its outer shell, allowing it to exist in a variety of oxidation states and to form different geometric configurations with many different ligands. The luminescence properties, lipophilicity, and cytotoxicity of complexes can be adjusted by changing the ligand of Re. This article mainly reviews the development of radionuclide ¹⁸⁸Re in radiotherapy and some innovative applications of Re as well as the different therapeutic approaches and imaging techniques used in cancer therapy. In addition, the current application and future challenges and opportunities of Re are also discussed. Full article

Surface scale is usually formed in the aerofoil part of as-cast nickel-based single crystal turbine blades by the strong interaction between the mould wall and the melt, and the subsequent oxidation of the fresh metallic surface of the casting. For better understanding of the scaling, the scaled region was investigated, and an interesting region containing hafnium oxides and a rhenium-rich particle was found. Generally, a continuous aluminium oxide layer was detected on the outer surface of the base material and covered the surface of an unscaled region. In contrast, there was no oxide on the surface of a scaled region, but it was replaced by several tiny particles remaining locally on the outer surface of the base material. SEM-EDX and TEM-EDX point analysis of these particles indicated not only the existence of high amounts of hafnium, but also several particles such as hafnium oxide, aluminium oxide, and even tiny metallic particles. Most of all, STEM-EDX point analysis clearly detected zirconium in the hafnium oxide. Furthermore, a rhenium-rich particle was also detected towards the outer surface of the base material, which suggested that the surface of the scaled region might be exposed to high enough temperatures to allow the diffusion of heavy alloying elements. Based on the observation, the formation mechanism of hafnium oxide containing zirconium and its meaning was discussed. Full article

Noncovalent interactions involving metals as electron acceptors are continuously under investigation. The term “matere bond” has been proposed to identify noncovalent donor–acceptor interactions where elements of group 7 of the periodic table play the role of the electrophilic site. Most of the works on matere bonds involve rhenium atoms usually in +7 oxidation state. This work emphasizes for the first time their importance in technetium derivatives in several oxidation states (+7, +6, +5, and +3). The Cambridge Structural Database (CSD) in combination with density functional theory (DFT) calculations are used to demonstrate the structure directing role of matere bonds in X-ray structures, even involving anion⋯anion interactions. Further characterization of the matere bonds is provided using Molecular Electrostatic Potential (MEP) surface calculations, the “Quantum Theory of Atoms in Molecules” (QTAIM), and Natural Bond Orbital (NBO) analyses. It should be emphasized that some types of matere bonds reported herein have not been previously described in literature. Full article

The structure and electrochemical characteristics of composites based on multi-walled carbon nanotubes (MWCNTs) and manganese oxide with the addition of rhenium oxide has been studied. It has shown that the decorating of the MWCNT surface with layers or nanoparticles of manganese oxide (Mn(III) + Mn(IV)) provides more than a twofold increase in the value of the specific capacitance at low potential scan rates. However, composites based only on manganese oxide exhibit poor electrochemical behavior and the value of the specific capacitance decreases rapidly with increasing potential scan rate due to the limitation of diffusion processes. The addition of rhenium oxide to composites significantly increases their electrochemical properties due to changes in the chemical composition and morphology of composites. Studies of the structure and chemical state have shown that an improvement in the specific capacitance is provided by increasing in the proportion of Mn(IV) oxide in such composites, which has the ability to rapidly and completely reverse redox reactions and has lower electrical resistance values, compared to Mn(III) oxide. A detailed analysis of the voltammetric data showed that an increase in the rate capability in composites with the addition of rhenium oxide can also be provided by increasing the availability of the electrode surface for electrolyte ions and increasing the amount of charge stored due to the formation of a double electric layer. Full article