Electroreduction of pertechnetate ions in concentrated acetate solutions

Kuznetsov, V. V.; Volkov, Mikhail A.; German, K. É.; Филатова, Е. В.; Belyakova, O. A.; Trigub, Alexander L.

doi:10.1016/j.jelechem.2020.114090

Cited by 8 publications

(6 citation statements)

References 34 publications

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“…It is interesting to note that Tc–C interatomic distances in the nanocomposite obtained by thermolysis are shorter than those in Tc–C cathodic deposits obtained by electrolysis of ammonia acetate solutions at high cathodic current densities (2.04 Å) . Therefore, one can conclude that the interaction between technetium and carbon atoms is stronger in the case of the product obtained by thermal decomposition.…”

Section: Resultsmentioning

confidence: 94%

“…It is interesting to note that Tc−C interatomic distances in the nanocomposite obtained by thermolysis are shorter than those in Tc−C cathodic deposits obtained by electrolysis of ammonia acetate solutions at high cathodic current densities (2.04 Å). 26 Therefore, one can conclude that the interaction between technetium and carbon atoms is stronger in the case of the product obtained by thermal decomposition. The formation of Tc−C bonds in the course of thermal decompositions of pertechnetates with large organic cations allows the assumption that the passivity of technetium to carbon is explained by its high melting point rather than a complete lack of affinity.…”

Section: Synthesis Of Hexamethyleneiminium Pertechnetate (Compound Ii...mentioning

confidence: 95%

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Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Kuznetsov,

German,

Nagovitsyna

et al. 2023

Inorg. Chem.

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Technetium–carbon nanophases are obtained by thermal decomposition of pertechnetates with large organic cations under an argon atmosphere. Parallel carbonization of organic cations (hexamethyleneiminium and triphenylguanidinium), which occurs during the thermal decomposition of their pertechnetates, leads to the formation of X-ray amorphous solid products. An X-ray absorption fine structure study revealed that they have a crystal structure containing technetium–carbon bonds with a length of 1.76 Å. After subsequent annealing treatment at 1073–1673 K, the synthesized technetium–carbon phase has a cubic lattice with an a of 4.01 ± 0.03 Å. The products of thermal decomposition of the same perrhenates are also X-ray amorphous; however, unlike that of pertechnetates, the distance between rhenium and carbon atoms in them is significantly greater (2.14 Å). After subsequent annealing, they have a hexagonal lattice. The electrochemical properties of technetium–carbon nanophases prepared by thermal decomposition of pertechnetates with large organic cations are different from the properties of those prepared with metallic technetium. The oxidation of technetium carbide to its oxides at the electrode surface observed in the first anodic scan of cyclic voltammograms can be used for the deposition of noble metal nanoclusters under open-circuit conditions to prepare composite catalysts for the hydrogen evolution reaction. Nanotechnetium in the amorphous carbon matrix can also be a prospective material for reactor transmutation of technetium to stable isotopically pure ruthenium-100.

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Section: Resultsmentioning

confidence: 94%

Section: Synthesis Of Hexamethyleneiminium Pertechnetate (Compound Ii...mentioning

confidence: 95%

Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Kuznetsov,

German,

Nagovitsyna

et al. 2023

Inorg. Chem.

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“…31−33 The literature states that the electroreduction mechanism of pertechnetate anions results in the creation of Tc(IV) compounds. 32,34,35 However, isolating individual compounds and determining their structure were not studied. Polymer-chain cluster complexes of Tc 2 (OOCCH 3 ) 5 were previously reported as obtained from Tc(VII) compounds.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc₈(μ-O)₈(RCOO)₁₆, Where R = CF₃, C₆H₅)─Potential Nanobuilding Units for Tc-MOFs

Volkov,

Abkhalimov,

Novikov

et al. 2024

Inorg. Chem.

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Herein, we studied the behavior of TcO4 – in trifluoroacetic anhydride (TFAA) under visible light irradiation in situ by UV–vis spectroscopy. One carboxylate of Tc(VII) C2F3O5Tc (1) and two wheel-like carboxylate clusters of Tc(IV) Tc8(μ-O)8(CF3COO)16 (2, 3) and Tc8(μ-O)8(C6H5COO)16 (4) were synthesized and analyzed using pXRD, TGA, UV–vis spectroscopy, and SCXRD techniques. According to SCXRD, it was found that Tc(IV) trifluoroacetate exists in two crystalline modifications. By UV–vis spectroscopy and DFT calculations, it was shown that the primary compound in the reaction system is trifluoroacetate Tc(VII). A technetium trifluoroacetate(VII) and Tc intermediates of unidentified nature both show photosensitivity. The influence of intermolecular noncovalent interactions on the volatility of trifluoroacetate and benzoate Tc(IV) is shown. The main regularities of chemical transformations of technetium in nonaqueous solutions of carboxylates have been revealed. The obtained data on the kinetics of the process suggest that technetium in trifluoroacetic anhydride can simultaneously exist in the form of Tc(VII), Tc(VI), Tc(V), and Tc(IV). Under laser ionization or prolonged heating, the formation of the Tc(II,III)-cluster is observed.

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“…In turn, Rajec and Maca ´s ˇek 23 reported the formation of hexachlorotechnetates(IV) as a result of electrochemical reduction of TcOCl ) are observed. 24 Dimeric Tc species are reported to be generated in concentrated aqueous formate [25][26][27] or acetate 28 solutions.…”

Section: A Introductionmentioning

confidence: 99%

“…In more concentrated hydrochloric acid solutions, other Tc complexes (Tc 2 Cl 8 2− ) are observed. 24 Dimeric Tc species are reported to be generated in concentrated aqueous formate 25–27 or acetate 28 solutions.…”

Section: Introductionmentioning

confidence: 99%

Choline chloride–formic acid mixture as a medium for the reduction of pertechnetates – electrochemical and spectroscopic studies

Połomski

DiBlasi

Dardenne

et al. 2023

Phys. Chem. Chem. Phys.

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Electroreduction of pertechnetate ions in concentrated acetate solutions

Cited by 8 publications

References 34 publications

Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc₈(μ-O)₈(RCOO)₁₆, Where R = CF₃, C₆H₅)─Potential Nanobuilding Units for Tc-MOFs

Choline chloride–formic acid mixture as a medium for the reduction of pertechnetates – electrochemical and spectroscopic studies

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Electroreduction of pertechnetate ions in concentrated acetate solutions

Cited by 8 publications

References 34 publications

Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies

Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc8(μ-O)8(RCOO)16, Where R = CF3, C6H5)─Potential Nanobuilding Units for Tc-MOFs

Choline chloride–formic acid mixture as a medium for the reduction of pertechnetates – electrochemical and spectroscopic studies

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Product

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Synthesis of Technetium Carboxylates: Wheel-Like Octanuclear Clusters (Tc₈(μ-O)₈(RCOO)₁₆, Where R = CF₃, C₆H₅)─Potential Nanobuilding Units for Tc-MOFs