Structure and solubility of tetrapropylammonium pertechnetate and perrhenate

German, K. É.; Grigoriev, Mikhail S.; Auwer, Christophe Den; Maruk, A. Ya.; Obruchnikova, Ya.A.

doi:10.1134/s0036023613060090

Cited by 12 publications

(7 citation statements)

References 6 publications

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“…Searching for functional materials to efficiently remove TcO 4 – and host lattices to trap technetium as waste forms are both highly desirable and remains a significant challenge. Although different types of precipitation agents have been used for separating and trapping 99 Tc, there is significant opportunity for designing improved strategies and describing the underlying molecular-scale mechanisms that govern 99 Tc separation. − More importantly, previous investigation on the inorganic host lattice such as sodalite show an incorporation preference toward NO 3 – over ReO 4 – /TcO 4 – . This phenomenon is typical following the well-known Hofmeister bias because NO 3 – possesses a higher charge density and smaller size than ReO 4 – /TcO 4 – and therefore higher affinity with the inorganic host lattice.…”

Section: Results and Discussionmentioning

confidence: 99%

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Zhu

Xiao

Dai

et al. 2017

Environ. Sci. Technol. Lett.

191

121

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We report one of the most efficient scavenger materials, a cationic crystalline coordination polymer SBN for trapping ReO 4 − , a surrogate for 99 TcO 4 − , as an anionic radioactive contaminant of great concern. The uptake capacity for ReO 4 − reaches 786 mg/g, a value noticeably higher than the state of art anion-exchange resins and other inorganic or hybrid anion sorbents. Once being captured, ReO 4− is greatly immobilized, as almost no ReO 4 − can be eluted using large excess of nitrate, carbonate, and phosphate anions. The processes are featured by a complete and irreversible single-crystal to single-crystal structural transformation from SBN to the ReO 4 − -incorporated phase (SBR). The coordination environments of NO 3 − and ReO 4 − probed by single-crystal structures clearly unravel the underlying mechanism, where each ReO 4 − in SBR binds to multiple Ag + sites forming strong Ag−O−Re bonds, and to 4,4′-bipyridine through a dense hydrogen bond network. These structural insights lead to a significant difference in solubility product constants between SBN and SBR, which is further confirmed by first principle calculations showing a large binding energy difference of 35.61 kcal/mol. To the best of our knowledge, SBR is the least soluble perrhenate/pertechnetate salt reported, which may be considered as a potential waste form for direct immobilization of TcO 4 − .

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Section: Results and Discussionmentioning

confidence: 99%

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Zhu

Xiao

Dai

et al. 2017

Environ. Sci. Technol. Lett.

191

121

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“…However, the high solubility of NH 4 TcO 4 in aqueous solution results in an inefficient removal of TcO 4 – from waste at low concentrations . By increasing the chain length of the quaternary ammonium salts, the solubility of the resulting compounds obviously decreases . The solubility of Me 4 NTcO 4 in water was measured to be 0.13 M, whereas that of Bu 4 NTcO 4 decreased to 4.2 × 10 –3 M. Despite this, the solubility of pertechnetate-based quaternary ammonium salts is still high.…”

Section: Pertechnetate Separation Materialsmentioning

confidence: 99%

Separation and Remediation of ⁹⁹TcO₄^– from Aqueous Solutions

2019

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Technetium-99 (99Tc) is one of the most-problematic radioisotopes in used nuclear fuel owing to its intrinsic features of a high fission yield, long half-life, high environmental mobility, volatile nature during waste vitrification, and its redox interface capability with actinides during used fuel repossessing. The selective separation of pertechnetate (TcO4 –) from legacy nuclear waste and contaminated natural water is therefore highly desirable but still a significant challenge, because the conditions of a strong radiation field, high ionic strength, high acidity/alkalinity, and large amounts of competing anions are often involved in these systems. Until now, there are a handful of functional materials that can efficiently remove TcO4 – from nuclear waste solutions with high uptake capacities, fast kinetics, and good selectivity, but room still remains to further improve our capabilities for controlling the contamination/separation of TcO4 –. In this Perspective, we discuss the current state of the art TcO4 – separation materials including precipitation agents, reducing materials, ion-exchange resins, inorganic cationic frameworks, cationic metal–organic frameworks (MOFs), and cationic polymeric networks (CPNs) materials. The intriguing separation mechanisms of these materials for TcO4 – are also disclosed, which may hopefully shed light on further development in this field.

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“…During the synthesis of the TPAP catalyst, crystals suitable for X‐ray analysis were obtained and its structure was determined. Pr 4 N[RuO 4 ] is isostructural with n Pr 4 N[ReO 4 ] and its Tc analogue, which was analyzed by powder X‐ray diffraction . In the present structure there was disorder in all four propyl arms of the cation, which contrasts with the well‐ordered rhenium structure.…”

Section: Resultsmentioning

confidence: 79%

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

et al. 2018

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The Ley–Griffith oxidation, which is catalyzed by tetra‐n‐propylammonium perruthenate (TPAP, nPr4N[RuO4]), is a popular method for not only controlled oxidation of primary alcohols to aldehydes, but also a host of other synthetically useful transformations. While the fundamental reaction mechanism has recently been elucidated, several key hydrogen‐bonding interactions between the reagents were implicated but not investigated. Herein the prevalence of H‐bonding between the co‐oxidant N‐methylmorpholine N‐oxide (NMO), the alcohol substrate, water and the perruthenate catalyst is established. These observations help to rationalize the importance of drying the reagents and lead to several practical suggestions.

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Structure and solubility of tetrapropylammonium pertechnetate and perrhenate

Cited by 12 publications

References 6 publications

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Separation and Remediation of ⁹⁹TcO₄^– from Aqueous Solutions

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

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Structure and solubility of tetrapropylammonium pertechnetate and perrhenate

Cited by 12 publications

References 6 publications

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Exceptional Perrhenate/Pertechnetate Uptake and Subsequent Immobilization by a Low-Dimensional Cationic Coordination Polymer: Overcoming the Hofmeister Bias Selectivity

Separation and Remediation of 99TcO4– from Aqueous Solutions

Hydrogen‐Bonding Interactions in the Ley–Griffith Oxidation: Practical Considerations for the Synthetic Chemist

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Separation and Remediation of ⁹⁹TcO₄^– from Aqueous Solutions