Straightforward and selective metal capture through CO<sub>2</sub>-induced self-assembly

Poisson, Guillaume; Germain, G.; Septavaux, Jean; Leclaire, Julien

doi:10.1039/c6gc02442d

“…This is probably related to difficulties of synthesizing these compounds in the crystalline state. At the same time, the corresponding systems with polyamines are of interest from the viewpoint of their application in technologies in carbon dioxide trapping and storage [31,34].…”

Section: Resultsmentioning

confidence: 99%

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Tsymbarenko

¹

,

Grebenyuk

²

,

Burlakova

³

et al. 2022

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Tetranuclear hydroxo complexes [La4(Deta)4(OH)4(Tfa)3(DetadcH)2](HTfa)(H2O)7(Tfa)3 (I) and [Nd4(Deta)4(OH)4(Tfa)3(DetadcH)2](H2O)n(Tfa)3 (II) with diethylene-N,N′-dicarbamate anions (DetadcH–) are synthesized for the first time by the reactions of lanthanum trifluoroacetate and neodymium trifluoroacetate with a solution of diethylenetriamine (Deta) in air under the self-controlled hydrolysis conditions and are characterized by X-ray diffraction, powder X-ray diffraction, IR spectroscopy, and elemental analysis. Compounds I and II contain the same-type complex cationic fragment with the cubane metal–oxygen core stabilized due to four chelate Deta ligands and two bridging DetadcH– ligands. The DFT calculations of the geometry and vibrational spectrum of the [La4(Deta)4(OH)4(Tfa)3(DetadcH)2]3+ complex cation are performed.

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“…Although no amplification was evidenced, we recently showed that oxophilic metal cations could, upon counter-anion exchange, selectively bind and co-precipitate the dicarbamates from such a library, while aminophilic metals mostly remained in solution. 22 Metal-induced amplification was herein quantified by monitoring and comparing the CO2-induced speciation of DETA by 1 H and 13 C NMR spectroscopy (qNMR) in the presence and absence of various pre-solubilized metal chlorides as leachate models. The first analyses were performed in methanol, a relevant solvent to observe the selective precipitation of metallocarbamate adducts for subsequent extractive purification.…”

Section: A(co 2 )mentioning

confidence: 99%

Simultaneous CO2 Capture and Metal Purification from Waste Streams

Leclaire¹,

Septavaux²,

Tosi³

et al. 2018

Preprint

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The process of carbon capture, which is one of the most mature yet cost-intensive technology proposed to mitigate global warming has herein been explored as a potential strategy to generate dynamic ligands for metal separation and recovery. Spontaneous CO2 fixation by industrial amines such as diethylenetriamine affords dynamic arrays of interconverting species, from which tailored subsets can be selected yielding organometallic adducts of contrasted solubility. Quantitative compositional analyses of the phases produced with varying CO2 loadings allow to elucidate the underpining self-sorting scenario induced by each metal, and to identify the conditions affording optimal individual separation by precipitation. To illustrate the potentiality of this approach, which could bring substantial added value to the CO2 capture and utilization chain value, bimetallic separation was conducted directly from exhaust gas of an internal combustrion engine vehicle, and the three constituents of the alloys used to produce the cathodes of electric vehicles were separated and recovered by successive CO2-induced selective precipitations. This study provides a potential framework to integrated CO2 capture and utilization and paves the way toward the design of CO2-sourced sustainable processes.<br>

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“…The capture selectivity S (i/ j) of metal i over species j is defined as: system (free amine, carbamates and bicarbonate) are identified 22 and precisely quantified 34 by comparative integration with respect to the internal reference using parameters and methods previously reported and validated. For graphical readability, curve fitting was achieved using a 3rd degree polynomial Lagrange function without further interpretation (R 2 > 0.990).…”

Section: Co2-metal Integratedmentioning

confidence: 99%

“…Although no amplification was evidenced, we recently showed that oxophilic metal cations could, upon counter-anion exchange, selectively bind and co-precipitate the dicarbamates from such a library, while aminophilic metals mostly remained in solution. 22 Metal-induced amplification was herein quantified by monitoring and comparing the CO2-induced speciation of DETA by 1 H and 13 C NMR spectroscopy (qNMR) in the presence and absence of various pre-solubilized metal chlorides as leachate models. The first analyses were performed in methanol, a relevant solvent to observe the selective precipitation of metallocarbamate adducts for subsequent extractive purification.…”

Section: A(co 2 )mentioning

confidence: 99%

Simultaneous CO2 Capture and Metal Purification from Waste Streams

Leclaire

¹

,

Septavaux²,

Tosi³

et al. 2018

Preprint

0

View full text Add to dashboard Cite

The process of carbon capture, which is one of the most mature yet cost-intensive technology proposed to mitigate global warming has herein been explored as a potential strategy to generate dynamic ligands for metal separation and recovery. Spontaneous CO2 fixation by industrial amines such as diethylenetriamine affords dynamic arrays of interconverting species, from which tailored subsets can be selected yielding organometallic adducts of contrasted solubility. Quantitative compositional analyses of the phases produced with varying CO2 loadings allow to elucidate the underpining self-sorting scenario induced by each metal, and to identify the conditions affording optimal individual separation by precipitation. To illustrate the potentiality of this approach, which could bring substantial added value to the CO2 capture and utilization chain value, bimetallic separation was conducted directly from exhaust gas of an internal combustrion engine vehicle, and the three constituents of the alloys used to produce the cathodes of electric vehicles were separated and recovered by successive CO2-induced selective precipitations. This study provides a potential framework to integrated CO2 capture and utilization and paves the way toward the design of CO2-sourced sustainable processes.<br>

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Straightforward and selective metal capture through CO₂-induced self-assembly

Abstract: A new process of rare earth metal capture employing carbon dioxide as a key component was designed and studied.

Cited by 10 publications

References 34 publications

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Simultaneous CO2 Capture and Metal Purification from Waste Streams

Simultaneous CO2 Capture and Metal Purification from Waste Streams

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Straightforward and selective metal capture through CO2-induced self-assembly

Abstract: A new process of rare earth metal capture employing carbon dioxide as a key component was designed and studied.

Cited by 10 publications

References 34 publications

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Tetranuclear Hydroxo Complexes of Rare-Earth Elements with the Cubane Core as Products of Self-Controlled Hydrolysis

Simultaneous CO2 Capture and Metal Purification from Waste Streams

Simultaneous CO2 Capture and Metal Purification from Waste Streams

Contact Info

Product

Resources

About

Straightforward and selective metal capture through CO₂-induced self-assembly