Central metal ion exchange in a coordination polymer based on lanthanide ions and di(2-ethylhexyl)phosphoric acid: Exchange rate and tunable affinity

Tasaki-Handa, Yuiko; Abe, Yukie; Ooi, Kenta; Tanaka, Mikiya; Wakisaka, Akihiro

doi:10.1016/j.jcis.2013.09.018

Cited by 21 publications

(16 citation statements)

References 21 publications

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“…The ATR–FTIR spectra ( Figure 5 b) show a doublet at approximately 1170 and 1100 cm –1 , supposedly because of the vibration of the POO – group. 44 This exact doublet shifted toward the value of Dy(DBP) 3 in the TiP_0:1_Dy sample. The Raman and UV–vis diffuse reflectance spectra were also checked before and after Dy 3+ loading, yet no evident changes were found.…”

Section: Results and Discussionmentioning

confidence: 92%

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process

Zhang

Hietala

Khriachtchev

et al. 2018

ACS Appl. Mater. Interfaces

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The lanthanides (Ln) are an essential part of many advanced technologies. Our societal transformation toward renewable energy drives their ever-growing demand. The similar chemical properties of the Ln pose fundamental difficulties in separating them from each other, yet high purity elements are crucial for specific applications. Here, we propose an intralanthanide separation method utilizing a group of titanium(IV) butyl phosphate coordination polymers as solid-phase extractants. These materials are characterized, and they contain layered structures directed by the hydrophobic interaction of the alkyl chains. The selective Ln uptake results from the transmetalation reaction (framework metal cation exchange), where the titanium(IV) serves as sacrificial coordination centers. The “tetrad effect” is observed from a dilute Ln3+ mixture. However, smaller Ln3+ ions are preferentially extracted in competitive binary separation models between adjacent Ln pairs. The intralanthanide ion-exchange selectivity arises synergistically from the coordination and steric strain preferences, both of which follow the reversed Ln contraction order. A one-step aqueous separation of neodymium (Nd) and dysprosium (Dy) is quantitatively achievable by simply controlling the solution pH in a batch mode, translating into a separation factor of greater than 2000 and 99.1% molar purity of Dy in the solid phase. Coordination polymers provide a versatile platform for further exploring selective Ln separation processes via the transmetalation process.

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Section: Results and Discussionmentioning

confidence: 92%

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process

Zhang

Hietala

Khriachtchev

et al. 2018

ACS Appl. Mater. Interfaces

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“…transmetalation selectivity wherein both the strength of the ligand-metal coordination bond and the ion-size compatibility were involved. [21][22][23] This is a particularly opportune example because ion recognition in some CCPs is governed by only one contributing factor, i. e., interaction with an anionic site that is offered by the functional groups of organic ligands [24][25][26][27][28] or the size adaptability caused by the crystallinity of the framework. [17,[29][30][31][32] We believe that transmetalation of phosphate CCPs has a potential to bring out a novel Ln 3 + selectivity because phosphate substances shows high selectivity over the lanthanide series.…”

Section: Introductionmentioning

confidence: 99%

“…To develop a novel system (or material) that exhibits a unique selectivity series, both factors need to be utilized comparably, i. e. binding strength and structural rigidity. Indeed, we have previously synthesized a CCP from Ln 3+ and phosphate ester ligands, and discovered an unusual Ln

_{1}^{3 +}

/Ln

_{2}^{3 +}

(Ln

_{1}^{3 +} \neq

_{2}^{3 +}

) transmetalation selectivity wherein both the strength of the ligand‐metal coordination bond and the ion‐size compatibility were involved . This is a particularly opportune example because ion recognition in some CCPs is governed by only one contributing factor, i. e., interaction with an anionic site that is offered by the functional groups of organic ligands or the size adaptability caused by the crystallinity of the framework …”

Section: Introductionmentioning

confidence: 99%

Transmetalation in a Ce(III)‐phosphoester Crystalline Coordination Polymer with an Exceptionally High Selectivity for Yb(III) and Lu(III)

Tasaki-Handa

Tsuda

Shibukawa

et al. 2020

Chemistry An Asian Journal

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A novel crystalline coordination polymer containing Ce3+ and bis(4‐nitrophenyl) phosphate (L), CeL3, was synthesized and its unique transmetalation selectivities toward Yb3+ and Lu3+ in the lanthanide series were evaluated. The relatively large difference in transmetalation selectivity between the neighboring Tm3+ and Yb3+ species is noteworthy because the reactivities of heavy lanthanides are generally considerably similar. The structural strain of the polymeric framework is likely responsible for this unusual trend. Powder X‐ray diffraction analysis indicated that, in the cases of only Yb3+ and Lu3+, large differences in their ionic sizes compared to that of Ce3+ in the parent framework may induce a structural strain after solid solution formation, while cleavage of the relatively weak Ce−O bond allows the formation of new Yb−O and Lu−O bonds with the incoming Yb3+ and Lu3+, respectively. Structural phase transitions likely caused by the heterogeneous nucleation of the Yb‐ (or Lu‐) type phase were also observed.

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“…This interest stems from their potential applications as functional materials such as gas storage, ion exchangers, catalysis, magnetism, and molecular sensing [22][23][24][25][26][27][28]. These compounds containing redox active ions of transition metals such as Fe, Co, Ni, Cu, Mn, Mo and V may have catalytic activity for reactions following a redox mechanism [29].…”

Section: Introductionmentioning

confidence: 99%

Investigation of the catalytic behavior of a Cu coordination polymer capped polyoxometalate as an oxidation catalyst

Farzaneh

Moghzi

2015

Reac Kinet Mech Cat

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A multifunctional organic-inorganic hybrid based on a Cu coordination polymer capped polyoxometalate (H 3 PMo 12 O 40 ) designated as compound 1 with [Cu I (4,4 0 -bipy)] 3 [PMo 10 VI Mo 2 V O 40 {Cu II (2,2 0 -bipy)}] formula was prepared using CuCl 2 Á2H 2 O, 4,4 0 -bipy, 2,2 0 -bipy and H 3 PMo 12 O 4 in water under hydrothemal conditions. The prepared compound 1 was characterized by FTIR, XRD and chemical analysis techniques. It was found that the compound successfully catalyzes the epoxidation of various alkenes such as diphenyl ethylene, trans-stilbene, cyclohexene, norbornene, styrene and cyclooctene and oxidation of alkanes such as fluorene, adamantane, diphenylmethane, cyclohexane and cyclooctane, in acetonitrile with 20-99 % conversion and 53-100 % selectivity with tert-butyl hydroperoxide as oxidant under optimized condition. This heterogeneous catalyst could be easily recovered and reused after reaction without loss of activity.

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Central metal ion exchange in a coordination polymer based on lanthanide ions and di(2-ethylhexyl)phosphoric acid: Exchange rate and tunable affinity

Cited by 21 publications

References 21 publications

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process

Intralanthanide Separation on Layered Titanium(IV) Organophosphate Materials via a Selective Transmetalation Process

Transmetalation in a Ce(III)‐phosphoester Crystalline Coordination Polymer with an Exceptionally High Selectivity for Yb(III) and Lu(III)

Investigation of the catalytic behavior of a Cu coordination polymer capped polyoxometalate as an oxidation catalyst

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