Mechanism of the Transfer of AuCl4– and TOA+ Ions Across the Liquid/Liquid Interface

Duong, Quynh; Tan, Yunshi; Corey, Jason; Anz, Samir J.; Sun, Peng

doi:10.1021/jp512909t

Cited by 8 publications

(8 citation statements)

References 23 publications

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“…Here, the HCl byproduct transfers from DCE to water; the dissociation constant of the acid in the organic phase can explain the lack of observed ion transfer current. We note that Duong et al have also studied this process using octanethiol as the reducing agent . They saw only a small change in the [AuCl 4 ] − transfer current, although the thiol was added to the aqueous phase and the time-scale of the reaction with thiol was not clear.…”

Section: Results and Discussionsupporting

confidence: 80%

“…This phase boundary potential prevents the loss of Au-containing ionic species into the aqueous phase because it is below that required for Au ion transfer. In the case of the TOA + Br – , which has also been used as a catalyst to transfer gold into the organic phase in the Brust–Schiffrin method, ion exchange proceeds as in process i though Br – is rather hydrophobic. , By contrast, TOA + and H + do not transfer between water and DCE because of their respective hydrophobicity and hydrophilicity, although a specific interaction between TOA + and [AuCl 4 ] − has recently been proposed …”

Section: Results and Discussionmentioning

confidence: 99%

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Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Uehara

Booth²,

Chang³

et al. 2015

J. Am. Chem. Soc.

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The mechanism of the Brust-Schiffrin gold nanoparticle synthesis has been investigated through the use of ion transfer voltammetry at the water/1,2-dichloroethane (DCE) solution interface, combined with X-ray absorption fine structure (XAFS) of the reaction between [AuCl4](-) and thiol (RSH) in homogeneous toluene (TL) solution. Ion transfer calculations indicate the formation of [AuCl2](-) at RSH/Au ratios from 0.2-2 with a time-dependent variation observed over several days. At RSH/Au ratios above 2 and after time periods greater than 24 h, the formation of Au(I)SR is also observed. The relative concentrations of reaction products observed at the liquid/liquid interface are in excellent agreement with those observed by XAFS for the corresponding reaction in a single homogeneous phase. BH4(-) ion transfer reactions between water and DCE indicate that the reduction of [AuCl4](-) or [AuCl2](-) to Au nanoparticles by BH4(-) proceeds in the bulk organic phase. On the other hand, BH4(-) was unable to reduce the insoluble [Au(I)SR]n species to Au nanoparticles. The number and size of the nanoparticles formed was dependent on the concentration ratio of RSH/Au, as well as the experimental duration because of the competing formation of the [Au(I)SR]n precipitate. Higher concentrations of nanoparticles, with diameters of 1.0-1.5 nm, were formed at RSH/Au ratios from 1 to 2.

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Section: Results and Discussionsupporting

confidence: 80%

Section: Results and Discussionmentioning

confidence: 99%

Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Uehara

Booth²,

Chang³

et al. 2015

J. Am. Chem. Soc.

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“…In metal ion extraction, a hydrophobic ligand is typically dissolved in the organic phase and coordinates with the metal ion either interfacially or in the bulk organic/aqeuous phase [13,14]. Conventional means of separation have been through physical mixing of the two phases [9,15]; however, as previously demonstrated [10][11][12]16], this process can also be investigated electrochemically using liquid|liquid electrochemistry performed at a polarizable interface between two immiscible electrolytic solutions (ITIES) [13,14,[17][18][19][20][21]. Furthermore, in order to reduce samples sizes and improve sensitivity, a micro-ITIES is often employed, such as at the tip of a pulled borosilicate glass capillary [11,16,[22][23][24].…”

Section: Introductionmentioning

confidence: 99%

Preparation and crystal structure of tetraoctylphosphonium tetrakis(pentafluorophenyl)borate ionic liquid for electrochemistry at its interface with water

2017

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With ongoing and expending global energy needs, nuclear power is likely to be a key energy source for many more generations. A key question is still the fate of spent nuclear fuel (SNF). SNF contains a great deal of valuable material. In order to improve safety and handling, herein is proposed relatively high melting point ionic liquid (IL) or organic ionic plastic crystals (OIPCs) for biphasic water|IL metal ion extraction. The proposed IL, tetraoctylphosphonium tetrakis(pentafluorophenyl)borate, P8888(C6F5)4, was discovered to have a melting point of ~55ºC and a high degree of order by differential scanning calorimetry and X-ray diffraction, respectively. In this way, the IL/OIPC could be used in ligand assisted metal ion extraction from water solutions at elevated temperatures and then 'frozen' at ambient conditions for facile manipulation and transport of the SNF. To test the feasibility of this, electrochemistry such as cyclic voltammetry at a water|IL micro-interface (25 µm in diameter) was employed to assess the thermodynamics of K + ligand assisted transfer. It was revealed that the TRUEX (Transuranium Extraction) ligand octyl(phenyl)-N,N'diisobutylcarbamoylphosphine oxide (CMPO) has a high to moderate coordination to K + at the w| P8888(C6F5)4, micro-interface. Two ligand to K + stoichiometries were determined to be 3:1 and 2:1, respectively.

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“…After a small amount of TOABr is added into the DCE phase, one can see another wave near 0.1 V (Wave B) in Figure . Our previous research shows that the presence of the hydrophilic bromide ion in the organic phase can only produce a background current and does not affect the study of the transfer of other ions . Therefore, wave B should be related to the transfer of TOA + .…”

Section: Resultsmentioning

confidence: 99%

Evaluation of the Stoichiometry between PtCl₆²⁻ and TOA⁺ Ions during the Liquid/Liquid Extraction

Nguyen

Dang

et al. 2018

Electroanalysis

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The transfer of PtCl62− ions into the organic phase facilitated by TOA+ is the very first step in the Brust‐Schiffrin (BS) two‐phase synthesis of monolayer protected Pt nanoparticles. However, the stoichiometry between TOA+ and PtCl62− during the facilitated transfer process is still unknown. In this paper, a hemispherical micro‐liquid/liquid interface, which is formed between a PtCl62− aqueous filled micropipette and an organic phase, has been employed to study the stoichiometry of TOA+ facilitated transfer of PtCl62−. Due to the even diffusion field at the hemispherical micro‐liquid/liquid interface, the theoretical i‐V curve for TOA+ facilitated transfer of PtCl62− can be derived in a simple way. By simulating the theoretical i‐V curve to the experimental voltammogram, the stoichiometry of TOA+ facilitated transfer of PtCl62− was evaluated to be 8.

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Mechanism of the Transfer of AuCl₄^– and TOA⁺ Ions Across the Liquid/Liquid Interface

Cited by 8 publications

References 23 publications

Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Preparation and crystal structure of tetraoctylphosphonium tetrakis(pentafluorophenyl)borate ionic liquid for electrochemistry at its interface with water

Evaluation of the Stoichiometry between PtCl₆²⁻ and TOA⁺ Ions during the Liquid/Liquid Extraction

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Mechanism of the Transfer of AuCl4– and TOA+ Ions Across the Liquid/Liquid Interface

Cited by 8 publications

References 23 publications

Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Electrochemical Insight into the Brust–Schiffrin Synthesis of Au Nanoparticles

Preparation and crystal structure of tetraoctylphosphonium tetrakis(pentafluorophenyl)borate ionic liquid for electrochemistry at its interface with water

Evaluation of the Stoichiometry between PtCl62− and TOA+ Ions during the Liquid/Liquid Extraction

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Product

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About

Mechanism of the Transfer of AuCl₄^– and TOA⁺ Ions Across the Liquid/Liquid Interface

Evaluation of the Stoichiometry between PtCl₆²⁻ and TOA⁺ Ions during the Liquid/Liquid Extraction