Optimization of transition metal nanoparticle-phosphonium ionic liquid composite catalytic systems for deep hydrogenation and hydrodeoxygenation reactions

Banerjee, Abhinandan; Scott, Robert W. J.

doi:10.1039/c4gc01716a

Cited by 18 publications

(16 citation statements)

References 74 publications

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“…S3 [19,20] (see SI) assuming spherical particles. For example, cNC for 160nm Ø particles were calculated to be 3×10 14 These microscopic observations support, at least semi-quantitatively, the existence of LiBH4…”

Section: Resultssupporting

confidence: 59%

“…In a typical metal NP-in-IL synthesis, LiBH4, dissolved in tetrahydrofuran (THF), is injected into an IL solution, containing a transition metal salt, under an inert atmosphere [13,14]. THF is then removed under high vacuum at 80°C.…”

Section: Resultsmentioning

confidence: 99%

“…These materials, either added intentionally or present as impurities, will likely influence IL solvent effectiveness or introduce new reactivity. Interestingly, for the specific case of metal-NP synthesis within an IL the supramolecular nature of the IL produces highly monodisperse particles with sizes ranging as low as 1-2nm [7,[10][11][12][13][14][15] when LiBH4 is used as a reducing agent. In most of these synthetic applications, and for the case of H2 storage, an excess of borohydride is required.…”

Section: Introductionmentioning

confidence: 99%

“…In most of these synthetic applications, and for the case of H2 storage, an excess of borohydride is required. It has been demonstrated, however, that adventitious borohydride and borate species can behave as Lewis acid catalysts themselves [14,16,17]. Indeed, Banerjee et al [14] showed both borohydride and borate provided efficient dehydrogenation of cyclohexanol within an IL.…”

Section: Introductionmentioning

confidence: 99%

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Single LiBH4 nanocrystal stochastic impacts at a micro water|ionic liquid interface

Stockmann

Lemineur

Liu

et al. 2019

Electrochimica Acta

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LiBH4 is often employed as a reducing agent for metal nanoparticle (NP) preparation but is inherently a solid-state H2 hydrogen storage agent. Herein it is shown, through a combination of electron/optical microscopies and single entity electrochemical study, that LiBH4 is stored in the solid state within an ionic liquid (IL) as nanocrystals (NCs). The electrochemical monitoring of an immiscible water|IL (w|IL) micro-liquid|liquid interface (LLI) shows interfacial charge exchange associated with the stochastic impacts of single NCs. Meanwhile, in situ optical monitoring of a w|metal or w|IL interface shows that such impacts are associated with the development of a H2-in-IL micro/nano-foam related to the poor solubility of H2. Both the presence of solid NCs and the latter H2-in-IL foam suggest that H2 release from LiBH4-in-IL is a slow, but likely controlled process. The rate of H2 production at a macroscopic LLI is further confirmed by gas chromatographic measurements, in very good agreement with microscopic observations. The electrochemical LLI provides unique investigative access to LiBH4 NCs and offers insight into H2 storage in ILs, or for direct borohydride fuel cells, as well as NP synthesis. Highlights:1. Single entity electrochemical detection of LiBH4 nanocrystals at a water|ionic liquid interface.2. Single H2 bubble generated from LiBH4 nanocrystals inside an ionic liquid.3. LiBH4 induced H2-in-ionic liquid foam at water|ionic liquid interface.

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Single LiBH4 nanocrystal stochastic impacts at a micro water|ionic liquid interface

Stockmann

Lemineur

Liu

et al. 2019

Electrochimica Acta

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“…Phosphonium ILs, one of the IL types, possess diverse physicochemical properties, and offer a wide spectrum of solutions for many challenging applications including solvents for reaction media, [6][7][8][9][10] extraction of metals, [11][12][13] lubricants, [14,15] electrolytes, [16,17] supercapacitors, [18,19] and CO 2 capture. [20][21][22] The possible tunability of four functional groups on phosphonium cation together with a wide range of anion creates opportunities for higher degree of rational design and superior properties as compared to other families of ILs.…”

Section: Introductionmentioning

confidence: 99%

Understanding Spectroscopic Features of Trihexyltetradecylphosphonium Chloride

Balci

Uzun

2016

ChemistrySelect

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A comprehensive structural and spectroscopic characterization of trihexyltetradecylphosphonium chloride, [P 666(14) ][Cl], was conducted by combining experiments with density functional theory (DFT) calculations. The structure of [P 666(14) ][Cl] was first characterized experimentally by IR and NMR spectroscopies. Then, conformer search was performed by DFT calculations at B3LYP/6-31 + G(d) level to elucidate the molecular structure and intermolecular interactions prevailing in the [P 666(14) ][Cl]. Vibrational and 1 H NMR spectra computed on the most stable conformer geometry were used to identify the features in the experimental spectroscopic data. Results revealed that experimental IR and NMR spectra correlated very well with the corresponding computational spectra confirming that the DFToptimized equilibrium geometry of the most-stable conformer represents a probable analogue to the experimental conformation. Consequently, hydrogen bonds between [CI] À and three a-hydrogens of [P 666(14) ] + closest to the anion were identified by Natural Bond Orbital (NBO) analysis confirmed by the shifts in the corresponding IR bands.

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Single‐Entity Electrochemical Detection of As‐Prepared Metallic and Dielectric Nanoparticle Stochastic Impacts in a Phosphonium Ionic Liquid

Ahmadinasab

Stockmann

2022

ChemElectroChem

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Nanoparticles (NPs) are of considerable interest, owing to their enhanced catalytic activity and optical properties. Ionic liquids (ILs) are employed as a medium to prepare small (<20 nm in diameter) and relatively low dispersity (typically, ±1–2 nm) NPs. While ensemble techniques (e. g., UV/Vis) can provide a great deal of information, increasingly, single‐entity electrochemistry (SEE) has been used to provide physical insight into individual NP catalysis and dynamics. Herein, Pt NP impact current spikes for particles prepared in the IL phase and based on electrocatalytic amplification (ECA) of the borohydride oxidation reaction (BOR) were recorded during i‐t measurements. Additionally, direct oxidative LiBH4 nanocrystal (NC) impact signals were observed herein for the first time. By quantifying the charge transferred during the stochastic collision events, the radius of the NCs (rNC) was calculated (∼5.5 nm) and compares favorably with TEM images. Critically, small additions (1 % v/v) of a molecular, polar organic solvent (tetrahydrofuran, THF) disrupt the ILs supramolecular fluidic nature, which enhances NC impact frequency and the aggregation of Pt NPs.

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Optimization of transition metal nanoparticle-phosphonium ionic liquid composite catalytic systems for deep hydrogenation and hydrodeoxygenation reactions

Abstract: Stable metal nanoparticles in tetraalkylphosphonium ionic liquids can catalyze hydrogenations, as well as phenol hydrodeoxygenation, owing to presence of adventitious borates.

Cited by 18 publications

References 74 publications

Single LiBH4 nanocrystal stochastic impacts at a micro water|ionic liquid interface

Single LiBH4 nanocrystal stochastic impacts at a micro water|ionic liquid interface

Understanding Spectroscopic Features of Trihexyltetradecylphosphonium Chloride

Single‐Entity Electrochemical Detection of As‐Prepared Metallic and Dielectric Nanoparticle Stochastic Impacts in a Phosphonium Ionic Liquid

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