Assembly of Nanoscale Objects at the Liquid/Liquid Interface

Booth, Samuel G.; Dryfe, Robert A. W.

doi:10.1021/acs.jpcc.5b07733

Cited by 124 publications

(113 citation statements)

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“…32,33,78 In addition, a blue shift of 4 cm -1 is also observed for the G band during the experiment. When the polarization is applied in the absence of aqueous phase K 4 [Fe(CN) 6 ] (Figure 6d), no spectroscopic changes are observed for the CNTs, confirming that the rest of the spectral data discussed here arise from PB deposition.…”

Section: Resultssupporting

confidence: 67%

“…At negative polarization, the transfer takes place with Cl -and BTPPA + from the aqueous and organic phases, respectively. [1][2][3][4][5]50 The presence of the CNTs at the interface increases the current in the voltammetry, as observed in Figure 2. This increase in current could be related to the presence of the Fe species within the CNTs, as no such increase in background current was observed in a previous study with CNTs (single-walled type) adsorbed at the L/L interface.…”

Section: Resultsmentioning

confidence: 67%

“…Although no significant change is observed in the voltammetric profile during the cycles, PB was deposited, to different degrees, in all the acidic media in the presence of CNTs, characterized by a clear blue color at the interface, while no PB formation was noted in the absence of CNTs. Consequently, it can be concluded that under these conditions, iron species from CNTs became available while no decomposition of K 4 [Fe(CN) 6 ] occurs, creating an ideal system for composite preparation.…”

Section: Resultsmentioning

confidence: 99%

“…As the laser tracks up through the interface, these bands are seen to decrease rapidly and then disappear once the laser reaches the aqueous phase, where no signal is present. When K 4 [Fe(CN) 6 ] is present in the aqueous phase, a small signal at 2132 cm -1 is observed within the meniscus of the L/L interface. However, with CNTs assembled at the interface, the profile changes significantly.…”

Section: Resultsmentioning

confidence: 99%

“…Driven by the decrease in the L/L interfacial free energy, particles dispersed or synthesized in a biphasic system spontaneously migrate to the interface formed by the two liquids. [3][4][5] Due to the ease of formation and robust nature of L/L interfaces, they have been utilized in a wide range of different applications. The L/L system can be used simply as a means to assemble previously synthesized materials into organized arrays or thin films, such as carbon nanostructures or metal nanoparticles.…”

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confidence: 99%

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Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Husmann

Booth

Zarbin

et al. 2018

J. Braz. Chem. Soc.

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The iron complex hexacyanoferrate (Fe 4 [Fe(CN) 6 ] 3 ), known as Prussian Blue (PB), was electrodeposited over a free-standing carbon nanotube (CNT) film assembled at the interface between two immiscible liquids, water and 1,2-dichlorobenzene. Polarization of the interface achieved through a fixed potential or under potential variation enabled iron present inside CNTs to generate a stable CNT/PB composite. We report herein on the observation that the deposition of PB is dependent on both the pH and applied potential. It was found that aqueous phases containing K 3 [Fe(CN) 6 ] can decompose under an applied potential, while those containing K 4 [Fe(CN) 6 ] presented more stable behavior making it a suitable precursor for PB synthesis. The electrodeposition and modification of the interface was followed by in situ spectroelectrochemical Raman spectroscopy, which indicated that an increase in signal due to PB formation was acompanied by changes in the CNT bands due to modification of the CNT walls by decoration with PB, forming a composite structure. Keywords: liquid-liquid interface, Prussian Blue, carbon nanotubes, immiscible liquids IntroductionBiphasic liquid/liquid (L/L) systems have been used for a long time, either for the study of interfacial electron and ion transfer reactions or for the synthesis and assembly of micro and nano-sized materials.1,2 The interface between two immiscible liquids provides a defect-free environment suitable for controlled homogeneous particle deposition. Driven by the decrease in the L/L interfacial free energy, particles dispersed or synthesized in a biphasic system spontaneously migrate to the interface formed by the two liquids. [3][4][5] Due to the ease of formation and robust nature of L/L interfaces, they have been utilized in a wide range of different applications. The L/L system can be used simply as a means to assemble previously synthesized materials into organized arrays or thin films, such as carbon nanostructures or metal nanoparticles. 6,7 Alternatively, materials can be both synthesized and assembled by using the L/L interface as the region of contact between reactants located in the different phases. [8][9][10] As an alternative to spontaneous reactions occurring at the point of contact between the two phases, material deposition can also occur by electrochemical polarization of the interface. 11,12 In addition to standard synthetic parameters such as concentration, time or pH, the applied potential and polarization of the interface between the two immiscible electrolyte solutions (ITIES) governs the rate of ion and electron transfer between the phases, allowing significant control over synthetic procedures. 1,2,13,14 By combining these different approaches to utilize the L/L interface, composite structures can be prepared using one material as the support and/or nucleation site for the other. 15,16 Previously, it has been observed that particle or polymer formation was possible, under stirring, on the surface of carbon nanostructures present in a L/L sy...

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Section: Resultssupporting

confidence: 67%

Section: Resultsmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Husmann

Booth

Zarbin

et al. 2018

J. Braz. Chem. Soc.

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Nanoscale Assembly of 2D Materials for Energy and Environmental Applications

et al. 2020

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Rational design of 2D materials is crucial for the realization of their profound implications in energy and environmental fields. The past decade has witnessed significant developments in 2D material research, yet a number of critical challenges remain for real‐world applications. Nanoscale assembly, precise control over the orientational and positional ordering, and complex interfaces among 2D layers are essential for the continued progress of 2D materials, especially for energy storage and conversion and environmental remediation. Herein, recent progress, the status, future prospects, and challenges associated with nanoscopic assembly of 2D materials are highlighted, specifically targeting energy and environmental applications. Geometric dimensional diversity of 2D material assembly is focused on, based on novel assembly mechanisms, including 1D fibers from the colloidal liquid crystalline phase, 2D films by interfacial tension (Marangoni effect), and 3D nanoarchitecture assembly by electrochemical processes. Relevant critical advantages of 2D material assembly are highlighted for application fields, including secondary batteries, supercapacitors, catalysts, gas sensors, desalination, and water decontamination.

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Freestanding Ultrathin Nanoparticle Membranes Assembled at Transient Liquid–Liquid Interfaces

Ouay

Guldin

Luo

et al. 2016

Adv Materials Inter

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as well as noncovalent [ 17,19 ] reticulation or through the coassembly of the NPs with polymers, [ 29 ] DNA [ 30 ] or peptides. [ 31 ] Besides the classical thin-fi lm assembly on a solid substrate (drop casting, [ 32 ] spincoating, [ 27,33 ] layer-by-layer deposition [ 8 ] ) followed by a detachment step, interfacial assembly, and especially liquid-liquid assembly, is a very effi cient way to obtain well-defi ned fi lms or membranes [34][35][36][37] (please note that in this context, we defi ne as membrane any freestanding thin layer, regardless of selective mass-transport properties). These approaches rely on the possibility of NPs to adsorb and pack into a dense network at an interface. This can occur if the free energy of the nanoparticles bound at the interface is lower than that of the NPs in either of the two phases. [38][39][40] The surface of NPs should thus possess specifi c wetting properties to guarantee a stable adsorption at the interface. Such behavior can be obtained using nanoparticles with a Janus-type anisotropic surface functionalization [ 41 ] or having systems that will spontaneously break their symmetry in situ. [ 42 ] This can also be obtained by carefully modifying locally the properties of one of the solvents to create a layer of intermediate characteristics, for instance, by injecting locally a compatibilizing reagent such as ethanol [ 43 ] or by applying an electric fi eld. [ 44 ] Hereby, we propose an innovative approach to achieve the formation of ultrathin free-standing and mechanically resilient membranes. The membranes are constituted of gold nanoparticles (AuNPs) that are reticulated by bridging mercaptopropyltrimethoxysilane (MPTMS) ligands which can cross-link through the formation of Si O Si bonds. Our approach relies on the formation of an unstable oil-in-water emulsion, in which AuNPs assemble at the surface of the oil droplets. Upon coalescence of the droplets, the decreasing available surface causes the AuNPs to close-pack and cross-link via the MPTMS ligands, forming an ultrathin membrane that remains freestanding in the water-phase. This dynamic interfacial assembly guarantees the presence of only a few NP-layers, with monolayer-thin domains easily obtained over several square-millimeters. Furthermore, the membranes can then be transferred onto solid or holey support substrates. This synthetic route is compatible with the presence of functional dopants that are physically immobilized in the AuNPs network, making this a promising way to form functional membranes by combining targeted properties through co-assembly. Since the preparation procedure involves the intimate contact of the water and oil phases A synthetic route is presented for the realization of ultrathin freestanding nanoparticle membranes that are built of gold nanoparticles protected with trimethoxysilane-bearing ligands. The mechanism relies on interfacial assembly in an oil-water mixture. Upon shaking, nanoparticles are transported to the liquid-liquid interface of the oil droplets and form a network thr...

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Assembly of Nanoscale Objects at the Liquid/Liquid Interface

Cited by 124 publications

References 143 publications

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Nanoscale Assembly of 2D Materials for Energy and Environmental Applications

Freestanding Ultrathin Nanoparticle Membranes Assembled at Transient Liquid–Liquid Interfaces

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