Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface

Robayo-Molina, Iván; Molina-Osorio, Andrés F.; Guinane, Luke; Tofail, Syed A. M.; Scanlon, Micheál D.

doi:10.1021/jacs.1c02481

Cited by 44 publications

(30 citation statements)

References 57 publications

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“…This can yield nanomaterials, potentially including quasi-2D materials, that are inaccessible in bulk solution. [27,28] Furthermore, certain interfaces between two immiscible electrolyte solutions (ITIES) may be electrochemically polarized, providing a driving force that may influence the kinetics of self-assembly or even enable electrosynthesis of interfacial thin films of materials. [29,30] Another consideration involves electrode architecture and the need to include conductive additives.…”

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confidence: 99%

Liquid Processing of Interfacially Grown Iron‐Oxide Flowers into 2D‐Platelets Yields Lithium‐Ion Battery Anodes with Capacities of Twice the Theoretical Value

Konkena

Kaur

Tian

et al. 2022

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papers have shown that converting bulk powder to 2D nanosheets yields significant capacity increases. [18][19][20] In addition, 2D platelet-shaped nanoparticles show great potential for use in battery electrodes due to shorter solid state diffusion lengths which can yield improved rate performance. [21] However, high aspect ratio 2D nanosheets can reduce the diffusion coefficient associated with ion transport within the electrolyte filled pores. [21] To avoid slow liquid phase diffusion while maintaining short solid state diffusion times, quasi-2D platelets with reduced aspect ratio are required. [21] This suggests that when using Fe 2 O 3 for battery applications there would be significant advantages to producing it in the form of quasi-2D platelets.Several synthetic routes have been proposed to generate nanoscale α-Fe 2 O 3 of various geometries including 2D platelets. [22][23][24][25] However, current methods are expensive to implement and typically include multiple complex steps which require high temperatures as well as templates or solid supports. A simpler alternative is to use a controllable, soft interfacial method to self-assemble well-defined and mesoporous nanostructures at an immiscible aqueous/organic interface. [26] The interface provides a defect-free, dimensionally-confined space to self-assemble unique 2D nanomaterials in a single step with perfect reproducibility. This can yield nanomaterials, potentially including quasi-2D materials, that are inaccessible in bulk solution. [27,28] Furthermore, certain interfaces between two immiscible electrolyte solutions (ITIES) may be electrochemically polarized, providing a driving force that may influence the kinetics of self-assembly or even enable electrosynthesis of interfacial thin films of materials. [29,30] Another consideration involves electrode architecture and the need to include conductive additives. For Fe 2 O 3 , a number of carbon-based additives including 2D graphene, 1D carbon (nanofibers/nanotubes), and 0D nanocarbon has been extensively explored. [10,[31][32][33][34] We believe significant advantages are to be had from using carbon nanotubes (CNTs) as the conductive additive. We and others have shown that incorporating CNTs in electrodes based on both 2D [35][36][37] and 3D [38] materials allows them to approach their theoretical capacity. This is because the high conductivity of the CNTs allows effective charge distribution increasing both initial capacity, stability, and rate performance. [38][39][40] In addition, CNTs provide mechanical reinforcement to the electrode without the need for any additional binder. [38] This is particularly important for iron oxide-based anodes, where a large volume expansion is often observed upon lithiation which leads to particle de-cohesion and poor cycling performance. [7] We have shown previously that nanotubes lead to electrode toughening which imparts stability even in silicon anodes which display very high volume expansion. [38] In this paper we will combine the advantages associated with quasi-2D...

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confidence: 99%

Liquid Processing of Interfacially Grown Iron‐Oxide Flowers into 2D‐Platelets Yields Lithium‐Ion Battery Anodes with Capacities of Twice the Theoretical Value

Konkena

Kaur

Tian

et al. 2022

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“…In addition, the characteristic absorption peak (204 nm) of the A3 molecule was redshifted by 3 nm (204 to 207 nm) with the increase in A3 concentration, indicating that the A3 molecule could form J-aggregation in the mixed solvent. Although the aggregation states of both A1 and A3 molecules changed with increasing concentration, the H-aggregation exhibited a higher thermodynamic stability than the J-aggregation . It led to the dissociation of the A1 molecule aggregation state, exhibiting a significant effect on the system entropy.…”

Section: Resultsmentioning

confidence: 95%

Tuning Rheological Behaviors of Supramolecular Aqueous Gels via Charge Transfer Interactions

Yang

Shen

et al. 2021

Langmuir

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Rheological properties are critical for determining real applications of supramolecular gels in various fields. Correspondingly, the modulation of gel rheology will be very important for meeting real requirements. In this aspect, a few strategies were applied to tune the rheological behaviors of supramolecular gels, but some specific interactions like charge transfer (CT) interactions were less explored at the molecular level. Herein, we report a pyrene-containing derivative of diphenylalanine as a donor gelator and naphthalenediimide or 3,5dinitrobenzene as matching acceptor molecules. It was found that the viscoelastic properties and strength of the original gel could be tuned through addition of different acceptor molecules to the original gel with changing the ratios of the selected acceptor molecules. As a result, storage modulus was continuously adjusted over a wide range from 190,000 to 50,000 Pa by CT interactions. Furthermore, the mechanism of the CT-induced change in rheological properties was understood and clarified through relevant techniques (e.g., UV−Vis, fluorescence, and FT-IR spectroscopy and TEM). The findings in this work would provide a novel strategy to modulate the rheological properties of supramolecular gels for adaption to broader fields of real applications.

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“…[ 5–11 ] As for the preparation method for supramolecular hydrogels, supramolecular self‐assembly as a new class of effective method has proven to be promising for the construction of complex superstructures based on noncovalent interaction with tailor‐made properties in a scalable and sustainable manner. [ 12,13 ] The principal advantage of noncovalent interactions is reversibility, which allows supramolecular hydrogels to be distinguished from the covalently cross‐linked polymeric cousins by dynamic character. [ 14–18 ] In most cases, of particular interest is that supramolecular hydrogels can be divided into single‐component hydrogels and multicomponent hydrogels and the latter greatly enriches the formation of new types of structures at various levels.…”

Section: Introductionmentioning

confidence: 99%

Reversibly Compressible Supramolecular Aerogels with Low Density and Sound Insulation Performance

Chen

et al. 2022

Adv Materials Inter

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self-assembly as a new class of effective method has proven to be promising for the construction of complex superstructures based on noncovalent interaction with tailor-made properties in a scalable and sustainable manner. [12,13] The principal advantage of noncovalent interactions is reversibility, which allows supramolecular hydrogels to be distinguished from the covalently cross-linked polymeric cousins by dynamic character. [14][15][16][17][18] In most cases, of particular interest is that supramolecular hydrogels can be divided into single-component hydrogels and multicomponent hydrogels and the latter greatly enriches the formation of new types of structures at various levels. [19] As supramolecular assemblies often cooperatively integrate two or more of the components, these assemblies can be endowed with unique synergistic properties rather than the mere combination of the individual properties of each component. [20,21] Aerogels are well-known flexible materials formed by replacing the liquid of a gel with the gas while retaining the 3D network structure. [22][23][24] Such materials have been widely utilized in a myriad of fields as a result of their striking properties, such as extremely low density, high porosity, and unique mechanical properties. [25][26][27][28][29][30] Up to now, various aerogels, such as carbon-based, silicon-based, and polymer aerogels, have been prepared through hydrothermal methods, chemical vapor deposition, 3D printing, and self-assembly. [31][32][33] Ideally, supramolecular aerogels can be derived from the parental hydrogels by depleting the contained water. Although there already appeared several supramolecular aerogels achieved from supramolecular organogels, hardly any were obtained from supramolecular hydrogels to the best of our knowledge. [23,24,[34][35][36] Compared with the mentioned above aerogels, supramolecular aerogels are achieved from small organic molecules in solvents with no requirement for any additional polymer binders and subsequently remove solvents, thus a supramolecular material with a 3D network structure is obtained. [7,37] Moreover, most of the supramolecular hydrogels consist of flexible fibers with a high aspect ratio. The fiber structure remaining after transferring to supramolecular aerogels gives them some mechanical properties to resist external stress stimulation, such as rigid or reversible compressibility. [38][39][40][41][42] Therefore, supramolecular aerogels are featured by simple preparation, low cost, easy degradation, energysaving, excellent mechanical properties, and environmental friendliness, which possess promising research prospects. [43] It is still a great challenge for supramolecular materials to be used as polymer systems. Here, reversibly compressible supramolecular aerogels with low density and sound insulation performance are reported, which are exclusively composed of small molecules. It is found that the mixture of melamine and isonicotinic acid can form supramolecular hydrogel. Then it could be transformed into aerogel v...

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Pathway Complexity in Supramolecular Porphyrin Self-Assembly at an Immiscible Liquid–Liquid Interface

Cited by 44 publications

References 57 publications

Liquid Processing of Interfacially Grown Iron‐Oxide Flowers into 2D‐Platelets Yields Lithium‐Ion Battery Anodes with Capacities of Twice the Theoretical Value

Liquid Processing of Interfacially Grown Iron‐Oxide Flowers into 2D‐Platelets Yields Lithium‐Ion Battery Anodes with Capacities of Twice the Theoretical Value

Tuning Rheological Behaviors of Supramolecular Aqueous Gels via Charge Transfer Interactions

Reversibly Compressible Supramolecular Aerogels with Low Density and Sound Insulation Performance

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