Salting-in species induced self-assembly of stable MOFs

Li, Ke; Yang, Jian; Gu, Jinlou

doi:10.1039/c9sc01447k

“…Our ongoing research demonstrated that Hofmeister ions had an important effect on the growth process of MOFs. [10] A series of salting-in ions can facilitate the crystallization of MOFs through a unique solubilization-mediating mechanism so that many stable MOFs could be obtained in aqueous phase and mild conditions, which are compatible for the self-assembly of soft templates. These early studies strongly inspired us to develop a rational polymeric surfactant self-assembly strategy to obtain ordered large-pore mesoMOFs with excellent chemical stability based on the Hofmeister effect.…”

mentioning

confidence: 99%

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Li

¹

,

Yang

²

,

Huang

³

et al. 2020

Self Cite

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Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large‐size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting‐in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large‐pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large‐pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.

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“…À ions would attract and bridge Ce nodes to the BDC ligands (mediating). [10] The local concentration of the MOF precursors would increase by the mediation of ClO 4 À ions, which promoted the growth of the crystallized MOFs around the Ce-PEO complexes coronas (Step 2). The experimental scenarios agree with our proposal that no mesoporous structure could be obtained in the absence of ClO 4…”

Section: Zuschriftenmentioning

confidence: 99%

“…Fortunately, the Hofmeister effect, first noted in 1888, provides us a new perspective for overcoming these inherent limitations. Our ongoing research demonstrated that Hofmeister ions had an important effect on the growth process of MOFs . A series of salting‐in ions can facilitate the crystallization of MOFs through a unique solubilization‐mediating mechanism so that many stable MOFs could be obtained in aqueous phase and mild conditions, which are compatible for the self‐assembly of soft templates.…”

Section: Figurementioning

confidence: 99%

“…Therefore, after BDC ligands were added, NaClO 4 would accumulate around the ligands, weakening their hydrophobic aggregation and thereby improving their aqueous solubility (solubilization) . Simultaneously, the abundant ClO 4 − ions would attract and bridge Ce nodes to the BDC ligands (mediating) . The local concentration of the MOF precursors would increase by the mediation of ClO 4 − ions, which promoted the growth of the crystallized MOFs around the Ce‐PEO complexes coronas (Step 2).…”

Section: Figurementioning

confidence: 99%

“…À ions would attract and bridge Ce nodes to the BDC ligands (mediating). [10] The local concentration of the MOF precursors would increase by the mediation of ClO 4 À ions, which promoted the growth of the crystallized MOFs around the Ce-PEO complexes coronas (Step 2). The experimental scenarios agree with our proposal that no mesoporous structure could be obtained in the absence of ClO 4 À (Supporting Information, Figure S4), and the pore ordering and the crystallinities of pore walls of Ce-HMMOF-P were improved with the increase of ClO 4 À /Ce feed ratio varying from 0 to 3.6.…”

Section: Zuschriftenmentioning

confidence: 99%

See 2 more Smart Citations

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Li

¹

,

Yang

²

,

Lin

³

et al. 2020

Self Cite

View full text Add to dashboard Cite

Ordered mesoporous metal–organic frameworks (mesoMOFs) were constructed with a uniform pore size up to about 10 nm and thick microporous walls, opening up the possibility for the mass diffusion of large‐size molecules through crystalline MOFs. The synergistic effects based on triblock copolymer templates and the Hofmeister salting‐in anions promote the nucleation of stable MOFs in aqueous phase and the in situ crystallization of MOFs around templates, rendering the generation of a microcrystal with periodically arranged large mesopores. The improved mass transfer benefiting from large‐pore channels, together with robust microporous crystalline structure, endows them as an ideal nanoreactor for the highly efficient digestion of various biogenic proteins. This strategy could set a guideline for the rational design of new ordered large‐pore mesoMOFs with a variety of compositions and functionalities and pave a way for their potential applications with biomacromolecules.

show abstract

Hollow Mesoporous Metal Organic Framework Single Crystals Enabled by Growth Kinetics Control for Enhanced Photocatalysis

Zhao,

Wang,

Sun

et al. 2023

Adv Funct Materials

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The tailored design of hollow mesoporous metal−organic framework (MOF) single crystals to realize the unimpeded mass transport and long‐range carrier migration for advanced photoelectric applications is attractive while being a major challenge. Here, a kinetically mediated micelle assembly strategy is presented to synthesize hollow UiO‐66(Ce) single crystals in 1,3,5‐trimethylbenzene (TMB)‐H2O emulsion system with Pluronic F127/P123 as dual surfactants. This synthesis features the employment of modulator acetic acid, which can coordinate growth kinetics of MOFs, allowing the nucleation of MOF on block polymer micelles and transforming the self‐assembly of block polymer/MOF composite monomicelles from water to TMB/H2O emulsion interface and the growth of MOF from aggregation to oriented attachment, and thus ensuring the formation of hollow mesoporous UiO‐66(Ce) single crystals. Moreover, a precise control in cavity diameter from ≈0 to ≈600 nm, mesopore structure from close to radial and dendritic can be achieved by tuning the amount of TMB and the ratio of F127/P123. As a result, the hollow mesoporous UiO‐66(Ce) single crystals with large radial mesopores (≈25 nm) and high surface area (≈1061 m2 g) exhibit excellent photocatalytic performance for H2 generation owing to enhanced permeability and suppressed electron‐hole combination.

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Salting-in species induced self-assembly of stable MOFs

Abstract: A general strategy based on the Hoffmeister effect is proposed for the aqueous-phase and mild synthesis of stable metal–organic frameworks.

Cited by 49 publications

References 44 publications

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Ordered Large‐Pore MesoMOFs Based on Synergistic Effects of TriBlock Polymer and Hofmeister Ion

Hollow Mesoporous Metal Organic Framework Single Crystals Enabled by Growth Kinetics Control for Enhanced Photocatalysis

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