Kinetics Driven by Hollow Nanoreactors: An Opportunity for Controllable Catalysis

Yu, Zhihao; Ji, Na; Li, Xiaoyun; Zhang, Rui; Qiao, Yina; Xiong, Jian; Liu, Jian; Lü, Xuebin

doi:10.1002/ange.202213612

Cited by 2 publications

(1 citation statement)

References 136 publications

(163 reference statements)

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“…Reaction mechanisms are affected by confinement inside nanoscale reactors such as calixarenes, cucurbiturils, cyclodextrins, metal–organic frameworks (MOF), and zeolites [ 1 ]. Confinement acts on the potential energy surface (PES) topology, which is responsible for the kinetics (catalyzing or inhibiting reaction channels) but also changes the thermodynamics of the reaction because of the different interactions that the supramolecular host establishes with the reactants/products of the reaction [ 2 , 3 , 4 , 5 ]. The confinement inside a chemical host can have two major effects: the first occurs when the shape/volume of the host cavity (partly) restrains the guest system, and the second occurs when new chemical interactions between the host and guest are established.…”

Section: Introductionmentioning

confidence: 99%

Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes

et al. 2022

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Nanoscale control of chemical reactivity, manipulation of reaction pathways, and ultimately driving the outcome of chemical reactions are quickly becoming reality. A variety of tools are concurring to establish such capability. The confinement of guest molecules inside nanoreactors, such as the hollow nanostructures of carbon nanotubes (CNTs), is a straightforward and highly fascinating approach. It mechanically hinders some molecular movements but also decreases the free energy of translation of the system with respect to that of a macroscopic solution. Here, we examined, at the quantum mechanics/molecular mechanics (QM/MM) level, the effect of confinement inside CNTs on nucleophilic substitution (SN2) and elimination (syn-E2 and anti-E2) using as a model system the reaction between ethyl chloride and chloride. Our results show that the three reaction mechanisms are kinetically and thermodynamically affected by the CNT host. The size of the nanoreactor, i.e., the CNT diameter, represents the key factor to control the energy profiles of the reactions. A careful analysis of the interactions between the CNTs and the reactive system allowed us to identify the driving force of the catalytic process. The electrostatic term controls the reaction kinetics in the SN2 and syn/anti-E2 reactions. The van der Waals interactions play an important role in the stabilization of the product of the elimination process.

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Section: Introductionmentioning

confidence: 99%

Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes

et al. 2022

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Probing Ion Diffusion and Ion Sieving through Hollow Porous Silica Shells by Imaging the Mobility of Colloids Inside the Shells

Watanabe,

Welling,

Mendes

et al. 2024

Adv Materials Inter

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Ionic transport through porous membranes and porous materials has received enormous attention due to its importance to many applications. An innovative methodology is proposed to study ion diffusion and ion sieving through mesoporous silica membranes (shells). The mobility of fluorescently labeled core particles within a hollow porous shell, filled with an index‐matched electrolyte solution, is observed using confocal laser scanning microscopy. The core motion range, i.e., the area explored by the core within the hollow compartment, sensitively changed depending on the local ionic concentration. Monitoring transitions in the core motion range is a practical way to detect which ions can migrate through the shells and on what timescale. For instance, lithium and chloride ions easily diffused through the porous silica shells, resulting in a core motion range that changed relatively quickly upon change of the ion concentrations outside of the shell. However, the motion range changed significantly slower upon changing to a bigger cation (tetraoctylammonium ion). This proof of principle experiment can be explained by the Gibbs‐Donnan effect, revealing that the detection of core motion ranges is a good probe to measure both ion diffusion and ion sieving through porous membranes.

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Kinetics Driven by Hollow Nanoreactors: An Opportunity for Controllable Catalysis

Cited by 2 publications

References 136 publications

Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes

Deciphering the Reactive Pathways of Competitive Reactions inside Carbon Nanotubes

Probing Ion Diffusion and Ion Sieving through Hollow Porous Silica Shells by Imaging the Mobility of Colloids Inside the Shells

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