Metal–Organic Frameworks with Target‐Specific Active Sites Switched by Photoresponsive Motifs: Efficient Adsorbents for Tailorable CO<sub>2</sub> Capture

Jiang, Yao; Tan, Peng; Qi, Shi‐Chao; Liu, Xiaoqin; Yan, Jiahui; Fan, Fan; Sun, Lin‐Bing

doi:10.1002/anie.201900141

Cited by 184 publications

(102 citation statements)

References 57 publications

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“…Additional control experiments demonstrated that a 10% decrease in CO 2 uptake corresponds to 10 °C increase in the overall temperature of the sample. Similar effects, albeit more pronounced (>40%) were found for nonfluorinated azobenzene-decorated UiO-66(Zr) 108 and DMOFs 109 upon in situ exposure to UV-light and in mixed composite materials with polymers as secondary adsorbents 110 . The opposite effect following azobenzene E→Z isomerization on the uptake of CO 2 in a porous organic polymer decorated with pendant azobenzenes was reported by Zhang and coworkers.…”

Section: Gas Uptake Storage Separation and Releasesupporting

confidence: 61%

Photoresponsive porous materials

et al. 2021

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Section: Gas Uptake Storage Separation and Releasesupporting

confidence: 61%

Photoresponsive porous materials

et al. 2021

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“…Since the affinity of most MOFs toward CO 2 is rather low, Sun and co‐workers used an UiO‐66 MOF with AB side groups and embedded tetraethylenepentamine to increase the CO 2 affinity . Similar to a previous study by these authors in mesoporous silica, due to the attractive interaction between cis AB and the amine, the attractive CO 2 adsorptions sites were blocked upon photoisomerization.…”

Section: Photoswitchable Mofs From Photochromic Moleculesmentioning

confidence: 94%

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

2019

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In recent years, a particularly attractive and novel strategy has become available for the fabrication of photoresponsive, porous, and crystalline molecular solids from appropriately functionalized chromophoric linkers. The crystallinity of these materials allows a rather straightforward description and analysis using theoretical methods, thus tremendously accelerating the design of novel materials. This new class of crystalline molecular solids is referred to as metal-organic frameworks, MOFs (or porous coordination polymers, PCPs). [1] MOFs are constructed from metal-/metal-oxo nodes and organic linkers (Figure 1). The incorporation of photoactive species into MOFs may be realized by using them as linkers (method L) or attaching them to a linker (method A), as shown in Figure 1a. In addition, the porosity of MOFs allows the loading of chromophoric compounds as guests (method G) into the pores of this interesting framework material.In this review article, we mainly focus on organic photoactive species, which are either simply loaded as guests into porous MOFs or used after appropriate functionalization as building blocks for the construction of the framework (methods L, A, and G). [2] It is important to note that in the context of photoresponsive behavior, MOFs carry a potential which by far exceeds that of nonporous coordination polymers. This is because simple loading of guest/solvent molecules of different size/polarity/functionality in the MOF pores can impart a large optical response, which is useful, e.g., for sensing applications. [3] As an example, the solvent-dependent optical response or solvatochromism [4] is illustrated in Figure 1b. Such effects cannot be realized for nonporous coordination polymers.The different types of photoresponsive molecules addressed in this review can be grouped into two classes. The first contains molecules where the structure remains essentially unchanged upon light-induced electronic excitation, and the second contains molecular species that change their structure or conformation upon absorption of photons (molecular switches).Light with a wavelength in the range 200-800 nm (6.2-1.5 eV) can excite a molecule to a transient excited electronic state. The transient state then decays to a low-energy state, either the parent ground state or another longer-lived excited state. Decay time scales are in the range 10 −12 -10 1 s, and the released energy can be radiative or nonradiative in nature. For many applications, nonradiative energy loss is unwanted, When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal-organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coo...

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“…Additionally, the π‐complexation‐based materials usually present limited stability especially when exposed to water and sulfides, 11,24 which is unfavorable for practical applications. By comparison, kinetic separation is considered as a more energy‐efficient way, as it provides the potential to achieve effective gas separation via mild physisorption interactions, which can greatly lower the energy cost to regenerate the adsorbents 25‐27 . However, there are only a handful of porous materials exhibiting really high efficiency for kinetics‐driven C 3 H 6 /C 3 H 8 separation, 3,28 because to precisely control over the pore size so as to match with the kinetic diameters of C 3 H 6 and C 3 H 8 is challenging.…”

Section: Introductionmentioning

confidence: 99%

Separation of propylene and propane with a microporous metal–organic framework via equilibrium‐kinetic synergetic effect

Ding

Zhang

et al. 2020

AIChE Journal

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Adsorption separation of olefin and paraffin can greatly lower the energy consumption associated with the currently utilized distillation technique but remains a great challenge. Herein, we report the efficient separation of propylene (C3H6) and propane (C3H8) in a phosphate anion‐functionalized metal–organic framework (MOF) ZnAtzPO4 by synergetic effect of equilibrium and kinetics. The material features periodically expanded and contracted apertures decorated with electronegative groups, offering eligible pore shape and pore chemistry to effectively trap C3H6 under moderate isosteric heat of adsorption (27.5 kJ mol−1) while obstruct the diffusion of C3H8. It simultaneously combines excellent thermodynamic selectivity (uptake ratio of 1.71) and kinetic selectivity (~31) for C3H6/C3H8 separation, meanwhile can be easily regenerated. Breakthrough experiment for C3H6/C3H8 gas mixture was conducted and confirmed the outstanding separation capability of ZnAtzPO4. The equilibrium and kinetics cooperative C3H6/C3H8 adsorption separation was for the first time found in anion‐functionalized MOFs, and further confirmed by computational studies.

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Metal–Organic Frameworks with Target‐Specific Active Sites Switched by Photoresponsive Motifs: Efficient Adsorbents for Tailorable CO₂ Capture

Cited by 184 publications

References 57 publications

Photoresponsive porous materials

Photoresponsive porous materials

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Separation of propylene and propane with a microporous metal–organic framework via equilibrium‐kinetic synergetic effect

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Metal–Organic Frameworks with Target‐Specific Active Sites Switched by Photoresponsive Motifs: Efficient Adsorbents for Tailorable CO2 Capture

Cited by 184 publications

References 57 publications

Photoresponsive porous materials

Photoresponsive porous materials

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

Separation of propylene and propane with a microporous metal–organic framework via equilibrium‐kinetic synergetic effect

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Product

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Metal–Organic Frameworks with Target‐Specific Active Sites Switched by Photoresponsive Motifs: Efficient Adsorbents for Tailorable CO₂ Capture