Reticular chemistry in the rational synthesis of functional zirconium cluster-based MOFs

Chen, Zhijie; Hanna, Sylvia L.; Redfern, Louis R.; Alezi, Dalal; İslamoğlu, Timur; Farha, Omar K.

doi:10.1016/j.ccr.2019.01.017

Cited by 377 publications

(289 citation statements)

References 163 publications

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“…Due to the exceptional chemical and thermal stability, UiO-66 has become one of the most studied MOFs since its invention in 2008 [43,[46][47][48][49]. UiO-66 can be easily functionalized with different functional groups on account of its isoreticular chemistry [5], however, a vast majority of these studies involve N,N-dimethylformamide (DMF), a toxic organic solvent, and elevated temperatures [5]. We recently reported an inexpensive, scalable, and environmentally benign procedure to synthesize UiO-66 derivatives (UiO-66-(COOH) 2 and UiO-66-F 4 ) in water at room temperature [42].…”

Section: Resultsmentioning

confidence: 99%

“…Metal-organic frameworks (MOFs) [1][2][3][4][5] are a promising class of crystalline porous materials with a wide range of applications including but not limited to heterogeneous catalysis [6][7][8][9][10], enzyme and nanoparticle encapsulation [11][12][13][14], water capture [15][16][17][18][19], gas storage, and separation [20][21][22][23][24][25]. Importantly, physical and chemical properties of MOFs can be fine-tuned with the help of reticular chemistry, where pre-selected molecular building blocks are combined to yield pre-designed frameworks for targeted applications [26][27][28][29][30].…”

Section: Introductionmentioning

confidence: 99%

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Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption

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Aqueous synthesis of metal–organic frameworks (MOFs) at room temperature offers many advantages such as reduction in the generation of toxic byproducts and operation costs, as well as increased safety in the material’s production. Functional group-bearing MOFs have received growing attention compared to nonfunctionalized analogues due to enhanced adsorption properties of the former in many cases. Here, we report an aqueous solution-based synthesis of a robust zirconium MOF, UiO-66-NO2, at room temperature. We evaluated the phase purity, porosity, thermal stability, particle morphology and size of the resulting material. High uptake, as well as near complete recyclability of water and ethanol vapor isotherms at room temperature supports the potential of UiO-66-NO2 as a solid adsorbent in adsorption-based cooling applications or water harvesting systems.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption

et al. 2019

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“…The pore size and topology of the framework can be finely tuned by selecting appropriate linkers and metal nodes. Isoreticular MOFs, defined as frameworks with the same structural topology, are formed by using a library of related organic linkers with different lengths and functionalities [16][17][18] . The tremendous control over pore size and chemical environment in isoreticular MOFs provides the ability to independently observe structural and chemical factors that impact electrochemical processes.…”

Section: Tunable Mof Attributes For Electrochemical Applicationsmentioning

confidence: 99%

Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices

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Metal-organic frameworks (MOFs) are a class of porous materials with unprecedented chemical and structural tunability. Their synthetic versatility, long-range order, and rich host-guest chemistry make MOFs ideal platforms for identifying design features for advanced functional materials. This review addresses synthetic approaches to control MOF attributes for realizing material properties such as charge conductivity, stability, surface area, and flexibility. Along with an updated account on MOFs employed in batteries and supercapacitors, new directions are outlined for advancing MOF research in emergent technologies such as solid-state electrolytes and battery operation in extreme environments. G lobal demands for clean energy storage and delivery continue to push developing technology to its limits. Batteries and supercapacitors are among the most promising technologies for electrical energy storage owing to their portability and compact size for on-demand usage. Despite their promise, chemical and physical limitations of existing materials hinder performance and require new, creative solutions. For instance, polymers and conductive carbon materials are relatively inexpensive, scalable, and synthetically tunable but can lack physical and chemical stability for device implementation. On the other hand, solid inorganic materials, such as metal oxides and silicon, are used as electrode materials due to their robust structure and redox-active sites. However, sluggish ion diffusion of metal oxides limit charge/ discharge rate capabilities and large volumetric changes lead to mechanical instability. Drawbacks in these current platforms motivate the discovery and development of new materials for advanced energy storage devices. Metal-organic frameworks (MOFs) are attractive candidates to meet the needs of nextgeneration energy storage technologies. MOFs are a class of porous materials composed of metal nodes and organic linkers. Their modular nature allows for great synthetic tunability, affording both fine chemical and structural control. With creative synthetic design, properties such as porosity, stability, particle morphology, and conductivity can be tailored for specific applications. As the needs of each energy storage device are different, this synthetic versatility of MOFs provides a method to optimize materials properties to combat inherent electrochemical

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“…For this reason, metal-organic frameworks (MOFs) with a high degree of tunability are attractive support materials (Vermoortele et al, 2012;Vandichel et al, 2015;Liu et al, 2018;Palmer et al, 2018). Constructed from metal or metal cluster nodes linked via multitopic organic ligands, MOFs are an increasing popular class of designer materials due to the ability to obtain highly crystalline, porous, and stable structures (Yaghi et al, 2003;Kitagawa et al, 2004;Furukawa et al, 2013;Jiao et al, 2018;Chen et al, 2019;Yang and Gates, 2019).…”

Section: Introductionmentioning

confidence: 99%

Restricting Polyoxometalate Movement Within Metal-Organic Frameworks to Assess the Role of Residual Water in Catalytic Thioether Oxidation Using These Dynamic Composites

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Comprised of high valent metal centers connected via oxide bonds, polyoxometalates (POMs) have a rich history in redox reactions. These discrete metal oxide clusters often are immobilized on heterogeneous supports to increase stability and allow for recyclability for catalytic reactions. One such support is the metal-organic framework (MOF), NU-1000. When POMs are installed into NU-1000, they are first sited in the mesoporous channel. Upon application of heat and removal of some physisorbed water, the POMs migrate to the microporous channel, where some active sites are blocked by the MOF linkers, resulting in lowered catalytic activity. To restrict this movement from the mesopore, we report here the use of two MOFs, naphthalene dicarboxylate-modified NU-1000 (NU-1000-NDC) and NU-1008, as supports for the Keggin-type polyoxometalate (POM), H 3 PW 12 O 40 . Upon the application of heat, these frameworks were found to hinder or prevent the movement of the POM between channels by blocking the aperture(s) connecting the mesoporous and microporous channels. The composite POM@MOF materials were used for the oxidation of a mustard gas simulant, 2-cholorethyl ethyl sulfide, using H 2 O 2 as the oxidant. The POM@MOF catalysts exhibit enhanced reactivity when compared to the POM or MOF alone, more than doubling the initial rates. The activity trend in PW 12 @NU-1000-NDC matched that in PW 12 @NU-1000, where the scCO 2 -activated sample poised the POM in the mesopores to give greater substrate accessibility and enhance the reaction rate compared to the heated sample where the POMs are poised in the micropores. Contrary to these observed trends, PW 12 @NU-1008 prohibits POM migration and performs superior when water has been removed at elevated temperatures as the active sites are more accessible in the mesoporous channel.

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Reticular chemistry in the rational synthesis of functional zirconium cluster-based MOFs

Cited by 377 publications

References 163 publications

Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption

Green Synthesis of a Functionalized Zirconium-Based Metal–Organic Framework for Water and Ethanol Adsorption

Metal-organic framework functionalization and design strategies for advanced electrochemical energy storage devices

Restricting Polyoxometalate Movement Within Metal-Organic Frameworks to Assess the Role of Residual Water in Catalytic Thioether Oxidation Using These Dynamic Composites

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