Synthesis of nanocrystals of Zr-based metal–organic frameworks with csq-net: significant enhancement in the degradation of a nerve agent simulant

Li, Peng; Klet, Rachel C.; Moon, Su‐Young; Wang, Yichen; Deria, Pravas; Peters, Aaron W.; Klahr, Benjamin M.; Park, Hea Jung; Al-Juaid, Salih S.; Hupp, Joseph T.; Farha, Omar K.

doi:10.1039/c5cc03398e

Cited by 205 publications

(191 citation statements)

References 61 publications

(15 reference statements)

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“…MOFs have been employed as catalysts and catalyst supports, in part because of their ordered nature, structural tunability, and permanent porosity . We and others have shown that fine‐tuning pore size, particle size, metal node connectivity and chemical composition can favorably affect the activity of MOF‐based catalysts in the hydrolysis of a nerve agent simulant, dimethyl 4‐nitrophenyl phosphate (DMNP). Importantly, DMNP has been shown to be effective for mimicking the reactivity of organophosphonate‐based nerve agents (Scheme ) .…”

Section: Figurementioning

confidence: 99%

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

et al. 2018

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Amino-functionalized zirconium-based metal-organic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly, the effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH , where the amino groups reside near the node, compared to UiO-67-m-NH , where they are directed away from the node. Herein, we show that the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents. The generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology. DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases; instead they control the microsolvation environment at the Zr -node active site and therefore increase the overall catalytic rates.

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Section: Figurementioning

confidence: 99%

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

et al. 2018

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“…In order to synthesize the MOF-525 crystals with various sizes, the additive amount of modulator (i.e., benzoic acid) during the synthetic process was changed to be 2.7 g, 2.0 g, 1.35 g, 1.1 g, and 0.9 g, respectively; similar strategies have been used to control the crystal size of other MOFs in literature. [42][43][44] The suspensions of MOF-525 crystals in DMF with a concentration of 20 mg/mL were prepared by the same protocol reported in details in the previous study. 41 For material characterizations, the dried powders of MOF-525 crystals were collected by the activation process reported previously.…”

Section: Preparation Of the Inks And Powders Of Mof-525 Crystalsmentioning

confidence: 99%

“…To synthesize zirconium-based porphyrinic MOF crystals with smaller sizes, benzoic acid, a well-known nucleation modulator for MOF synthesis, [42][43][44] was used at various concentrations in the solvothermal synthesis. The scanning electron microscopy (SEM) images of the synthesized MOF powders are shown in Fig.…”

Section: Ink Formulationmentioning

confidence: 99%

Inkjet-printed porphyrinic metal–organic framework thin films for electrocatalysis

Kung

Chang

et al. 2016

J. Mater. Chem. A

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In this study, a simple and effective direct inkjet printing method was developed to prepare porphyrinic metal-organic framework (MOF) thin films for electrocatalysis. First, crystals of a zirconium-based porphyrinic MOF (MOF-525) with crystal sizes ranging from 100 to 700 nm were synthesized by adjusting the content of benzoic acid in the solvothermal synthetic process. The synthesized crystals showed similar surface area of 2500 m 2 /g with a unique pore size of 1.85 nm. However, some structural defects was found in the smallest crystals of 100 nm due to the fast crystallization process. After suspended in dimethylformamide, the MOF crystal suspensions were inkjet printed to fabricate uniform MOF-525 thin film patterns. With the help of great precision in liquid deposition, thicknesses of the printed MOF-525 thin films can be accurately controlled by the number of printed layers. With smaller crystal size, the printed MOF thin films showed more compact stacking and better contact with the substrate. The printed MOF thin films were applied for electrocatalytic nitrite oxidation. The effects of both film thickness and crystal size on printed film morphology and electrocatalytic activity were investigated in details. The printed MOF nitrite sensor showed a great detection limit of 0.72 μM and a high sensitivity of 40.6 μA/mM-cm 2 . In summary, this study demonstrated the feasibility of the proposed printing process for electrochemically addressable MOF thin films and can be further applied for many other electrochemical applications.

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“…[6] Metal-organic frameworks (MOFs) are self-assembled, and atomically precise porous materials comprising metal ions/clusters and organic linkers. [8] We and others have shown that fine-tuning pore size, [9] particle size, [10] metal node connectivity [11] and chemical composition [12] can favorably affect the activity of MOF-based catalysts in the hydrolysis of anerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP). [8] We and others have shown that fine-tuning pore size, [9] particle size, [10] metal node connectivity [11] and chemical composition [12] can favorably affect the activity of MOF-based catalysts in the hydrolysis of anerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP).…”

mentioning

confidence: 99%

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

et al. 2018

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View full text Add to dashboard Cite

Amino-functionalized zirconium-based metalorganic frameworks (MOFs) have shown unprecedented catalytic activity compared to non-functionalized analogues for hydrolysis of organophosphonate-based toxic chemicals. Importantly,t he effect of the amino group on the catalytic activity is significantly higher in the case of UiO-66-NH 2 , where the amino groups reside near the node,c ompared to UiO-67-m-NH 2 ,w here they are directed away from the node. Herein, we showt hat the proximity of the amino group is crucial for fast catalytic activity towards hydrolysis of organophosphonate-based nerve agents.T he generality of the observed amine-proximity-dictated catalytic activity has been tested on two different MOF systems which have different topology.DFT calculations reveal that amino groups on all the MOFs studied are not acting as Brønsted bases;i nstead they control the microsolvation environment at the Zr 6 -node active site and therefore increase the overall catalytic rates.

show abstract

Synthesis of nanocrystals of Zr-based metal–organic frameworks with csq-net: significant enhancement in the degradation of a nerve agent simulant

Cited by 205 publications

References 61 publications

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

Inkjet-printed porphyrinic metal–organic framework thin films for electrocatalysis

Presence versus Proximity: The Role of Pendant Amines in the Catalytic Hydrolysis of a Nerve Agent Simulant

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