Tuning the Properties of MOF‐808 via Defect Engineering and Metal Nanoparticle Encapsulation

Hardian, Rifan; Dissegna, Stefano; Ullrich, Aladin; Llewellyn, Philip; Coulet, Marie‐Vanessa

doi:10.1002/chem.202005050

Cited by 51 publications

(39 citation statements)

References 61 publications

(89 reference statements)

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“…[7] The structure of the MOF is dictated by coordination of organic linker molecules to its metal-oxo cluster secondary building unit (SBU), and strongly impacts the catalytic activity. [23][24][25][26][27][28][29][30][31][32][33][34] In our studies, metal node connectivity has profoundly impacted the reactivity of Zr-MOFs towards the peptide bond, with the 6-connected MOF-808 hydrolysing the model substrate glycylglycine much faster (t 1/2 = 0.71 h) than NU-1000 (8-connected, t 1/2 = 120 h) and UiO-66 (formally 12-connected, t 1/2 = 243 h). [12][13][14] These studies also confirmed that Zr-MOFs are highly stable and can be used for multiple reaction cycles with minimal loss of activity.…”

Section: Introductionmentioning

confidence: 97%

Enhancing the Catalytic Activity of MOF‐808 Towards Peptide Bond Hydrolysis through Synthetic Modulations

Simms

Parac‐Vogt

2021

Chemistry A European J

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The performance of MOFs in catalysis is largely derived from structural features, and much work has focused on introducing structural changes such as defects or ligand functionalisation to boost the reactivity of the MOF. However, the effects of different parameters chosen for the synthesis on the catalytic reactivity of the resulting MOF remains poorly understood. Here, we evaluate the role of metal precursor on the reactivity of Zr-based MOF-808 towards hydrolysis of the peptide bond in the glycylglycine model substrate. In addition, the effect of synthesis temperature and duration has been investigated. Surprisingly, the metal precursor was found to have a large influence on the reactivity of the MOF, surpassing the effect of particle size or number of defects. Additionally, we show that by careful selection of the Zr-salt precursor and temperature used in MOF syntheses, equally active MOF catalysts could be obtained after a 20 minute synthesis compared to 24 h synthesis.

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Section: Introductionmentioning

confidence: 97%

Enhancing the Catalytic Activity of MOF‐808 Towards Peptide Bond Hydrolysis through Synthetic Modulations

Simms

Parac‐Vogt

2021

Chemistry A European J

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“…4 However, these 12 linkers around the metal clusters block the active sites excessively that are potentially critical to the catalytic and adsorptive performance of the frameworks. 5 In this regard, several strategies have been studied to control the features of MOFs, 6 in particular, the introduction of mixed linkers, 7 mixed metals, 8 and linker functionalization 9 into the MOF structures. For example, UiO-66 containing dicarboxylate-based mixed linkers showed superior charge separation and photoactivity performance than that with neat linkers.…”

Section: Introductionmentioning

confidence: 99%

Tailoring Defect Density in UiO-66 Frameworks for Enhanced Pb(II) Adsorption

et al. 2021

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Defect engineering of metal organic frameworks offers potential prospects for tuning their features toward particular applications. Herein, two series of defective UiO-66 frameworks were synthesized via changing the concentration of the linker and synthetic temperature of the reaction. These defective materials showed a significant improvement in the capability of Pb(II) removal from wastewater. This strategy for defect engineering not only created additional active sites, more open framework, and enhanced porosity but also exposed more oxygen groups, which served as the adsorption sites to improve Pb(II) adsorption. A relationship among degree of defects, texture features, and performances for Pb(II) removal was successfully developed as a proof-of-concept, highlighting the importance of defect engineering in heavy metal remediation. To investigate the kinetic and adsorption isotherms, we performed adsorption experiments influenced by the time and concentration of the adsorbate, respectively. For the practicality of the materials, the most significant parameters such as pH, temperature, adsorbent concentration, selectivity, and recyclability as well as simulated natural surface water were also examined. This study provides a clue for the researchers to design other advanced defective materials for the enhancement of adsorption performance by tuning the defect engineering.

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“…The highly crystalline MOF-808 S (Figure S5, Supporting Information) has also been found to have some inherent crystal defects (1.87 linkers per SBU), similar to earlier reports. 54 Furthermore, a combination of 1 H NMR spectroscopy and ICP-OES was used to accurately quantify the defect density in MOF-808 A−D. 62,63 From 1 H NMR data, the amount of H 3 BTC and formic acid in the structure could be estimated, while from ICP-OES, the amount of Zr in the MOFs could be determined (detailed analysis, calculation, and spectra are provided in Supporting Information, Section S3.4).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

et al. 2022

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Controlled incorporation of missing-linker defect sites could be achieved in four sister metal−organic frameworks (MOFs) of MOF-808, namely, MOF-808 A−D via modulated synthesis. An impressive enhancement in proton conductivity is observed in these sister MOFs (increase from 10 −3 to 10 −1 S cm −1 ) as compared to a highly crystalline, low-in-defect variant of MOF-808. MOF-808 C, having optimized defect density, shows a proton conductivity of 2.6 × 10 −1 S cm −1 at 80 °C and 98% relative humidity−the highest value reported to date for pure MOF-based proton conductors without extensive structural modifications. The introduction of defects induces super-protonic conductivity by modifying different properties, like porosity, water sorptivity, and acidity. Furthermore, an assembly of this super proton-conducting MOF with Pt�a versatile hydrogen evolution reaction (HER) catalyst, has been studied with the objective to influence the catalytic activity. This MOFcatalyst assembly was found to have lower overpotential requirements, owing to an increase in local acidity and efficient proton management around the catalyst.

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Tuning the Properties of MOF‐808 via Defect Engineering and Metal Nanoparticle Encapsulation

Cited by 51 publications

References 61 publications

Enhancing the Catalytic Activity of MOF‐808 Towards Peptide Bond Hydrolysis through Synthetic Modulations

Enhancing the Catalytic Activity of MOF‐808 Towards Peptide Bond Hydrolysis through Synthetic Modulations

Tailoring Defect Density in UiO-66 Frameworks for Enhanced Pb(II) Adsorption

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

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