Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni

Yang, Jing; Morelock, Cody R.; Burtch, Nicholas C.; Mounfield, William P.; Hungerford, Julian; Walton, Krista S.

doi:10.1021/acs.iecr.5b03843

Cited by 162 publications

(110 citation statements)

References 44 publications

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“…The other patterns at 2Θ: 6.6°, 9.5°, 11.6° and 13.4° all come from CuBTC framework which is in agreement with the simulated XRD of pure CuBTC (Figure b). The patterns of mixed‐metal maghemite anchored AgCuBTC and mixed‐metal maghemite anchored NiCuBTC are very similar to their parent (Figure c–d) confirming the maintenance of the framework of CuBTC during modification as expected from the literature ,,…”

Section: Resultssupporting

confidence: 83%

The First C−Cl Activation in Ullmann C−O Coupling by MOFs

2018

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It was found that introduction of only 0.03 mol % Ag(I) into the framework of Cu3(BTC)2 ⋅ xH2O in maghemite anchored CuBTC activated the inert CuBTC astonishingly to exhibit unexpected high catalytic activity for C−Cl activation in coupling of chloroarenes with phenols without the use of expensive ligands. This is the first application of mixed‐metal MOFs in the C−X activation. Putting reusability and activity together, a TON over 15000 was obtained which is the highest TON compared with all its precedents even better than the results by Pd catalysts.

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Section: Resultssupporting

confidence: 83%

The First C−Cl Activation in Ullmann C−O Coupling by MOFs

2018

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“…a permanent loss of capacity. 6,30 Having established that the Ni sample is stable to water, stability testing was extended to the second stage and the Ni-CPO-27 sample was subjected to the wet flue gas exposure. Figure 4 shows the raw signal acquired during the final wet flue gas exposure.…”

Section: Stability Testsmentioning

confidence: 99%

Accelerated degradation of MOFs under flue gas conditions

et al. 2016

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The zero length column (ZLC) technique is used to investigate the stability of Mg- and Ni-CPO-27 metal–organic framework (MOF) crystals in the presence of water and humid flue gas. The design of the ZLC enables the stability test to be conducted over a considerably shorter time period and with lower gas consumption than other conventional techniques. A key advantage over other experimental methods for testing the stability of adsorbents is the fact that the ZLC allows us to quantify the amount adsorbed of every component present in the gas mixture. The developed protocol is based on a two-stage stability test. The samples were first exposed to a humid carbon dioxide and helium mixture in order to study the effect of water on the carbon dioxide adsorption capacity of the samples. In the second stage the samples were exposed to a flue gas mixture containing water. From the preliminary water stability test, the Ni-sample exhibited the highest tolerance to the presence of water, retaining approximately 85% of its pristine CO2 capacity. The Mg-MOFs deactivated rapidly in the presence of water. The Ni-CPO-27 was then selected for the second stage of the protocol in which the material was exposed to the wet flue gas. The sample showed an initial drop in CO2 capacity after the first exposure to the wet flue gas, followed by a stabilisation of the performance over several cycles.

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“…48 Concerning MOF-74, Jiao and co-workers have synthesized and characterized a series of MM-MOF-74 structures, replacing some of the Mg metal centers of Mg-MOF-74 with either Ni or Co atoms. 49 Their results show that the addition of a small amount of Ni (16 mol%) remarkably enhances the water stability of those systems.…”

Section: Introductionmentioning

confidence: 97%

Understanding and controlling water stability of MOF-74

et al. 2016

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Metal organic framework (MOF) materials in general, and MOF-74 in particular, have promising properties for many technologically important processes. However, their instability under humid conditions severely restricts practical use. We show that this instability and the accompanying reduction of the CO2 uptake capacity of MOF-74 under humid conditions originate in the water dissociation reaction H2O → OH+H at the metal centers. After this dissociation, the OH groups coordinate to the metal centers, explaining the reduction in the MOF's CO2 uptake capacity. This reduction thus strongly depends on the catalytic activity of MOF-74 towards the water dissociation reaction. We further show that-while the water molecules themselves only have a negligible effect on the crystal structure of MOF-74-the OH and H products of the dissociation reaction significantly weaken the MOF framework and lead to the observed crystal structure breakdown. With this knowledge, we propose a way to suppress this particular reaction by modifying the MOF-74 structure to increase the water dissociation energy barrier and thus control the stability of the system under humid conditions.

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Tuning the Kinetic Water Stability and Adsorption Interactions of Mg-MOF-74 by Partial Substitution with Co or Ni

Cited by 162 publications

References 44 publications

The First C−Cl Activation in Ullmann C−O Coupling by MOFs

The First C−Cl Activation in Ullmann C−O Coupling by MOFs

Accelerated degradation of MOFs under flue gas conditions

Understanding and controlling water stability of MOF-74

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