Tuning the nitric oxide release behavior of amino functionalized HKUST-1

Peikert, Katharina; McCormick, Laura J.; Cattaneo, Damiano; Duncan, Morven J.; Hoffmann, Frank; Khan, Arafat Hossain; Bertmer, Marko; Morris, Russell E.; Fröba, Michael

doi:10.1016/j.micromeso.2015.06.020

Cited by 42 publications

(54 citation statements)

References 42 publications

(31 reference statements)

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“…The incorporation of amino-functionalized trimesic acid linkers into HKUST-1 improved the quantity of NO released, but the stability remained poor. 203 Fe3O(OH)(BDC)3 (Fe-MIL-88) and a series of functionalized derivatives adsorb between 1 and 2.5 mmol NO g -1 MOF with no loss of crystallinity. 204 For therapeutic applications, only 5-14% of NO was released upon exposure to humid conditions, and it was noted that most of the NO was likely released prior to the measurement run, suggesting that these materials do not bind NO tightly enough to be stable for long term storage.…”

Section: No X Occurrence Applicationsmentioning

confidence: 99%

Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture

2019

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Metal-organic frameworks (MOFs) have demonstrated their utility for a variety of applications involving the storage, separation, and sensing of weakly interacting gases of high purity. Exposure to more realistic, impure gas streams and interactions with corrosive and coordinating gases raises the question of chemical robustness, which remains a paramount concern for practical applications of MOFs. However, factors that determine the stability of MOFs remain incompletely understood. Although past researchers attempted to categorize framework materials as either thermodynamically stable or kinetically stable, recent work has elucidated an energetic penalty for porosity for all materials in this class with respect to a dense material. The metastability of porous phases has important implications for the design of materials for gas storage, heterogeneous catalysts, and electronic materials. Here, we focus on two main strategies for stabilization of the porous phase, either by using inert metal ions, or by increasing the heterolytic metal-ligand bond strength, both of which increase the activation barrier for framework collapse. These two strategies have led to exceptionally robust materials for the capture of coordinating and corrosive gases such as water vapor, ammonia, H2S, SO2, NOx, and even elemental halogens, and we review the progress in designing stable materials for these gases. Looking forward, we envision that the continued pursuit of strategies for kinetic stabilization in the synthesis of new MOFs will provide increasing numbers of robust frameworks suited to harsh conditions, and that short-term stability towards these challenging gases will be predictive of long-term stability for applications in less demanding environments.

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Section: No X Occurrence Applicationsmentioning

confidence: 99%

Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture

2019

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“…Following, after the purge with N 2 at 130 °C in mZIF‐8 there was a partial release of a small proportion of the retained NO, showing that these new sites had also a strong interaction. Such increase in the nitric oxide retention can be explained because the generation of a larger amount of exposed Zn−OH and nitrogen‐containing terminal groups in the mZIF‐8 surface, as it was previously demonstrated, which can interact with this molecule in a similar way to what happened with amino functionalized MOFs . The boosting effect achieved by the post‐synthetic modification in the nitric oxide retention has great practical relevance in the capture of this dangerous environmental pollutant gas.…”

Section: Resultsmentioning

confidence: 99%

“…Such increase in the nitric oxide retention can be explained because the generation of a larger amount of exposed ZnÀ OH and nitrogen-containing terminal groups in the mZIF-8 surface, as it was previously demonstrated, which can interact with this molecule in a similar way to what happened with amino functionalized MOFs. [42,43] The boosting effect achieved by the post-synthetic modification in the nitric oxide retention has great practical relevance in the capture of this dangerous environmental pollutant gas. In addition, the strong retention of nitric oxide onto the ZIF-8 centres could be useful in medical applications, since the use of MOFs as nitric oxide dosing vehicles for local anesthetic has been proposed.…”

Section: Molecular Interaction With Nitric Oxidementioning

confidence: 99%

Post‐Synthetic Modification of ZIF‐8 Crystals and Films through UV Light Photoirradiation: Impact on the Physicochemical Behavior of the MOF

et al. 2019

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The physicochemical modification of Metal‐Organic Frameworks (MOFs) is a current challenge in the search to improve their performance in different technological applications. In this work we analyze the post‐synthetic modification of ZIF‐8 crystals and films through a simple and clean treatment that involves the exposure to a UV lamp under environmental conditions. It is demonstrated that a short treatment alters the MOF structure and chemistry, providing a modified ZIF‐8 due to partial disconnections of its structure which increase the amount of terminal surface species such as Zn−OH and −C=N‐H, but without compromising the overall MOF structure, specific surface area or thermal stability. Additionally, it leads to changes in several properties of the ZIF‐8, such as its capacity to accumulate charge through pseudocapacitive processes, its interaction with nitric oxide and its light absorption behavior. This strategy of modifying ZIF‐8 without the use of chemicals through a gentle disconnection of its own structure could open new perspectives of post‐functionalization of crystals and films of ZIF‐8 to be used in a wide range of applications.

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“…65 A variety of MOFs featuring open metal sites, such as, HKUST-1, the MOF-74 (CPO-27) family, and MIL-88(Fe) derivatives, have been explored for the purpose of NO storage and release, but these do not enable further NO reactivity. [66][67][68][69][70][71][72][73] Of relevance here are reports where NO engages in reactivity mimicking that of metalloenzymes. For instance, cation exchange of Fe(II) into MOF-5 yields Fe-MOF-5 featuring a FeZn 3 O cluster in the SBU.…”

Section: Nitrogen Monoxidementioning

confidence: 99%