Impact of Synthesis Parameters on the Formation of Defects in HKUST‐1

Zhang, Wenhua; Kauer, Max; Guo, Ping; Kunze, Sebastian; Cwik, Stefan; Wang, Yuemin; Epp, Konstantin; Kieslich, Gregor; Fischer, Roland A.

doi:10.1002/ejic.201601239

Cited by 41 publications

(45 citation statements)

References 43 publications

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“…The disassembly of 1 copper cluster and 4 linkers (paddlewheels) was considered the main reason of defect formation in HKUST-1 45,46 ; an illustration of this mechanism is shown in Fig. 8a,b.…”

Section: Resultsmentioning

confidence: 99%

Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy

Doan

Sartbaeva

Eloi

et al. 2019

Sci Rep

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Introducing hierarchical pore structure to microporous materials such as metal-organic frameworks (MOFs) can be beneficial for reactions where the rate of reaction is limited by low rates of diffusion or high pressure drop. This advantageous pore structure can be obtained by defect formation, mostly via post-synthetic acid etching, which has been studied extensively on water-stable MOFs. Here we show that a water-unstable HKUST-1 MOF can also be modified in a corresponding manner by using phosphoric acid as a size-selective etching agent and a mixture of dimethyl sulfoxide and methanol as a dilute solvent. Interestingly, we demonstrate that the etching process which is time- and acidity- dependent, can result in formation of defective HKUST-1 with extra interconnected hexagonal macropores without compromising on the bulk crystallinity. These findings suggest an intelligent scalable synthetic method for formation of hierarchical porosity in MOFs that are prone to hydrolysis, for improved molecular accessibility and diffusion for catalysis.

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Section: Resultsmentioning

confidence: 99%

Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy

Doan

Sartbaeva

Eloi

et al. 2019

Sci Rep

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“…According to their spatial extent, one distinguishes between short-range, mid-range, and long-range heterogeneities (Figure 1D and Figure 4), which may be characterized with dedicated spectroscopic methods (Box 1). Typical examples of short-range, subnanometer-scale heterogeneities are point defects, which are found as undercoordinated metal sites in, for example, MIL-53(Al,V) [41], or as isolated linker and node vacancies in, for instance, UiO-66 and HKUST-1 [42][43][44][45]. When these short-range heterogeneities coalesce, mid-range heterogeneities may arise of up to a few tens of nanometers in size.…”

Section: Trends Trends In In Chemistry Chemistrymentioning

confidence: 99%

Towards modeling spatiotemporal processes in metal–organic frameworks

Speybroeck

Vandenhaute

Hoffman

et al. 2021

Trends in Chemistry

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Metal-organic frameworks (MOFs) are hybrid materials constructed from metal clusters linked by organic linkers, which can be engineered for target functional applications in, for example, catalysis, sensing, and storage. The dynamic response of MOFs on external stimuli can be tuned by spatial heterogeneities such as defects and crystal size as well as by operating conditions such as temperature, pressure, moisture, and external fields. Modeling the spatiotemporal evolution of MOFs under operating conditions and at length and time scales comparable with experimental observations is extremely challenging. Herein, we give a status on modeling spatiotemporal processes in MOFs under working conditions and reflect on how modeling can be reconciled with in situ spectroscopy measurements. HighlightsMetal-organic frameworks (MOFs) can respond in an anomalous way to external stimuli, giving rise to dynamic bond rearrangement and/or large-amplitude structural transformations without breakage of the crystal.

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“…Thus, countless numbers of MOFs can be synthesized using different metal and organic linkers. [13][14][15] Generally, MOFs are synthesized as powders using solvo/hydrothermal techniques at elevated temperatures and high pressure. Such synthesis techniques require the extensive use of chemicals and specific activation techniques (e.g.…”

Section: Introductionmentioning

confidence: 99%

Electrodeposited Metal Organic Framework toward Excellent Hydrogen Sensing in an Ionic Liquid

Azhar

Hussain

Tadé

et al. 2020

ACS Appl. Nano Mater.

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The synthesis of thin films of metal organic frameworks (MOFs) is a rapidly growing area owing to the use of these highly functional nanomaterials for various applications. In this study, a thin layer of a typical MOF, copper benzene tricarboxylate (HKUST-1), was synthesized by electrodeposition on a glassy carbon (GC) electrode using a potential-step chronoamperometric technique at room temperature. Various characterization techniques including Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used to verify the successful deposition of the MOF film and its structure. The electrodeposited MOF crystals showed cuboctahedral morphology with macropores. The MOF-modified electrode was applied for hydrogen gas sensing in a room temperature ionic liquid (RTIL) for the first time.A four-fold increase in current was observed compared to a precious metal surface, i.e. platinum, and the electrode exhibited significant catalytic activity compared to the bare GC electrode, making it a very promising low cost material for hydrogen gas sensing applications.

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Impact of Synthesis Parameters on the Formation of Defects in HKUST‐1

Cited by 41 publications

References 43 publications

Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy

Defective hierarchical porous copper-based metal-organic frameworks synthesised via facile acid etching strategy

Towards modeling spatiotemporal processes in metal–organic frameworks

Electrodeposited Metal Organic Framework toward Excellent Hydrogen Sensing in an Ionic Liquid

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