Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Klein, Ryan A.; Shulda, Sarah; Maguères, Pierre Le; Richardson, Rachelle K.; Morris, William; Brown, Craig M.; McGuirk, C. Michael

doi:10.1039/d1sc04618g

Cited by 25 publications

(63 citation statements)

References 88 publications

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“…The reversible structural transition of ZIF-65(Zn) is studied in detail and compared to other flexible ZIFs. To the best of our knowledge, the drastic contraction and expansion of the SOD cage and very large breathing effect (6.4 Å) reported herein for ZIF-65(Zn) are uncommon 25 , 29 , 39 , 44 , 57 .…”

Section: Introductionmentioning

confidence: 51%

“…The drastic displacive transition (6.4 Å) in the SOD cage (8.6 Å for II, 10.6 Å for III, and 15.0 Å for I) is indicative of the very large breathing effect of the ZIF-65(Zn) framework. During the transition of classical ZIF-7-II 44 to ZIF-7-I 14 , the adsorption of the guest molecules induces a small swelling of the SOD cage (11.3 Å × 16.1 Å–14.3 Å × 15.8 Å, Supplementary Fig. 14 ).…”

Section: Resultsmentioning

confidence: 99%

“…14 ). ZIFs reported to date typically feature a small displacive transition due to the rigid zeolite topology 25 , 29 , 39 , 44 , 57 (Supplementary Fig. 14 and Supplementary Table 5 ).…”

Section: Resultsmentioning

confidence: 99%

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Large breathing effect in ZIF-65(Zn) with expansion and contraction of the SOD cage

et al. 2022

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The flexibility and guest-responsive behavior of some metal-organic frameworks (MOFs) indicate their potential in the fields of sensors and molecular recognition. As a subfamily of MOFs, the flexible zeolitic imidazolate frameworks (ZIFs) typically feature a small displacive transition due to the rigid zeolite topology. Herein, an atypical reversible displacive transition (6.4 Å) is observed for the sodalite (SOD) cage in flexible ZIF-65(Zn), which represents an unusually large breathing effect compared to other ZIFs. ZIF-65(Zn) exhibits a stepwise II → III → I expansion between an unusual ellipsoidal SOD cage (8.6 Å × 15.9 Å for II) and a spherical SOD cage (15.0 Å for I). The breathing behavior of ZIF-65(Zn) varies depending on the nature of the guest molecules (polarity and shape). Computational simulations are employed to rationalize the differences in the breathing behavior depending on the structure of the ZIF-65(Zn) cage and the nature of the guest-associated host–guest and guest–guest interactions.

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Section: Introductionmentioning

confidence: 51%

Section: Resultsmentioning

confidence: 99%

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Large breathing effect in ZIF-65(Zn) with expansion and contraction of the SOD cage

et al. 2022

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“…NU-100 shows amounts of 14 and 2 wt% at 100 bar and 1 bar, respectively [73]. [73]; copyright (2019) with permission from Nature R Zeolitic imidazolate frameworks (ZIFs) are a class of MOFs that has a simila ogy to zeolites [74][75][76][77]. Zhan et al synthesized the core-shell structure of ZIFs for oshka-type ZIFs via a step-wise liquid-phase epitaxial growth to evaluate the s mechanism [78].…”

Section: Non-carbonaceous Materials For Hydrogen Storagementioning

confidence: 99%

“…The dominant factors for the spillover effect are demonstrated also includi perature, hydrogen concentration, and pressure via multi-layer ZIF nanocubes as (Figure 6). Zeolitic imidazolate frameworks (ZIFs) are a class of MOFs that has a similar topology to zeolites [74][75][76][77]. Zhan et al synthesized the core-shell structure of ZIFs for Matryoshkatype ZIFs via a step-wise liquid-phase epitaxial growth to evaluate the spillover mechanism [78].…”

Section: Non-carbonaceous Materials For Hydrogen Storagementioning

confidence: 99%

Recent Progress Using Solid-State Materials for Hydrogen Storage: A Short Review

et al. 2022

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With the rapid growth in demand for effective and renewable energy, the hydrogen era has begun. To meet commercial requirements, efficient hydrogen storage techniques are required. So far, four techniques have been suggested for hydrogen storage: compressed storage, hydrogen liquefaction, chemical absorption, and physical adsorption. Currently, high-pressure compressed tanks are used in the industry; however, certain limitations such as high costs, safety concerns, undesirable amounts of occupied space, and low storage capacities are still challenges. Physical hydrogen adsorption is one of the most promising techniques; it uses porous adsorbents, which have material benefits such as low costs, high storage densities, and fast charging–discharging kinetics. During adsorption on material surfaces, hydrogen molecules weakly adsorb at the surface of adsorbents via long-range dispersion forces. The largest challenge in the hydrogen era is the development of progressive materials for efficient hydrogen storage. In designing efficient adsorbents, understanding interfacial interactions between hydrogen molecules and porous material surfaces is important. In this review, we briefly summarize a hydrogen storage technique based on US DOE classifications and examine hydrogen storage targets for feasible commercialization. We also address recent trends in the development of hydrogen storage materials. Lastly, we propose spillover mechanisms for efficient hydrogen storage using solid-state adsorbents.

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Chemoselectivity Inversion of Responsive Metal–Organic Frameworks by Particle Size Tuning in the Micrometer Regime

Abylgazina,

Senkovska,

Engemann

et al. 2024

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Gated adsorption is one of the unique physical properties of flexible metal–organic frameworks with high application potential in selective adsorption and sensing of molecules. Despite recent studies that have provided some guidelines in understanding and designing structural flexibility for controlling gate opening by chemical modification of the secondary building units, currently, there is no established strategy to design a flexible MOF showing selective gated adsorption for a specific guest molecule. In a present contribution it is demonstrated for the first time, that the selectivity in the gate opening of a particular compound can be tuned, changed, and even reversed using particle size engineering DUT‐8(Zn) ([Zn2(2,6‐ndc)2(dabco)]n, 2,6‐ndc = 2,6‐naphthalenedicarboxylate, dabco = 1,4‐diazabicyclo‐[2.2.2]‐octane, DUT = Dresden University of Technology) experiences phase transition from open (op) to closed (cp) pore phase upon removal of solvent from the pores. Microcrystals show selective reopening in the presence of dichloromethane (DCM) over alcohols. Crystal downsizing to micron size unexpectedly reverses the gate opening selectivity, causing DUT‐8(Zn) to open its nanosized pores for alcohols but suppressing the responsivity toward DCM.

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Structural resolution and mechanistic insight into hydrogen adsorption in flexible ZIF-7

Abstract: Hydrogen induced flexibility in MOFs can be leveraged to increase useable gas storage capacities. Here hydrogen adsorption isothermal and in situ powder neutron diffraction measurements combine to reveal the mechanism driving flexibility in ZIF-7.

Cited by 25 publications

References 88 publications

Large breathing effect in ZIF-65(Zn) with expansion and contraction of the SOD cage

Large breathing effect in ZIF-65(Zn) with expansion and contraction of the SOD cage

Recent Progress Using Solid-State Materials for Hydrogen Storage: A Short Review

Chemoselectivity Inversion of Responsive Metal–Organic Frameworks by Particle Size Tuning in the Micrometer Regime

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