A flexible Zr-MOF with dual stimulus responses to temperature and guest molecules

Ji, Zhenyu; Di, Zhengyi; Li, Hengbo; Zou, Shuixiang; Wu, Mingyan; Hong, Maochun

doi:10.1016/j.inoche.2021.108597

Cited by 5 publications

(2 citation statements)

References 39 publications

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“…In recent years, metal-organic frameworks (MOFs) have attracted considerable interest, due to the unique pore structure and flexible framework, which focus on many applications such as catalysis, gas separation, and storage, sensing, drug delivery, energy, environment. [18,19,28] The net framework structure of MOFs is composed of metal ions or clusters through the bridging of organic ligands. Most MOFs have large flexibility, which depends on the presence of much weaker interactions (coordination bonds, hydrogen bonds or π-π stacking).…”

Section: Introductionmentioning

confidence: 99%

Zero thermal expansion in metal–organic framework with imidazole dicarboxylate ligands

Gao¹,

Jiao²,

Li³

2022

Chinese Phys. B

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Exploring new abnormal thermal expansion materials is important to understand the nature of thermal expansion. Metal-Organic Framework (MOF) with unique structure flexibility is ideal material to study the thermal expansion. This work adopts the high-resolution variable-temperature powder X-ray diffraction to investigate the structure and intrinsic thermal expansion in Sr-MOF ([Sr(DMPhH2IDC)2]n). It has the unique honeycomb structure with 1D channels along c-axis direction, the a-b plane displays layer structure. The thermal expansion behavior has strong relationship with the structure, ZTE appears in the a-b plane and large PTE along c-axis direction. The possible mechanism is that the a/b layers have enough space for the transverse thermal vibration of polydentate ligands, while along the c-axis direction is not. This work not only reports one interesting zero thermal expansion material, but also provides new understand for thermal expansion mechanism from the perspective of structural model.

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Section: Introductionmentioning

confidence: 99%

Zero thermal expansion in metal–organic framework with imidazole dicarboxylate ligands

Gao¹,

Jiao²,

Li³

2022

Chinese Phys. B

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“…To the best of our knowledge, QPF-1 exhibits the first flexible porphyrin-Zr MOF despite the strong Zr-carboxylate bond, and the considerable breathing amplitude comparable to other reported flexible Zr-MOFs. [15,[29][30][31] As mentioned above, guests with various spatial sizes can result in different packing forces, which further affect the degree of the porphyrin distortion. Therefore, we can conclude that not only the degree of nonplanarity can be precisely manipulated but also a partial distortion of the porphyrins in a single crystal grain can be readily achieved (Figure 5), engendering unique MOF properties.…”

Section: Resultsmentioning

confidence: 99%

Guest‐Stimulated Nonplanar Porphyrins in Flexible Metal−Organic Frameworks

Qian

Wang

et al. 2023

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Nonplanar porphyrins with out‐of‐plane distortions play crucial roles in many biological functions and chemical applications. The artificial construction of nonplanar porphyrins usually involves organic synthesis and modification, which is a highly comprehensive approach. However, incorporating porphyrins into guest‐stimulated flexible systems allows to manipulate the porphyrin distortion through simple ad/desorption of guest molecules. Here, a series of porphyrinic zirconium metal−organic frameworks (MOFs) is reported that exhibit guest‐stimulated breathing behavior. X‐Ray diffraction analysis and skeleton deviation plots confirm that the material suffers from porphyrin distortion to form a ruffled geometry under the desorption of guest molecules. Further investigation reveals that not only the degree of nonplanarity can be precisely manipulated but also the partial distortion of porphyrin in a single crystal grain can be readily achieved. As Lewis acidic catalyst, the MOF with nonplanar Co‐porphyrin exhibits active properties in catalyzing CO2/propylene oxide coupling reactions. This porphyrin distortion system provides a powerful tool for manipulating nonplanar porphyrins in MOFs with individual distortion profiles for various advanced applications.

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Wide Temperature Sieving of n‐Butene and iso‐Butene by a Zinc‐Based Coordination Network with Record Separation

Li,

Zhang

et al. 2024

Adv Funct Materials

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Separating n‐butene and iso‐butene through adsorption represents a viable and energy‐efficient strategy. However, developing porous adsorbents that can effectively discern the subtle differences between these isomers remains a significant challenge. This study demonstrates that a zinc‐based coordination network (CALF‐20) exhibits a slight pore expansion with increasing temperature, creating nanochannels that preferentially adsorb n‐butene over iso‐butene. This unique temperature‐dependent dynamic behavior enables effective sieving of n‐butene from iso‐butene within the temperature range of 273 to 423 K, a phenomenon not previously observed. Notably, CALF‐20 exhibits the highest n‐butene adsorption capacity (2.62 mmol g−1) and the highest selectivity ratio (14.7) among sieving materials reported to date for n‐butene isomers. Modeling calculations show that dynamic factors play a significant role in achieving such high adsorption separation capabilities. At medium temperatures, the initial separation of n‐butene and iso‐butene is achievable, which may provide a foundation for the future design of adsorbents intended to achieve efficient separation of n‐butene/iso‐butene under comparable temperature conditions. In the future, the intricate structure dynamics and enhanced capacity for molecular recognition will offer a new pathway for developing advanced sieving materials.

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A flexible Zr-MOF with dual stimulus responses to temperature and guest molecules

Cited by 5 publications

References 39 publications

Zero thermal expansion in metal–organic framework with imidazole dicarboxylate ligands

Zero thermal expansion in metal–organic framework with imidazole dicarboxylate ligands

Guest‐Stimulated Nonplanar Porphyrins in Flexible Metal−Organic Frameworks

Wide Temperature Sieving of n‐Butene and iso‐Butene by a Zinc‐Based Coordination Network with Record Separation

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