Reticular chemistry at the atomic, molecular, and framework scales

Zhang, Yue‐Biao; Li, Qiaowei; Deng, Hexiang

doi:10.1007/s12274-020-3226-6

Cited by 11 publications

(7 citation statements)

References 55 publications

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“…Formed by connecting metal ions or metal clusters through organic struts, metal–organic frameworks (MOFs) are a new class of hybrid porous materials that mark them out as prominent candidates for numerous emerging applications, for example, gas storage and separation, − heterogeneous catalysis, − sensing, − drug delivery, − and water harvesting, − just to name a few. A major driving force behind the recent explosion of interest in MOFs lies with their amenability to design using the reticular principle, which is unattainable for traditional porous materials. − In particular, with respect to gas separation, crystal engineering of MOFs enables ultrafine control over pore size/shape and surface environment to realize enhanced or even sieving separation . Specifically, for C 2 H 2 /CO 2 separation, since Kitagawa and co-workers for the first time introduced the prototypal C 2 H 2 selective sorbent in 2005, there has been little progress in this domain, and only a handful of MOFs out of 70,000+ total have been reported to be effective. − Until very recently, there is a striking upsurge in developing highly efficient C 2 H 2 selective MOF sorbents, ,,− ,,− achieving the highest known C 2 H 2 /CO 2 (50:50) separation selectivity of 185 .…”

Section: Introductionmentioning

confidence: 99%

Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

et al. 2021

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Physical separation of C 2 H 2 from CO 2 on metal−organic frameworks (MOFs) has received substantial research interest due to the advantages of simplicity, security, and energy efficiency. However, that C 2 H 2 and CO 2 exhibit very close physical properties makes their separation exceptionally challenging. Previous work appeared to mostly focused on introducing open metal sites that aims to enhance the C 2 H 2 affinity at desired sites, whereas the reticular manipulation of organic components has rarely been investigated. In this work, by reticulating preselected amino and hydroxy functionalities into isostructural ultramicroporous chiral MOFs Ni 2 (L-asp) 2 (bpy) (MOF-NH 2 ) and Ni 2 (L-mal) 2 (bpy) (MOF-OH)we targeted efficient C 2 H 2 uptake and C 2 H 2 /CO 2 separation, which outperforms most benchmark materials. Explicitly, MOF-OH adsorbs substantial amount of C 2 H 2 with record storage density of 0.81 g mL −1 at ambient conditions, which even exceeds the solid density of C 2 H 2 at 189 K. In addition, MOF-OH gave IAST selectivity of 25 toward equimolar mixture of C 2 H 2 /CO 2 , which is nearly twice higher than that of MOF-NH 2 . Notably, the adsorption enthalpies for C 2 H 2 at zero converge in both MOFs are remarkably low (17.5 kJ mol −1 for MOF-OH and 16.7 kJ mol −1 for MOF-NH 2 ), which to our knowledge are the lowest among efficient rigid C 2 H 2 sorbents. The efficiencies of both MOFs for the separation of C 2 H 2 /CO 2 are validated by multicycle breakthrough experiments. DFT calculations provide molecular-level insight over the adsorption/ separation mechanism. Moreover, MOF-OH can survive in boiling water for at least 1 week and can be easily scaled up to kilograms eco-friendly and economically, which is very crucial for potential industrial implementation.

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Section: Introductionmentioning

confidence: 99%

Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

et al. 2021

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“…Metal ions/clusters as the secondary building units (SBUs) in periodic frameworks provide the possibility to modulate the physicochemical properties of MOFs. , In the progressive development of reticular chemistry, − most SBUs exist in isolated forms, such as mononuclear metal cations, metal-carboxylate clusters, or molecular building blocks . However, there is a class of MOFs in which SBUs are infinite in 1D. − They are referred to as rod SBUs. − Typically, rod MOFs possess a 1D pore structure and remarkable stability advantages (such as MIL-53, MOF-74, and UTSA-30).…”

Section: Introductionmentioning

confidence: 99%

Rational Synthesis of a Stable Rod MOF for Ultrasensitive Detection of Nitenpyram and Nitrofurazone in Natural Water Systems

Wang

Yang

et al. 2022

J. Agric. Food Chem.

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Overuse of nitenpyram and nitrofurazone in agricultural products poses enormous risks to ecosystems, and effective detection and quantification of these residual pollutants are of great concern. Although several strategies have been established for detecting nitenpyram and nitrofurazone in water, searching for a new sensor material with great sensitivity, selectivity, and recyclability remains challenging. Here, we design and synthesize a stable metal–organic framework (MOF) (Zn-CPTA) by employing an organic linker based on the coordination features of benzene-1,4-dicarboxylate and picolinic acid. Zn-CPTA is a 3D framework built from Zn–O–Zn chains called rod secondary building units, which contains 1D open channels modified by uncoordinated carboxyl O atoms and exhibits impressive chemical stability in aqueous solutions within a pH range from 2 to 12. Especially, fluorescent Zn-CPTA can quickly and sensitively detect nitenpyram and nitrofurazone in aqueous solutions with a high quenching constant and low detection limit (LOD) (K SV values for nitenpyram and nitrofurazone are 1.67 × 104 and 1.02 × 105 M–1 with LOD of 0.625 and 0.126 μM, respectively), as well as outstanding selectivity and recyclability. Notably, the LOD value is the lowest among the reported MOFs used for nitrofurazone detection. Besides, experiments and density functional theory calculations are combined to explain the quenching mechanism. Finally, the practical application of Zn-CPTA was further explored in real environment samples with satisfactory recoveries.

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“…[8][9][10][11][12][13][14][15][16] MetalÀorganic frameworks (MOFs) are extended structures constructed by metal-based clusters as inorganic secondary building units (SBUs) and organic linkers via strong bonds. [17][18][19][20][21][22][23][24][25][26] MOFs have been exhibiting extraordinary properties in gas adsorption and separation, [27][28][29][30][31] catalysis, [32][33][34][35] and energy storage, [36][37][38][39] which are attributed to their robust structures with high porosity and tailored interactions with various guests. Undoubtedly, these characteristics bring new thinking to the vacancy chemistry of MOFs, and following three points can be distilled.…”

Section: Introductionmentioning

confidence: 99%

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

Pang

Yang

2022

Small Structures

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Vacancies in crystalline materials are missing single atoms and missing clusters of atoms in the ordered lattice. In reticular structures such as metal−organic frameworks (MOFs), vacancy can exist in the form of organic linker vacancy, inorganic cluster vacancy, and macroscopic vacancy. In last decade, extensive researches have been developed in exploring the formation, arrangement, and functions of vacancies in MOFs. In this review, an overview of progress in introducing structural vacancies into MOFs either by de novo synthesis or by postsynthetic modification is provided. Different spatial arrangements of vacancies (random, site‐selective, and correlated/ordered) are also highlighted, with an emphasis on new synthetic strategies and mechanisms, and advanced characterization methods needed to control vacancies in a sophisticated manner. Furthermore, enhanced gas adsorption, precise framework grafting, and efficient molecular conversion empowered by vacancies in MOFs are summarized. Future opportunities in this field are envisioned by considering vacancies as a new kind of constituents to reshape the MOF backbone and pores for higher structural complexities and tailored functions.

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Reticular chemistry at the atomic, molecular, and framework scales

Cited by 11 publications

References 55 publications

Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

Rational Synthesis of a Stable Rod MOF for Ultrasensitive Detection of Nitenpyram and Nitrofurazone in Natural Water Systems

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

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Reticular chemistry at the atomic, molecular, and framework scales

Cited by 11 publications

References 55 publications

Efficient C2H2/CO2 Separation in Ultramicroporous Metal–Organic Frameworks with Record C2H2 Storage Density

Efficient C2H2/CO2 Separation in Ultramicroporous Metal–Organic Frameworks with Record C2H2 Storage Density

Rational Synthesis of a Stable Rod MOF for Ultrasensitive Detection of Nitenpyram and Nitrofurazone in Natural Water Systems

Vacancies in Metal−Organic Frameworks: Formation, Arrangement, and Functions

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Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density

Efficient C₂H₂/CO₂ Separation in Ultramicroporous Metal–Organic Frameworks with Record C₂H₂ Storage Density