Microporous lanthanide metal-organic frameworks
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Abstract Microporous metal-organic frameworks (MOFs) based on lanthanide metal ions or clusters represent a group of porous materials, featuring interesting coordination, electronic, and optical properties. These attractive properties in combination with the porosity make microporous lanthanide MOFs (Ln-MOFs) hold the promise for various applications. This review is to provide an overview of the current status of the research in microporous Ln-MOFs, and highlight their potential as types of multifunctional materials for applications in gas/solvent adsorption and separation, luminescence and chemical sensing and catalysis.Specific surface area
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A novel blue-emitting Zn(II) MOF featuring parallel 2D+2D interpenetrated layers and tubelike channels was generated and shown to efficiently accommodate lanthanide(III) cations (Ln3+ = Eu3+, Tb3+, or a mixture of Eu3+/Tb3+), resulting in the Ln3+-encapsulated functional materials with a tunable emission color, including red, green, and nearly pure white light. Furthermore, the thermal-responsive luminescence was investigated for the lanthanide-codoped MOF to exhibit the chromic transition from white at room temperature to blue around liquid nitrogen temperature.
Blueshift
Liquid nitrogen
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Abstract Microporous metal-organic frameworks (MOFs) based on lanthanide metal ions or clusters represent a group of porous materials, featuring interesting coordination, electronic, and optical properties. These attractive properties in combination with the porosity make microporous lanthanide MOFs (Ln-MOFs) hold the promise for various applications. This review is to provide an overview of the current status of the research in microporous Ln-MOFs, and highlight their potential as types of multifunctional materials for applications in gas/solvent adsorption and separation, luminescence and chemical sensing and catalysis.
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Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the Cu II metal nodes in MOFs can be transformed into Cu I via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of Cu I and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.
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Four microporous lanthanide metal–organic frameworks (MOFs), namely Ln(BTC)(H2O)(DMF)1.1(Ln = Tb, Dy, Er and Yb, DMF = dimethylformamide, H3BTC = benzene-1,3,5-tricarboxylic acid), have been used for selective adsorption of Pb(ii ) and Cu(ii ).
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Abstract Hierarchically porous metal–organic frameworks (HP‐MOFs) have attracted great attention owing to their advantages over microporous MOFs in some applications. Despite many attempts, the development of a facile approach to generate HP‐MOFs remains a challenge. Herein we develop a new strategy, namely the modulation of cation valence, to create hierarchical porosity in MOFs. Some of the Cu II metal nodes in MOFs can be transformed into Cu I via reducing vapor treatment (RVT), which partially changes the coordination mode and thus breaks coordination bonds, resulting in the formation of HP‐MOF based on the original microporous MOF. Both the experimental results and the first‐principles calculation show that it is easy to tailor the amount of Cu I and subsequent hierarchical porosity by tuning the RVT duration. It is found that the resultant HP‐MOFs perform much better in the capture of aromatic sulfides than the original microporous MOF.
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Solvothermal synthesis
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A novel pillar-layer porous lanthanide metal–organic framework [Tb3(ODA)3(BPDC)3Na2]n·Gx (UTSA-222, G = guest molecules) was constructed from an organic ligand [1,1′-biphenyl]-4,4′-dicarboxylate (BPDC2−) and a lanthanide metalloligand [Tb(ODA)]+ (H2ODA = oxydiacetic acid). The UTSA-222 contains two-dimensional intersecting channels with the Brunauer–Emmett–Teller surface area and pore volume of 703 m2 g–1 and 0.344 cm3 g–1, respectively, for the activated sample. It shows moderately high adsorption selectivity for C2H2/CO2 and C2H2/CH4 separations at 1 atm and room temperature.
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H2TFBDC lanthanide complexes emitting white light was synthesized and a luminescent sensor for the detection of benzaldehyde has been produced.
Luminescent Measurements
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