Recent progress on porous MOFs for process-efficient hydrocarbon separation, luminescent sensing, and information encryption.

The development of porous materials for ethylene (C2H4) separation and purification, a very important separation process in the chemical industry, is urgently needed but quite challenging. In particular, the realization of selectivity-reversed adsorption (namely, C2H4 is not preferentially adsorbed) and the simultaneous capture of multinary coexisting impurities such as ethane (C2H6) and acetylene (C2H2) will significantly simplify process design and reduce energy and cost consumption, but such porous materials are quite difficult to design and have not yet been fully explored. In this work, by employing an aromatic-rich bithiophene-based tetraisophthalate ligand, we solvothermally fabricated an anionic In(III)-based framework termed ZJNU-115 featuring In(COO)4 as an inorganic secondary building unit as well as one-dimensional channels. Due to the absence of unsaturated metallic sites, together with aromatic-rich channel surface decorated with abundant hydrogen-bonding acceptors of carboxylate oxygen and thiophene sulfur atoms, desolvated ZJNU-115 exhibited an unusual adsorption relationship with respect to C2 hydrocarbons, namely, simultaneous and preferable capture of C2H6 and C2H2 over C2H4 at the temperatures investigated, thus representing a rare metal-organic framework (MOF) with the promising potential for one-step adsorption-phase purification of C2H4 from a trinary C2 hydrocarbon mixture. Compared to a few of the MOFs reported for such an application, ZJNU-115 displayed simultaneously good adsorption selectivities of both C2H2 and C2H6 over C2H4. Furthermore, its separation potential can be postsynthetically tailored by substituting dimethylammonium (Me2NH2+) counterions with tetraalkyl ammonium ions (NR4+; R = Me, Et, or n-Pr). More importantly, ZJNU-115 was stable in various organic solvents as well as aqueous solutions with pH values ranging from 5 to 9, thus laying a solid foundation for its practical applications. The design principle and the performance regulation strategy adopted in this work will offer valuable guidance for the contrapuntal construction of porous MOFs employed for direct multicomponent purification of C2H4 with improved performance.

Rational Construction and Performance Regulation of an In(III)-Tetraisophthalate Framework for One-Step Adsorption-Phase Purification of C 2 H 4 from C 2 Hydrocarbons.

One-step separation of C2H4 from ternary C2H2/C2H4/C2H6 hydrocarbon mixtures is of great significance in the industry but is challenging due to the similar sizes and physical properties of C2H2, C2H4, and C2H6. Here, we report an anion-pillared hybrid ultramicroporous material, CuTiF6-TPPY, that has the ability of selective recognition of C2H4 over C2H2 and C2H6. The 4,6-connected fsc framework of CuTiF6-TPPY exhibits semi–cage-like one-dimensional channels sustained by porphyrin rings and TiF62− pillars, which demonstrates the noticeably enhanced adsorption of C2H2 and C2H6 over C2H4. Dynamic breakthrough experiments confirm the direct and facile high-purity C2H4 (>99.9%) production from a ternary gas mixture of C2H2/C2H6/C2H4 (1/9/90, v/v/v) under ambient conditions. Computational studies and in situ infrared reveal that the porphyrin moieties with large π-surfaces form multiple van der Waals interactions with C2H6; meanwhile, the polar TiF62− pillars form C–H•••F hydrogen bonding with C2H2. In contrast, the recognition sites for C2H4 in the framework are less marked.

Synergistic binding sites in a hybrid ultramicroporous material for one-step ethylene purification from ternary C2 hydrocarbon mixtures

Recent advances in adsorptive separation of ethane and ethylene by C2H6-selective MOFs and other adsorbents

The preferential capture of ethane (C2H6) over ethylene (C2H4) presents a very cost-effective and energy-saving means applied to adsorptive separation and purification of C2H4 with a high product purity, which is however challenged by low selectivity originating from their similar molecular sizes and physical properties. Substituent engineering has been widely employed for selectivity regulation and improvement, but its effect on C2H6/C2H4 separation has been rarely explored to date. In this work, four isoreticular coordination framework compounds based on 5-(pyridin-3-yl)isophthalate ligands bearing different substituents were rationally constructed. As revealed by isotherm measurements, thermodynamic studies, and IAST computations, they exhibited promising utility for C2H6/C2H4 separation with moderate adsorption heat and a high uptake amount at a relatively low-pressure domain. Furthermore, the C2H6/C2H4 separation potential can be finely tuned and optimized via purposeful substituent alteration. Most remarkably, functionalization with a nonpolar methyl group yielded an improved separation efficiency compared to its parent compound. This work offers a good reference value for enhancing the C2H6/C2H4 separation efficiency of MOFs by engineering the pore microenvironment and dimensions via substituent manipulation.

Improving Ethane/Ethylene Separation Performance of Isoreticular Metal-Organic Frameworks via Substituent Engineering.

Solvothermal assembly of copper(II) cations and 5-(pyridine-3-yl)isophthalate linkers bearing different position-substituted methyl groups afforded four ligand-induced metal-organic framework (MOF) isomers as a platform for investigating diverse selective gas adsorption properties and understanding the positional effect of methyl functionality. Single-crystal X-ray diffraction (SCXRD) analyses showed that, when the methyl substituent is at the para position with respect to the pyridinic N atom, the resultant framework compound ZJNU-27 features an eea-type topology, while the other three solids possess an isoreticular structure with an rtl-type topology when the methyl group is situated at the other positions. As revealed by N2 physi-adsorption measurements at 77 K, they exhibit moderate specific surface areas ranging from 584 to 1182 m2 g-1 and distinct degrees of framework flexibility, which are heavily dependent on the methyl position. Comprehensive gas adsorption studies show that they are capable of effectively separating three pairs of binary gas mixtures including C2H2-CH4, CO2-CH4, and CO2-N2 couples. Moreover, their uptake capacities and adsorption selectivities can be tailored by altering the methyl position. In addition, their framework hydro-stability is also influenced by the methyl position. Compared to ZJNU-27 and ZJNU-28, ZJNU-26 and ZJNU-29 exhibit poorer stability against H2O, although the methyl group is more close to inorganic secondary building units (SBUs), which are believed to originate from the steric effect of the methyl group. Overall, the four MOFs display the methyl position-dependent network architectures, framework flexibilities, and selective gas adsorption properties as well as hydrostabilities. The findings observed in this work not only demonstrate the importance of the positional effect of the functional group but also highlight that engineering the substituent position is a potential strategy for achieving the modulation of MOF structures and properties.

A Series of Metal-Organic Framework Isomers Based on Pyridinedicarboxylate Ligands: Diversified Selective Gas Adsorption and the Positional Effect of Methyl Functionality.

To enrich structural chemistry and widen the application prospects of MOFs (metal-organic frameworks), the development of a synthetic strategy to realize structural and functional modulation is highly demanded. By implementation of the linker bent-angle engineering strategy, three banana-like diisophthalate linkers with distinct bent angles were designed and synthesized. The inclusion of the targeted linkers into MOFs through solvothermal assembly with CuCl2·2H2O under identical conditions yielded three crystalline solids featuring diversified topological structures as revealed by X-ray crystallographic studies. Furthermore, functional explorations indicated that they are promising solid adsorbents for acetylene (C2H2) purification application with structurally dependent separation potentials. The results reported in this study illustrated a rare example of modulating the topological structures and separation efficiencies of MOFs by engineering the ligand bent angles.

Ligand Bent-Angle Engineering for Tuning Topological Structures and Acetylene Purification Performances of Copper-Diisophthalate Frameworks.

Implementation of lanthanide–organic frameworks (LOFs) as solid adsorbents has been frequently handicapped by their permanent porosity being difficult to establish owing to the remarkable flexibili...

Lianglan Yue

Papers

Rational Construction and Performance Regulation of an In(III)-Tetraisophthalate Framework for One-Step Adsorption-Phase Purification of C 2 H 4 from C 2 Hydrocarbons.

Improving Ethane/Ethylene Separation Performance of Isoreticular Metal-Organic Frameworks via Substituent Engineering.

A Series of Metal-Organic Framework Isomers Based on Pyridinedicarboxylate Ligands: Diversified Selective Gas Adsorption and the Positional Effect of Methyl Functionality.

Ligand Bent-Angle Engineering for Tuning Topological Structures and Acetylene Purification Performances of Copper-Diisophthalate Frameworks.

Lanthanide-Organic Frameworks Featuring Three-Dimensional Inorganic Connectivity for Multipurpose Hydrocarbon Separation.