Tetranuclear Cu^IICluster as the Ten Node Building Unit for the Construction of a Metal–Organic Framework for Efficient C₂H₂/CO₂Separation

Abstract

Rational design of high nuclear copper clusterbased metal-organic frameworks has not been established yet. Herein, we report a novel MOF (FJU-112) with the ten-connected tetranuclear copper cluster [Cu 4 -(PO 3 ) 2 (μ 2 -H 2 O) 2 (CO 2 ) 4 ] as the node which was capped by the deprotonated organic ligand of H 4 L (3,5-Dicarboxyphenylphosphonic acid). With BPE (1,2-Bis(4-pyridyl)ethane) as the pore partitioner, the pore spaces in the structure of FJU-112 were divided into several smaller cages and smaller windows for efficient gas adsorption and separation. FJU-112 exhibits a high separation performance for the C 2 H 2 /CO 2 separation, which were established by the temperature-dependent sorption isotherms and further confirmed by the labscale dynamic breakthrough experiments. The grand canonical Monte Carlo simulations (GCMC) studies show that its high C 2 H 2 /CO 2 separation performance is contributed to the strong π-complexation interactions between the C 2 H 2 molecules and framework pore surfaces, leading to its more C 2 H 2 uptakes over CO 2 molecules.

Vertex Strategy in Layered 2D MOFs: Simultaneous Improvement of Thermodynamics and Kinetics for Record C2H2/CO2 Separation Performance

“…22−25 It is expected to achieve efficient separation between mixtures with slight differences such as C 2 H 2 /CO 2 . Researchers have reported various MOFs for C 2 H 2 /CO 2 separation recently, 26−33 where major efforts have been made to adjust the 3D framework to generate appropriate pore space, for instance, introducing open metal sites, 7,34,35 introducing polar functional groups, 36−39 constructing hydrogen bonding nanotraps, 40 pore space partition strategies, 41,42 constructing interpenetration structures, 29 ligand derivatization, 11,32,33,43 partial linker substitution strategy, 44 induced-fit transformation strategy, 45 etc. Significant progress has been made by these contributions, but the design of C 2 H 2 selective adsorbents that combines high adsorption capacity with high selectivity remains a challenge.…”

pH-Stable Zn(II) Coordination Polymer as a Multiresponsive Turn-On and Turn-Off Fluorescent Sensor for Aqueous Medium Detection of Al(III) and Cr(VI) Oxo-Anions

“…In this context, coordination polymers (CPs) and/or metal–organic frameworks (MOFs) are attracting immense interest due to their intriguing properties, such as an accessible high surface area, ordered crystalline structure, permanent porosity, functional tunability, structural diversity, unique flexibility, and variable morphologies. − In particular, owing to the presence of well-organized chromophores (Lewis acid and basic sites) in their chemically tailorable framework, CPs/MOFs exhibit excellent luminescent properties. ,, Such superior properties make them fascinating as an effective sensing probe for the detection of variable analytes including toxic metal ions, hazardous anions, explosives, antibiotics, pesticides, and small organic molecules. ,,− Moreover, the specific host–guest interactions between the incoming analytes and the accessible functional groups of the framework bring more advantages in terms of easy operability, fast responsivity, high selectivity, good sensitivity, and multiple recyclabilities . − Taking advantage of such superiorities, although a large number of CPs/MOFs have been explored for the rapid detection of toxic metal cations and noxious oxo-anions individually or combinedly having turn-off luminescence only, ,,,, multiresponsive behavior with one turn-off and another turn-on luminescent detection by a single CP/MOF platform remains unexplored so far. Compared to single-analyte recognition, frameworks showing simultaneous and rapid sensing for multiple analytes are highly desirable and on-demand as they can increase the versatility and multipurpose usage possibility of the developed sensory materials. ,− On the other hand, although a decent number of coordination frameworks have displayed excellent luminescent performance with high sensitivity and selectivity, their insufficient hydrolytic stability, as well as chemical instability, , forced them to detect targeted analytes in a nonaqueous medium. , However, to make the developed framework affordable and easy to handle, it is desirable to develop robust sensor materials that ca...…”

Cu-MOFs with Rich Open Metal and F Sites for Separation of C2H2 from CO2 and CH4

“…As a functional porous material, metal–organic frameworks (MOFs) exhibit excellent adsorption performance in gas adsorption and separation due to their adjustable pore structures and high specific surface areas. ,− However, given their similarity, C 2 H 2 /CO 2 separation is only achieved in a few MOFs; in particular, separations for ternary mixtures are even rarer. As we know, both high storage capacity and significant selectivity play important roles in efficient separation of gas mixtures. , Thus, the designed MOFs can balance the relationship between the two factors skillfully to achieve excellent separation. − The functionality-driven design of MOFs necessitates the judicious choice of metal nodes and organic ligands as well as the formation of secondary building units (SBUs). − Some SBUs based on O-centered M x O y cores have enhanced interactions with C 2 H 2 to drive selectivity due to the abundance of open metal sites (OMSs). ,− This has been shown to be an effective strategy in much of the reported work.…”