Systemic regulation of binding sites in porous coordination polymers for ethylene purification from ternary C2 hydrocarbons.

The global demand for poly-grade ethylene (C2H4) is increasing annually. However, the energy-saving purification of this gas remains a major challenge due to the similarity in molecular properties among the ternary C2 hydrocarbons. To address this challenge, we report an approach of systematic tuning of the pore environment with organic sites (from -COOH to -CF3, then to -CH3) in porous coordination polymers (PCPs), of which NTU-73-CH3 shows remarkable capability for the direct production of poly-grade C2H4 from ternary C2 hydrocarbons under ambient conditions. In comparison, the precursor structure of NTU-73-COOH is unable to purify C2H4, while NTU-73-CF3 shows minimal ability to harvest C2H4. This is because the changed binding sites in the NTU-73-series not only eliminate the channel obstruction caused by the formation of gas clusters, but also enhance the interaction with acetylene (C2H2) and ethane (C2H6), as validated by in situ crystallographic and Raman analysis. Our findings, in particular the systematic tuning of the pore environment and the efficient C2H4 purification by NTU-73-CH3, provide a blueprint for the creation of advanced porous families that can handle desired tasks.

Fine-regulation of gradient gate-opening in nanoporous crystals for sieving separation of ternary C3 hydrocarbons.

The adsorptive separation of ternary propyne (C3H4)/propylene (C3H6)/propane (C3H8) mixtures is of significant importance due to its energy efficiency. However, achieving this process using an adsorbent has not yet been accomplished. To tackle such a challenge, herein, we present a novel approach of fine-regulation of the gradient of gate-opening in soft nanoporous crystals. Through node substitution, an exclusive gate-opening to C3H4 (17.1 kPa) in NTU-65-FeZr has been tailored into a sequential response of C3H4 (1.6 kPa), C3H6 (19.4 kPa), and finally C3H8 (57.2 kPa) in NTU-65-CoTi, of which the gradient framework changes have been validated by in situ powder X-ray diffractions and modeling calculations. Such a significant breakthrough enables NTU-65-CoTi to sieve the ternary mixtures of C3H4/C3H6/C3H8 under ambient conditions, particularly, highly pure C3H8 (99.9%) and C3H6 (99.5%) can be obtained from the vacuum PSA scheme. In addition, the fully reversible structural change ensures no loss in performance during the cycling dynamic separations. Moving forward, regulating gradient gate-opening can be conveniently extended to other families of soft nanoporous crystals, making it a powerful tool to optimize these materials for more complex applications.

Tuning Multiple Counter-Anions in Porous Coordination Polymers with lcy Topology for Acetylene/Ethylene Separation.

The efficient separation of acetylene (C2H2) and ethylene (C2H4) is an important and complex process in the industry. Herein, we report a new family of lcy-topologic coordination frameworks (termed NTU-90 to NTU-92) with Cu3MF6 (M = Si, Ti, and Zr) nodes. These charged frameworks are compensated by different counterbalanced ions (MF62-, BF4-, and Cl-), yielding changes in the size of the window apertures. Among these frameworks, NTU-92-a (activated NTU-92) shows good adsorption selectivity of C2H2/C2H4 and also significant ability in recovering both highly pure C2H4 (99.95%) and C2H2 (99.98%). Our work not only presents a potential alternative for energy-saving purification of C2 hydrocarbons but also provides a new approach for tuning the function of charged porous materials.

Highly Efficient CO2 Capture from Wet-Hot Flue Gas by a Robust Trap-and-Flow Crystal.

Highly selective CO2 capture from flue gas based on adsorption technology is among the largest challenge on the horizon, due to its high temperature (>333 K), lower partial pressure (0.1-0.2 bar), and competition from water. Due to the designable and tunable pore system, porous coordination polymers (PCPs) have been considered as the most exciting discoveries in porous materials. However, the rational design and function-led preparation of the pore system that permits highly selective CO2 capture from flue gas (CO2/N2/O2/CO/H2O) remains a great challenge. Herein, we report a highly selective CO2 capture from wet-hot (363 K, RH = 40%) flue gas by a robust trap-and-flow crystal (NTU-67). Crystallographic analysis showed that the flow channel provides plausible CO2 traffic, while the confined trap works as an accommodation for captured gas molecules. Further, the hydrophobic pore surface endows the function of the channels that are not influenced by hot moisture, a major obstacle to overcome direct CO2 capture by PCPs. The integral nature of NTU-67, including good stability in SO2, meets the key prerequisites that are usually considered for practical applications. The molecular insight and highly efficient CO2 capture make us believe that different nanospace with their own duties may be extended into ingenious design of more advanced adsorbents for cost-effective and promising for CO2 capture from flue gas.

Metal-Organic Framework Nanoparticles with Universal Dispersibility through Crown Ether Surface Coordination for Phase-Transfer Catalysis and Separation Membranes.

Dispersing metal-organic framework (MOF) solids in stable colloids is crucial for their availability and processibility. Herein, we report a crown ether surface coordination approach for functionalizing the surface-exposed metal sites of MOF particles with amphiphilic carboxylated crown ether (CEC ). The surface-bound crown ethers significantly improve MOF solvation without compromising the accessible voids. We demonstrate that CEC -coated MOFs exhibit exceptional colloidal dispersibility and stability in 11 distinct solvents and six polymer matrices with a wide range of polarities. The MOF-CEC can be instantaneously suspended in immiscible two-phase solvents as an effective phase-transfer catalyst and can form various uniform membranes with enhanced adsorption and separation performance, which highlights the effectiveness of crown ether coating.

Pore engineering of metal-organic frameworks for ethylene purification.

Ethylene production is an important and direct indicator related to the development of the petrochemical industry in a country. However, the separation and purification of ethylene is an extremely energy-consuming process. In this review, the latest progress in the purification of ethylene using metal organic frameworks (MOFs), a new type of physical adsorbent, is summarized according to four classifications of pore engineering, including pore surface functionalization, molecular sieving, controlled framework softness and dynamic pore-dominated molecular diffusion. Finally, the current challenges and future prospects in this field are also discussed.

Tuning Gate-Opening of a Flexible Metal-Organic Framework for Ternary Gas Sieving Separation.

In comparison with the fast development of binary mixture separations, ternary mixture separations are significantly more difficult and have rarely been realized by a single material. Herein, a new strategy of tuning the gate-opening pressure of flexible MOFs is developed to tackle such a challenge. As demonstrated by a flexible framework NTU-65, the gate-opening pressure of ethylene (C2 H4 ), acetylene (C2 H2 ), and carbon dioxide (CO2 ) can be regulated by temperature. Therefore, efficient sieving separation of this ternary mixture was realized. Under optimized temperature, NTU-65 adsorbed a large amount of C2 H2 and CO2 through gate-opening and only negligible amount of C2 H4 . Breakthrough experiments demonstrated that this material can simultaneously capture C2 H2 and CO2 , yielding polymer-grade (>99.99 %) C2 H4 from single breakthrough separation.

Finely Tuned Porous Coordination Polymers To Boost Methane Separation Efficiency.

Absorbents with high breakthrough efficiency and weak host-guest interaction are considered to be promising candidates for an energy-saving process in feasible pressure/volume swing adsorption (PSA/VSA). Herein, two groups of finely designed Fe- and Co-based porous coordination polymers (PCPs) are proposed and validated; these possess hourglass-shaped nanochannels, through the cooperation of T-shaped ligands with shifted methyl groups. Featuring optimal nanochannels, high static adsorption, and relatively lower binding energy, one of these polymers, named NTU-30, enables significant C2 H6 /CH4 and C2 H4 /CH4 breakthrough efficiency, with approximately 1.0 or 0.6 g CH4 (100 %) harvested from the corresponding mixtures using 1 g of sample at ambient temperature. Furthermore, the positive effect of aromatic sites within NTU-30 is detected and investigated through an in situ IR study.

Enhanced Breakthrough Efficiency by a Chemically Stable Porous Coordination Polymer with Optimized Nanochannel.

High separation efficiency is very important for process of pressure swing adsorption (PSA) in the industry. Herein, we propose a fine design of chemically stable porous coordination polymers (PCPs) with optimized nanochannel by strategy of inserting and shifting shortest alkyl group on T-shaped ligand. Remarkably, the synergistic effect of optimized nanochannel, unique crystal morphology and fitted channel enable sharply enhanced breakthrough efficiency of C2H6/4/CH4, 1.17 or 0.77 g of CH4 can be separated from corresponding dual mixtures (2/8, v/v) by 1 g of NTU-25 at 273 K, which was further validated and understood by controlled experiments and density functional theory (DFT) computations.

Unified meso-pores and dense Cu2+ sites in porous coordination polymers for highly efficient gas storage and separation.

Unified meso-pores and dense open metal sites (OMS) in porous coordination polymers (PCPs) allow highly promising H2 and C2-hydrocarbon storage, as well as rapid and efficient C2H2/4 enrichment from CO2 mixtures. The positive function of the OMS, associated with guest thermodynamics, was well revealed by in situ infrared (IR) spectroscopy study.

Natural gas purification using a porous coordination polymer with water and chemical stability.

Porous coordination polymers (PCPs), constructed by bridging the metals or clusters and organic linkers, can provide a functional pore environment for gas storage and separation. But the rational design for identifying PCPs with high efficiency and low energy cost remains a challenge. Here, we demonstrate a new PCP, [(Cu4Cl)(BTBA)8·(CH3)2NH2)·(H2O)12]·xGuest (PCP-33⊃guest), which shows high potential for purification of natural gas, separation of C2H2/CO2 mixtures, and selective removal of C2H2 from C2H2/C2H4 mixtures at ambient temperature. The lower binding energy of the framework toward these light hydrocarbons indicates the reduced net costs for material regeneration, and meanwhile, the good water and chemical stability of it, in particular at pH = 2 and 60 °C, shows high potential usage under some harsh conditions. In addition, the adsorption process and effective site for separation was unravelled by in situ infrared spectroscopy studies.