Separation of High-Purity C2H2 from Binary C2H2/CO2 Using Robust Al-Based MOFs Comprising Nitrogen-Containing Heterocyclic Dicarboxylate.

In this study, three nitrogen-containing aluminum-based metal-organic frameworks (Al-MOFs), namely, CAU-10pydc, MOF-303, and KMF-1, were investigated for the efficient separation of a C2H2/CO2 gas mixture. Among these three Al-MOFs, KMF-1 demonstrated the highest selectivity for C2H2/CO2 separation (6.31), primarily owing to its superior C2H2 uptake (7.90 mmol g-1) and lower CO2 uptake (2.82 mmol g-1) compared to that of the other two Al-MOFs. Dynamic breakthrough experiments, using an equimolar binary C2H2/CO2 gas mixture, demonstrated that KMF-1 achieved the highest separation performance. It yielded 3.42 mmol g-1 of high-purity C2H2 (>99.95%) through a straightforward desorption process under He purging at 298 K and 1 bar. To gain insights into the distinctive characteristics of the pore surfaces of structurally similar CAU-10pydc and KMF-1, we conducted computational simulations using canonical Monte Carlo and dispersion-corrected density functional theory methods. These simulations revealed that the secondary amine (C2N-H) groups in KMF-1 played a more significant role in differentiating between C2H2 and CO2 compared to that of the N atoms in CAU-10pydc and MOF-303. Consequently, KMF-1 emerged as a promising adsorbent for the separation of high-purity C2H2 from binary C2H2/CO2 gas mixtures.

Design of Pore Properties of an Al-Based Metal-Organic Framework for the Separation of an Ethane/Ethylene Gas Mixture via Ethane-Selective Adsorption.

A series of Al-based isomorphs (CAU-10H, MIL-160, KMF-1, and CAU-10pydc) were synthesized using isophthalic acid (ipa), 2,5-furandicarboxylic acid (fdc), 2,5-pyrrole dicarboxylic acid (pyrdc), and 3,5-pyridinedicarboxylic acid (pydc), respectively. These isomorphs were systematically investigated to identify the best adsorbent for effectively separating C2H6/C2H4. All CAU-10 isomorphs exhibited preferential adsorption of C2H6 over that of C2H4 in mixture. CAU-10pydc exhibited the best C2H6/C2H4 selectivity (1.68) and the highest C2H6 uptake (3.97 mmol g-1) at 298 K and 1 bar. In the breakthrough experiment using CAU-10pydc, 1/1 (v/v) and 1/15 (v/v) C2H6/C2H4 gas mixtures were successfully separated into high-purity C2H4 (>99.95%), with remarkable productivities of 14.0 LSTP kg-1 and 32.0 LSTP kg-1, respectively, at 298 K. Molecular simulations revealed that the exceptional separation performance of CAU-10pydc originated from the increased porosity and reduced electron density of the pyridine ring of pydc, leading to a relatively larger decrease in π-π interactions with C2H4 than in the C-H···π interactions with C2H6. This study demonstrates that the pore size and geometry of the CAU-10 platform are modulated by the inclusion of heteroatom-containing benzene dicarboxylate or heterocyclic rings of dicarboxylate-based organic linkers, thereby fine-tuning the C2H6/C2H4 separation ability. CAU-10pydc was determined to be an optimum adsorbent for this challenging separation.

Fabrication of Hierarchical, Porous, Bimetallic, Zeolitic Imidazolate Frameworks with the Incorporation of Square Planar Pd and Its Catalytic Application.

Bimetallic zeolitic imidazolate frameworks (ZIFs) containing two different metal ions can exhibit superior performances when applied in heterogeneous catalysis. Herein, we present a facile one-pot synthesis method for PdCo-ZIFs with various Pd/Co ratios, where Pd(II) ions are successfully incorporated into the Co node sites of the ZIF structure. The local structure of the bimetallic ZIFs was comprehensively investigated by pore-structure, X-ray absorption fine structure, and in situ CO adsorption Fourier transform infrared analyses. The results demonstrated that the framework comprises different coordination geometries of Co (tetrahedral) and Pd (square planar) ions connected by the benzimidazolate ligand. Notably, the inherently nonporous, 2D Co-ZIF structure was transformed into a hierarchical porous structure, and the PdCo-ZIFs exhibited a significantly increased concentration of defects and distorted Co sites. Based on these results, the catalytic performances of the synthesized ZIFs in the cycloaddition of CO2 to epoxides were evaluated under a cocatalyst and solvent-free conditions. The PdCo-ZIFs exhibited significantly higher catalytic activity (maximum turnover frequency, TOF = 2501 h-1) than Co-ZIF (TOF = 65 h-1) and Pd-ZIF (no activity), which revealed that the undercoordinated Co sites with distorted structure are the active sites rather than the incorporated Pd ions. This study provides a facile one-pot method for synthesizing bimetallic ZIFs with mixed-coordination modes, hierarchical porous structures, and modified defect concentrations, which would expand the library of structurally diverse bimetallic ZIFs toward various applications.

An Amine-Functionalized Ultramicroporous Metal-Organic Framework for Postcombustion CO2 Capture.

Among the most promising methods by which to capture CO2 from flue gas, the emission of which has accelerated global warming, is energy-efficient physisorption using metal-organic framework (MOF) adsorbents. Here, we present a novel cuprous-based ultramicroporous MOF, Cu(adci)-2 (adci- = 2-amino-4,5-dicyanoimidazolate), which was rationally synthesized by combining two strategies to design MOF physisorbents for enhanced CO2 capturing, i.e., aromatic amine functionalization and the introduction of ultramicroporosity (pore size <7 Å). Synchrotron powder X-ray diffraction and a Rietveld analysis reveal that the Cu(adci)-2 structure has one-dimensional square-shaped channels, in each of which all affiliated ligands, specifically NH2 groups at the 2-position of the imidazolate ring, have the same orientation, with a pair of NH2 groups therefore facing each other on opposite sides of the channel walls. While Cu(adci)-2 exhibits a high CO2 adsorption capacity (2.01 mmol g-1 at 298 K and 15 kPa) but a low zero-coverage isosteric heat of adsorption (27.5 kJ mol-1), breakthrough experiments under dry and 60% relative humidity conditions show that its CO2 capture ability is retained even in the presence of high amounts of moisture. In a Monte Carlo simulation and a radial distribution analysis, the preferential CO2 binding site of Cu(adci)-2 was predicted to be between two ligands, forming a sandwich-like structure and implying that its CO2 adsorption properties originate from the enhancement of Lewis base-acid and London dispersion interactions due to the amino groups and ultramicroporosity, respectively.

High-Performance Adsorbent for Ethane/Ethylene Separation Selected through the Computational Screening of Aluminum-Based Metal-Organic Frameworks.

The development of a high-performance ethane (C2H6)-selective adsorbent for the separation of ethane/ethylene (C2H6/C2H4) gas mixtures has been investigated for high-efficiency adsorption-based gas separation. Herein, we investigated Al-based metal-organic frameworks (MOFs) to identify an efficient C2H6-selective adsorbent (CAU-11), supported by a computational simulation study. CAU-11 exhibited numerous advantageous properties (such as low material cost, structural robustness, high reaction yield, and high C2H6/C2H4 selectivity) compared to other Al-based MOFs, indicating immense potential as a C2H6-selective adsorbent. CAU-11 exhibited preferential C2H6 adsorption in single-component gas adsorption experiments, and its predicted ideal adsorption solution theory selectivity of C2H6/C2H4 was over 2.1, consistent with the simulation analysis. Dynamic breakthrough experiments using representative compositions of the C2H6/C2H4 gas mixture confirmed the excellent separation ability of CAU-11; it produced high-purity C2H4 (>99.95%) with productivity values of 0.79 and 2.02 mol L-1 while repeating the cyclic experiment with 1:1 and 1:15 v/v C2H6/C2H4 gas mixtures, respectively, at 298 K and 1 bar. The high C2H6/C2H4 separation ability of CAU-11 could be attributed to its non-polar pore environment and optimum pore dimensions which strengthen the interaction of its pores (via C-H···π interactions) with C2H6 to a greater extent than with C2H4.

Immobilization of a trimeric ruthenium cluster in mesoporous chromium terephthalate and its catalytic application.

Molecular trimeric ruthenium carboxylate clusters (Ru3 clusters) have been introduced into the pore channels of mesoporous metal-organic framework chromium terephthalate [MIL-101(Cr)] by employing a facile two-step post-synthetic strategy in which diamine hooks anchored on the framework metal nodes of the MOF are used to covalently immobilize the Ru3 clusters. The catalytic activity of the isolated Ru3 clusters in the pore channels of the MOF was significantly improved compared to the bulk counterpart.

Rational design of a robust aluminum metal-organic framework for multi-purpose water-sorption-driven heat allocations.

Adsorption-driven heat transfer technology using water as working fluid is a promising eco-friendly strategy to address the exponential increase of global energy demands for cooling and heating purposes. Here we present the water sorption properties of a porous aluminum carboxylate metal-organic framework, [Al(OH)(C6H3NO4)]·nH2O, KMF-1, discovered by a joint computational predictive and experimental approaches, which exhibits step-like sorption isotherms, record volumetric working capacity (0.36 mL mL-1) and specific energy capacity (263 kWh m-3) under cooling working conditions, very high coefficient of performances of 0.75 (cooling) and 1.74 (heating) together with low driving temperature below 70 °C which allows the exploitation of solar heat, high cycling stability and remarkable heat storage capacity (348 kWh m-3). This level of performances makes this porous material as a unique and ideal multi-purpose water adsorbent to tackle the challenges of thermal energy storage and its further efficient exploitation for both cooling and heating applications.

Microporous 3D Graphene-like Zeolite-Templated Carbons for Preferential Adsorption of Ethane.

Microporous 3D graphene-like carbons were synthesized in Faujasite (FAU)-, EMT-, and beta-zeolite templates using the recently developed Ca2+ ion-catalyzed synthesis method. The microporous carbons liberated from these large-pore zeolites (0.7-0.9 nm) retain the structural regularity of zeolite. FAU-, EMT-, and beta zeolite-templated carbons (ZTCs) with faithfully constructed pore diameters of 1.2, 1.1, and 0.9 nm, respectively, and very large Brunauer-Emmet-Teller areas (2700-3200 m2 g-1) were obtained. We have discovered that these schwarzite-like carbons exhibit preferential adsorption of ethane over ethylene at pressures in the range of 1-10 bar. The curved graphene structure, consisting of a diverse range of carbon polygons with a narrow pore size of ∼1 nm, provides abundant adsorption sites in micropores and retains its ethane selectivity at pressures up to 10 bar. After varying the oxygen content in the beta ZTC, the ethane and ethylene adsorption isotherms show that the separation ability is not significantly affected by surface oxygen groups. Based on these adsorption results, a breakthrough separation procedure using a C2H4/C2H6 gas mixture (9:1 molar ratio) is demonstrated to produce ethylene with a purity of 99.9%.

Porous Metal-Organic Framework CUK-1 for Adsorption Heat Allocation toward Green Applications of Natural Refrigerant Water.

The development of new water adsorbents that are hydrothermally stable and can operate more efficiently than existing materials is essential for the advancement of water adsorption-driven chillers. Most of the existing benchmark materials and related systems in this field suffer from clear limitations that must be overcome to meet global requirements for sustainable and green energy production and utilization. Here, we report the energy-efficient water sorption properties of three isostructural metal-organic frameworks (MOFs) based on the simple ligand pyridine-2,4-dicarboxylate, named M-CUK-1 [M3(µ3-OH)2(2,4-pdc)2] (where M = Co2+, Ni2+, or Mg2+). The highly hydrothermally stable CUK-1 series feature step-like water adsorption isotherms, relatively high H2O sorption capacities between P/P0 = 0.10-0.25, stable cycling, facile regeneration, and, most importantly, benchmark coefficient of performance values for cooling and heating at a low driving temperature. Furthermore, these MOFs are prepared under green hydrothermal conditions in aqueous solutions. Our joint experimental-computational approach revealed that M-CUK-1 integrates several optimal features, resulting in promising materials as advanced water adsorbents for adsorption-driven cooling and heating applications.

Molecular Encapsulation of Trimeric Chromium Carboxylate Clusters in Metal-Organic Frameworks and Propylene Sorption.

Oxo-bridged trimeric chromium acetate clusters [Cr3 O(OOCCH3 )6 (H2 O)3 ]NO3 have been encapsulated for the first time in the mesoporous cages of the chromium terephthalate MIL-101(Cr). The isolated clusters in MIL-101(Cr) have increased affinity towards propylene compared to propane, due to generation of a new kind of pocket-based propylene-binding site, as supported by DFT calculations.

Highly selective adsorption of p-xylene over other C8 aromatic hydrocarbons by Co-CUK-1: a combined experimental and theoretical assessment.

High quality crystalline Co-CUK-1 can be synthesized rapidly and efficiently by a microwave-assisted method. The resulting microporous coordination material is a highly effective adsorbent for the separation of xylene isomers and ethylbenzene, as demonstrated here through sorption isotherm analysis, Ideal Adsorbed Solution Theory (IAST) calculations, and grand canonical Monte Carlo (GCMC) simulations. Co-CUK-1 showed high sorption capacity and high adsorption selectivity for p-xylene over the corresponding m- and o-isomers, and ethylbenzenes. According to the data obtained from IAST and GCMC simulations, the Co-CUK-1 is found to strongly favour p-xylene adsorption because p-xylene molecules undergo well-defined molecular packing in the 1-D channels; by comparison, the packing efficiencies of o-xylene, m-xylene and ethylbenzene are significantly lower, as is evidenced by lower saturation capacities.

Protonated MIL-125-NH2: Remarkable Adsorbent for the Removal of Quinoline and Indole from Liquid Fuel.

The removal of nitrogen-containing compounds (NCCs) from fossil fuels prior to combustion is currently of particular importance, and so we investigated an adsorptive method using metal-organic frameworks (MOFs) for the removal of indole (IND) and quinoline (QUI), which are two of the main NCCs present in fossil fuels. We herein employed an amino (-NH2)-functionalized MIL-125 (MIL-125-NH2) MOF, which was further modified by protonation (P-MIL-125-NH2). These modified MOFs exhibited extraordinary performance in the adsorption of both IND (as representative neutral NCC) and QUI (as representative basic NCC). These MOFs were one of the most efficient adsorbents for the removal of NCCs. For example, P-MIL-125-NH2 showed the highest adsorption capacity for QUI among ever reported adsorbent. The improved adsorption of IND was explained by H-bonding and cation-π interactions for MIL-125-NH2 and P-MIL-125-NH2, respectively, while the mechanisms for QUI were H-bonding and acid-base interactions, respectively. This is a rare phenomenon for a single material (especially not with very high porosity) to exhibit such remarkable performances in the adsorption of both basic QUI and neutral IND. The adsorption results obtained using regenerated MIL-125-NH2 and P-MIL-125-NH2 also showed that these materials can be used several times without any severe degradation.

Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites.

Selective dinitrogen binding to transition metal ions mainly covers two strategic domains: biological nitrogen fixation catalysed by metalloenzyme nitrogenases, and adsorptive purification of natural gas and air. Many transition metal-dinitrogen complexes have been envisaged for biomimetic nitrogen fixation to produce ammonia. Inspired by this concept, here we report mesoporous metal-organic framework materials containing accessible Cr(III) sites, able to thermodynamically capture N2 over CH4 and O2. This fundamental study integrating advanced experimental and computational tools confirmed that the separation mechanism for both N2/CH4 and N2/O2 gas mixtures is driven by the presence of these unsaturated Cr(III) sites that allows a much stronger binding of N2 over the two other gases. Besides the potential breakthrough in adsorption-based technologies, this proof of concept could open new horizons to address several challenges in chemistry, including the design of heterogeneous biomimetic catalysts through nitrogen fixation.

Enhanced adsorptive desulfurization with flexible metal-organic frameworks in the presence of diethyl ether and water.

Several metal-organic frameworks (MOFs) were employed in adsorptive desulfurization in the presence of oxygen-containing compounds (OCCs). Unlike conventional MOFs and activated carbon, flexible MOFs with a MIL-53 topology showed remarkable performances for the desulfurization in the presence of OCCs.

Adsorptive Separation of Acetylene from Light Hydrocarbons by Mesoporous Iron Trimesate MIL-100(Fe).

A reducible metal-organic framework (MOF), iron(III) trimesate, denoted as MIL-100(Fe), was investigated for the separation and purification of methane/ethane/ethylene/acetylene and an acetylene/CO2 mixtures by using sorption isotherms, breakthrough experiments, ideal adsorbed solution theory (IAST) calculations, and IR spectroscopic analysis. The MIL-100(Fe) showed high adsorption selectivity not only for acetylene and ethylene over methane and ethane, but also for acetylene over CO2 . The separation and purification of acetylene over ethylene was also possible for MIL-100(Fe) activated at 423 K. According to the data obtained from operando IR spectroscopy, the unsaturated Fe(III) sites and surface OH groups are mainly responsible for the successful separation of the acetylene/ethylene mixture, whereas the unsaturated Fe(II) sites have a detrimental effect on both separation and purification. The potential of MIL-100(Fe) for the separation of a mixture of C2 H2 /CO2 was also examined by using the IAST calculations and transient breakthrough simulations. Comparing the IAST selectivity calculations of C2 H2 /CO2 for four MOFs selected from the literature, the selectivity with MIL-100(Fe) was higher than those of CuBTC, ZJU-60a, and PCP-33, but lower than that of HOF-3.

Herniation pits as a radiographic indicator of pincer-type femoroacetabular impingement in symptomatic patients.

PURPOSE: The role of herniation pits as a radiographic indicator is still debated. This case-control study was to determine (1) the prevalence and sizes of herniation pits and (2) the relationship between herniation pits and femoral and acetabular bony morphology consistent with femoroacetabular impingement. METHODS: This comparative study was performed on 151 patients (151 hips; median patient age 46 years; range 16-73 years) with mechanical symptoms, who underwent multi-detector computed tomography (MDCT) arthrography (the symptomatic group), and an age-, gender-, site (left or right)-, and time (at diagnosis)-matched group of control patients that underwent multi-detector computed tomography due to an ureter stone (the asymptomatic group). Two orthopaedic surgeons reviewed images to evaluate the prevalence, sizes of herniation pits, and relationship with morphological abnormality. RESULTS: The prevalences of herniation pits in symptomatic and asymptomatic groups were 23.8 % (36/151) and 3.3 % (5/151), respectively (OR 9.14, 95 % CI 3.47-24.30; p < 0.001). Herniation pits were found to be significantly associated with pincer-type abnormality (p = 0.034), especially central acetabular retroversion (p < 0.001). CONCLUSIONS: This study shows that the prevalence of herniation pits is higher in symptomatic patients with femoroacetabular impingement, and herniation pits are associated with central acetabular retroversion. Furthermore, herniation pits were also found to be a useful predictor of pincer-type femoroacetabular impingement.

History of bioelectrical study and the electrophysiology of the primo vascular system.

Background. Primo vascular system is a new anatomical structure whose research results have reported the possibility of a new circulatory system similar to the blood vascular system and cells. Electrophysiology, which measures and analyzes bioelectrical signals tissues and cells, is an important research area for investigating the function of tissues and cells. The bioelectrical study of the primo vascular system has been reported by using modern techniques since the early 1960s by Bonghan Kim. This paper reviews the research result of the electrophysiological study of the primo vascular system for the discussion of the circulatory function. We hope it would help to study the electrophysiology of the primo vascular system for researchers. This paper will use the following exchangeable expressions: Kyungrak system = Bonghan system = Bonghan circulatory system = primo vascular system = primo system; Bonghan corpuscle = primo node; Bonghan duct = primo vessel. We think that objective descriptions of reviewed papers are more important than unified expressions when citing the papers. That said, this paper will unify the expressions of the primo vascular system.

Molecular sensing and discrimination by a luminescent terbium-phosphine oxide coordination material.

PCM-15 is a robust and recyclable sensor for the effective discrimination of a wide range of small molecules. Sensing is achieved by direct attenuation of the luminescence intensity of Tb(III) ions within the material. A competition study involving trace amounts of NH3 in H2 gas shows that PCM-15 can be used to quantitatively detect trace analytes.

Toward a theory of the primo vascular system: a hypothetical circulatory system at the subcellular level.

This paper suggests a theoretical framework for the primo vascular system (PVS), a hypothetical circulatory system, in which extracellular DNA microvesicles interact to form and break down cell structures. Since Bonghan Kim reported the existence of Bonghan ducts and the SNU research team reinvestigated and named it the PVS, there has been series of studies trying to examine its structure and functions. In this paper, we hypothesize that the PVS is the network system in which extracellular DNA microvesicles circulate and interact at the subcellular level, forming and breaking down cell structures. This idea integrates A. Béchamp's idea of microzymas and Bonghan Kim's idea of sanals. A proof of this idea may complement modern medical theory, perhaps providing an essential clue for an alternative solution dealing with modern healthcare problem.

Composition of the extracellular matrix of lymphatic novel threadlike structures: is it keratin?

Background. The lumen of novel threadlike structures (NTSs) is enclosed by a single layer of endothelial cells surrounded by extracellular matrix (ECM). We hypothesized that collagen may be a component of the ECM associated with lymphatic NTSs. Methods. Six female New Zealand white rabbits were anesthetized, and the NTS structures within lymphatic vessels were identified by contrast-enhanced stereomicroscopy or alcian blue staining. Isolated NTS specimens were stained with acridine orange, YOYO-1, and 1,1'-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (DiI). The structural and molecular composition of the ECM was investigated using transmission electron microscopy (TEM), electrospray ionization-mass spectrometry, and proteomic analysis. Results. The lymph vessel wall was stained red by DiI, and rod-shaped nuclei were stained green by YOYO-1. The area surrounding the NTS was also stained red and contained green rod-shaped nuclei. TEM images showed that the NTS consisted of many ECM fibers and the ECM fibers appeared to be ~100 nm in diameter and had narrowly spaced striated bands. Proteomic analysis of the lymphatic NTS-associated ECM identified 4 proteins: keratin 10, cytokeratin 3, cytokeratin 12, and soluble adenylyl cyclase. Conclusion. The TEM study suggested that the lymphatic NTS-associated ECM did not contain collagen. This was confirmed by proteomic analysis, which showed that keratin was the major component of the ECM.