Reverse Separation of Carbon Dioxide and Acetylene in Two Isostructural Copper Pyridine-Carboxylate Frameworks.

Separating acetylene from carbon dioxide is important but highly challenging due to their similar molecular shapes and physical properties. Adsorptive separation of carbon dioxide from acetylene can directly produce pure acetylene but is hardly realized because of relatively polarizable acetylene binds more strongly. Here, we reverse the CO and CH separation by adjusting the pore structures in two isoreticular ultramicroporous metal-organic frameworks (MOFs).

Molecular-Sieving Separation of Methanol/Benzene Azeotrope by a Flexible Metal-Organic Framework.

Separation of methanol/benzene azeotrope mixtures is very challenging not only by the conventional distillation technique but also by adsorbents. In this work, we design and synthesize a flexible Ca-based metal-organic framework MAF-58 consisting of cheap raw materials. MAF-58 shows selective methanol-induced pore-opening flexibility.

Pore chemistry and geometry control in a metal azolate framework for one-step ethylene purification from quinary gas mixture.

In the petrochemical industry, obtaining polymer-grade ethylene from complex light-hydrocarbon mixtures by one-step separation is important and challenging. Here, we successfully prepared the Metal-Azolate Framework 7 (MAF-7) with pore chemistry and geometry control to realize the one-step separation of ethylene from cracking gas with up to quinary gas mixtures (propane/propylene/ethane/ethylene/acetylene). Based on the tailor-made pore environment, MAF-7 exhibited better selective adsorption of propane, propylene, ethane and acetylene than ethylene, and the adsorption ratios of ethane/ethylene and propylene/ethylene are as high as 1.

Observation of Interpenetrated Topology Isomerism for Covalent Organic Frameworks with Atom-Resolution Single Crystal Structures.

Rational control and understanding of isomerism are of significance but still remain a great challenge in reticular frameworks, in particular, for covalent organic frameworks (COFs) due to the complicated synthesis and energy factors. Herein, reaction of 3,3',5,5'-tetra(4-formylphenyl)-2,2',6,6'-tetramethoxy-1,1'-biphenyl (TFTB) with 3,3',5,5'-tetrakis(4-aminophenyl)bimesityl (TAPB) under different reaction conditions affords single crystals of two 3D COF isomers, namely, USTB-20-dia and USTB-20-qtz. Their structures with resolutions up to 0.

Linkage conversions in single-crystalline covalent organic frameworks.

Single-crystal X-ray diffraction is a powerful characterization technique that enables the determination of atomic arrangements in crystalline materials. Growing or retaining large single crystals amenable to it has, however, remained challenging with covalent organic frameworks (COFs), especially suffering from post-synthetic modifications. Here we show the synthesis of a flexible COF with interpenetrated qtz topology by polymerization of tetra(phenyl)bimesityl-based tetraaldehyde and tetraamine building blocks.

Pore Modulation of Hydrogen-Bonded Organic Frameworks for Efficient Separation of Propylene.

Developing hydrogen-bonded organic frameworks (HOFs) that combine functional sites, size control, and storage capability for targeting gas molecule capture is a novel and challenging venture. However, there is a lack of effective strategies to tune the hydrogen-bonded network to achieve high-performance HOFs. Here, a series of HOFs termed as HOF-ZSTU-M (M=1, 2, and 3) with different pore structures are obtained by introducing structure-directing agents (SDAs) into the hydrogen-bonding network of tetrakis (4-carboxyphenyl) porphyrin (TCPP).

Construction of Fluorinated Propane-Trap in Metal-Organic Frameworks for Record Polymer-Grade Propylene Production under High Humidity Conditions.

Propane/propene (C H /C H ) separation is essential in the petrochemical industry but challenging because of their similar physical and chemical properties. Adsorptive separation with C H -selective porous materials can energy-efficiently produce high-purity C H , which is highly promising for replacing conventional cryogenic distillation but suffers from unsatisfactory performance. Herein, through the precise incorporation of fluorinated functional groups into the confined pore space, a new fluorinated metal-organic framework (FDMOF-2) featuring the unique and strong C H -trap is successfully constructed.

How Reproducible are Surface Areas Calculated from the BET Equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials.

Identifying the Gate-Opening Mechanism in the Flexible Metal-Organic Framework UTSA-300.

Atomic-level understanding of the gate-opening phenomenon in flexible porous materials is an important step toward learning how to control, design, and engineer them for applications such as the separation of gases from complex mixtures. Here, we report such mechanistic insight through an in-depth study of the pressure-induced gate-opening phenomenon in our earlier reported metal-organic framework (MOF) Zn(dps)(SiF) (dps = 4,4'-dipyridylsulfide), also called UTSA-300, using isotherm and calorimetry measurements, infrared spectroscopy, and simulations. UTSA-300 is shown to selectively adsorb acetylene (CH) over ethylene (CH) and ethane (CH) and undergoes an abrupt gate-opening phenomenon, making this framework a highly selective gas separator of this complex mixture.

Fine pore engineering in a series of isoreticular metal-organic frameworks for efficient CH/CO separation.

The separation of CH/CO is not only industrially important for acetylene purification but also scientifically challenging owing to their high similarities in physical properties and molecular sizes. Ultramicroporous metal-organic frameworks (MOFs) can exhibit a pore confinement effect to differentiate gas molecules of similar size. Herein, we report the fine-tuning of pore sizes in sub-nanometer scale on a series of isoreticular MOFs that can realize highly efficient CH/CO separation.

An Adaptive Hydrogen-Bonded Organic Framework for the Exclusive Recognition of p-Xylene.

Separation of xylene isomers is one of the most important but most challenging and energy-intensive separation processes in the petrochemical industry. Here, we report an adaptive hydrogen-bonded organic framework (HOF-29) constructed from a porphyrin based organic building block 4,4',4'',4'''-(porphyrin-5,10,15,20-tetrayl) tetrabenzonitrile (PTTBN), exhibiting the exclusive molecular recognition of p-xylene (pX) over its isomers of o-xylene (oX) and m-xylene (mX), as clearly demonstrated in the single crystal structure transformation and H NMR studies. Single crystal structure studies show that single-crystal-to-single-crystal transformation from the as-synthesized HOF-29 to the pX exclusively included HOF-29⊃pX is triggered by the encapsulation of pX molecules, accompanied by sliding of the 2D layers and local distortion of the ligand, which provides multiple C-H⋅⋅⋅π interactions.

Single-crystal superprotonic conductivity in an interpenetrated hydrogen-bonded quadruplex framework.

A proton-transporting pathway is crucial to the conduction mechanism in fuel cells and biological systems. Here, we report a novel 5-fold interpenetrated three-dimensional (3D) hydrogen-bonded quadruplex framework, which exhibits an ultrahigh single-crystal proton conductivity of 1.2(1) × 10 S cm at 95 °C and 98% relative humidity, benefitting from the spiral HO/HO chains in 1D pore channels studded with COOH/COO groups.

Old Materials for New Functions: Recent Progress on Metal Cyanide Based Porous Materials.

Cyanide is the simplest ligand with strong basicity to construct open frameworks including some of the oldest compounds reported in the history of coordination chemistry. Cyanide can form numerous cyanometallates with different transition metal ions showing diverse geometries. Rational design of robust extended networks is enabled by the strong bonding nature and high directionality of cyanide ligand.

A Molecular Compound for Highly Selective Purification of Ethylene.

Purification of C H from an C H /C H mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF ) Bp]Cu} has features very desirable in an olefin-paraffin separation material.

Highly Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Metal-Organic Framework.

Separating carbon dioxide from fuel gases like hydrocarbons by physical adsorbents is industrially important and more energy-efficient than traditional liquid extraction or cryogenic distillation methods. It is very important while very challenging to develop CO -selective adsorbents, considering CO is less polarizable than light hydrocarbon molecules, particularly those simultaneously with almost identical molecular dimensions and physical properties, such as acetylene. Herein, an ultramicroporous metal-organic framework constructed from copper(II) and 5-fluoropyrimidin-2-olate, termed Cu-F-pymo, is carefully studied under different activations for inverse separation of CO from C H .

Achieving High Performance Metal-Organic Framework Materials through Pore Engineering.

Achieving high performance functional materials has been a long-term goal for scientists and engineers that can significantly promote science and technology development and thus benefit our society and human beings. As well-known porous materials, metal-organic frameworks (MOFs) are crystalline open frameworks made up of molecular building blocks linked by strong coordination bonds, affording pore space for storing and trapping guest molecules. In terms of porosity, MOFs outperform traditional porous materials including zeolites and activated carbon, showing exceptional porosity with internal surface area up to thousands of square meters per gram of sample and with periodic pore sizes ranging from sub-nanometer to nanometers.

Ethylene/ethane separation in a stable hydrogen-bonded organic framework through a gating mechanism.

Porous materials are very promising for the development of cost- and energy-efficient separation processes, such as for the purification of ethylene from ethylene/ethane mixture-an important but currently challenging industrial process. Here we report a microporous hydrogen-bonded organic framework that takes up ethylene with very good selectivity over ethane through a gating mechanism. The material consists of tetracyano-bicarbazole building blocks held together through intermolecular CN···H-C hydrogen bonding interactions, and forms as a threefold-interpenetrated framework with pores of suitable size for the selective capture of ethylene.

A Microporous Hydrogen-Bonded Organic Framework for the Efficient Capture and Purification of Propylene.

Adsorptive separation of propylene/propane (C H /C H ) mixture is desired for its potential energy saving on replacing currently deployed and energy-intensive cryogenic distillation. Realizing efficient C H /C H separation in the emerging hydrogen-bonded organic frameworks (HOFs) is very challenging owing to the lack of functional sites for preferential gas binding. By virtue of crystal engineering, we herein report a functionalized HOF (HOF-16) with free -COOH sites for the efficient separation of C H /C H mixtures.

Realization of Ethylene Production from Its Quaternary Mixture through Metal-Organic Framework Materials.

Ethylene production from oxidative coupling of methane is a sustainable and economically attractive alternative to that through traditional hydrocarbon cracking technology. However, efficient ethylene separation from the complex reaction mixture is a daunting challenge that hinders the practical adoption of this technology. Herein, we report the efficient adsorptive separation of the CH/CO/CH/CH mixture using three representative metal-organic frameworks (MOFs) (UTSA-74, MOF-74, and HKUST-1) with diverse open metal sites.

Electrostatically Driven Selective Adsorption of Carbon Dioxide over Acetylene in an Ultramicroporous Material.

Separating acetylene from carbon dioxide is important but highly challenging owing to their similar physical properties and molecular dimensions. Herein, we report highly efficient electrostatically driven CO /C H separation in an ultramicroporous cadmium nitroprusside (Cd-NP) with compact pore space and complementary electrostatic potential well fitting for CO , thus enabling molecular quadrupole moment recognition of CO over C H . This material shows a high CO /C H uptake ratio of 6.

Isoreticular Microporous Metal-Organic Frameworks for Carbon Dioxide Capture.

The isoreticular principle has been applied to construct two copper metal-organic framework (MOF) analogues with different porosities for the adsorptive capture of CO from N and CH at 1 atm and 298 K. By using a 4-substituted isophthalate linker with a bulky nitro group, the microporous MOF [Cu(BDC-NO)(DMF)] ( or ; HBDC-NO = 4-nitroisophthalic acid and DMF = ,'-dimethylformamide) has been synthesized with topology, showing a compact pore structure with a size of 6.0 × 7.

Doubly Interpenetrated Metal-Organic Framework of pcu Topology for Selective Separation of Propylene from Propane.

Adsorptive separation is an appealing alternative technology to reduce the high energy and capital cost of the distillation separation of propylene/propane; however, it is very challenging to realize. A new flexible metal-organic framework (MOF) material [Zn(BDC-Cl)(PyTTz)] with a doubly interpenetrated pillared paddle wheel structure of (primitive cubic) topology has been realized for this difficult separation for the first time. Through a judicious choice of linkers, the framework has small pore apertures that lead to much more propylene adsorption than propane.

An Ultramicroporous Metal-Organic Framework for High Sieving Separation of Propylene from Propane.

Highly selective adsorptive separation of olefin/paraffin through porous materials can produce high purity olefins in a much more energy-efficient way than the traditional cryogenic distillation. Here we report an ultramicroporous cobalt gallate metal-organic framework (Co-gallate) for the highly selective sieving separation of propylene/propane at ambient conditions. This material possesses optimal pore structure for the exact confinement of propylene molecules while excluding the slightly large propane molecules, as clearly demonstrated in the neutron diffraction crystal structure of Co-gallate⊃0.

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 (C H ), acetylene (C H ), and carbon dioxide (CO ) can be regulated by temperature.

Hydrogen-Bonded Organic Frameworks as a Tunable Platform for Functional Materials.

As a novel class of porous crystalline materials, hydrogen-bonded organic frameworks (HOFs), self-assembled from organic or metal-organic building blocks through intermolecular hydrogen-bonding interactions, have attracted more and more attention. Over the past decade, a number of porous HOFs have been constructed through judicious selection of H-bonding motifs, which are further enforced by other weak intermolecular interactions such as π-π stacking and van der Waals forces and framework interpenetration. Since the H-bonds are weaker than coordinate and covalent bonds used for the construction of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), HOFs have some unique features such as mild synthesis condition, solution processability, easy healing, and regeneration.