Sulfonate Functional Ultramicroporous Materials with Suitable Pore Size and Layer-Stacked Structure for C4 Olefins Purification.

Selective recognition of 1,3-butadiene from complex olefin isomers is vital for 1,3-butadiene purification, but the lack of porous materials with suitable pore structures results in poor selectivity and low capacity in C4 olefin separation. Herein, two sulfonate-functionalized organic frameworks, ZU-601 and ZU-602, are designed and show impressive separation performance toward C4 olefins. Benefiting from the suitable aperture size caused by the flexibility of coordinated organic ligand, ZU-601, ZU-602 that are pillared with different sulfonate anions could discriminate C4 olefin isomers with high uptake ratio: 1,3-butadiene/1-butene (207), 1,3-butadiene/trans-2-butene (10.1). Meanwhile, their layer-stacked structure enables the utilization of both intra- and interlayer space, enhancing the accommodation of guest molecules. ZU-601 exhibits record high 1,3-butadiene adsorption capacity of 2.90 mmol g-1 (0.5 bar, 298 K) among the reported flexible porous materials with high 1,3-butadiene/1-butene selectivity. The breakthrough experiments confirm their superior separation ability even for all five C4 olefin isomers, and the molecular-level structural change is well elucidated via powder, crystal analysis, and simulation studies. The work provides ideas toward advanced materials design with simultaneous high separation capacity and high separation selectivity for challenging separations.

Precise Construction of Nitrogen-Enriched Porous Ionic Polymers as Highly Efficient Sulfur Dioxide Adsorbent.

Porous ionic polymers with unique features have exhibited high performance in various applications. However, the fabrication of functional porous ionic polymers with custom functionality and porosity for efficient removal of low-concentration SO2 remains challenging. Herein, a novel nitrogen-enriched porous ionic polymer NH2Py-PIP is prepared featuring high-content nitrogen sites (15.9 wt.%), adequate ionic sites (1.22 mmol g-1), and a hierarchical porous structure. The proposed construction pathway relies on a tailored nitrogen-functionalized cross-linker NH2Py, which effectively introduces abundant functional sites and improves the porosity of porous ionic polymers. NH2Py-PIP with a well-engineered SO2-affinity environment achieves excellent SO2/CO2 selectivity (1165) and high SO2 adsorption capacity (1.13 mmol g-1 at 0.002 bar), as well as enables highly efficient and reversible dynamic separation performance. Modeling studies further elucidate that the nitrogen sites and bromide anions collaboratively promote preferential adsorption of SO2. The unique design in this work provides new insights into constructing functional porous ionic polymers for high-efficiency separations.

Highly Efficient Separation of Intermediate-Size m-Xylene from Xylenes via a Length-Matched Metal-Organic Framework with Optimal Oxygen Sites Distribution.

Xylene separation is crucial but challenging, especially for the preferential separation of the intermediate-size m-xylene from xylene mixtures. Herein, exploiting the differences in molecular length and alkyl distribution among xylenes, we present a length-matched metal-organic framework, formulated as Al(OH)[O2C-C4H2O-CO2], featuring an effective pore size corresponding to m-xylene molecular length combined with multiple negative O hydrogen bond donors distribution, can serve as a molecular trap for efficient preferential separation of the intermediate-size m-xylene. Benchmark separation performance was achieved for separating m-xylene from a ternary mixture of m-xylene/o-xylene/p-xylene, with simultaneous record-high m-xylene uptake (1.3 mmol g-1) and m-xylene/p-xylene selectivity (5.3) in the liquid-phase competitive adsorption. Both vapor- and liquid-phase fixed-bed tests confirmed its practical separation capability with benchmark dynamic m-xylene/p-xylene and m-xylene/o-xylene selectivities, as well as excellent regenerability. The selective and strong m-xylene binding affinity among xylene molecules was further elucidated by simulations, validating the effectiveness of such a pore environment for the separation of intermediate-size molecules.

A Robust Metal-Organic Framework with Scalable Synthesis and Optimal Adsorption and Desorption for Energy-Efficient Ethylene Purification.

Adsorptive separation is an energy-efficient alternative, but its advancement has been hindered by the challenge of industrially potential adsorbents development. Herein, a novel ultra-microporous metal-organic framework ZU-901 is designed that satisfies the basic criteria raised by ethylene/ethane (C2 H4 /C2 H6 ) pressure swing adsorption (PSA). ZU-901 exhibits an "S" shaped C2 H4 curve with high sorbent selection parameter (65) and could be mildly regenerated. Through green aqueous-phase synthesis, ZU-901 is easily scalable with 99 % yield, and it is stable in water, acid, basic solutions and cycling breakthrough experiments. Polymer-grade C2 H4 (99.51 %) could be obtained via a simulating two-bed PSA process, and the corresponding energy consumption is only 1/10 of that of simulating cryogenic distillation. Our work has demonstrated the great potential of pore engineering in designing porous materials with desired adsorption and desorption behavior to implement an efficient PSA process.

CO2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation.

Superbase-derived task-specific ionic liquids (STSILs) represent one of the most attractive and extensively studied systems in carbon capture via chemisorption, in which the obtained CO2 uptake capacity has a strong relationship with the basicity of the anions. High energy input in desorption and side reactions caused by the strong basicity of the anions are still unsolved issues. The development of other customized STSILs leveraging an alternative driving force to achieve efficient CO2 chemisorption/desorption is highly desirable yet challenging. In this work, carbanion-derived STSILs were developed for efficient CO2 chemisorption via a carboxylic acid formation pathway. The STSIL with the deprotonated malononitrile molecule ([MN]) as the anion exhibited much higher CO2 uptake capacity than the one derived from 2-methylmalononitrile ([MMN]). Notably, this trend was opposite to their basicity ([MN] < [MMN]). Detailed characterization of the products, supported by density functional theory simulations of spectra and calculations of the reaction energetics, demonstrated that carboxylic acid was formed upon reacting with CO2 via proton transfer in [MN]-derived STSILs but not in the case of [MMN] due to lack of an α-H. The preference of the carboxylic acid product over carboxylate formation was driven by the extended conjugation among the central sp2 carbon, the as-formed carboxylic acid, and the two nitrile groups. The achievements made in this work provide an alternative design principle of STSILs by leveraging the extended conjugation in the CO2-integrated product.

Photoinduced Strong Metal-Support Interaction for Enhanced Catalysis.

Strong metal-support interaction (SMSI) construction is a pivotal strategy to afford thermally robust nanocatalysts in industrial catalysis, but thermally induced reactions (>300 °C) in specific gaseous atmospheres are generally required in traditional procedures. In this work, a photochemistry-driven methodology was demonstrated for SMSI construction under ambient conditions. Encapsulation of Pd nanoparticles with a TiOx overlayer, the presence of Ti3+ species, and suppression of CO adsorption were achieved upon UV irradiation. The key lies in the generation of separated photoinduced reductive electrons (e-) and oxidative holes (h+), which subsequently trigger the formation of Ti3+ species/oxygen vacancies (Ov) and then interfacial Pd-Ov-Ti3+ sites, affording a Pd/TiO2 SMSI with enhanced catalytic hydrogenation efficiency. The as-constructed SMSI layer was reversible, and the photodriven procedure could be extended to Pd/ZnO and Pt/TiO2.

Tailoring the Pore Size and Chemistry of Ionic Ultramicroporous Polymers for Trace Sulfur Dioxide Capture with High Capacity and Selectivity.

Here we demonstrate the deep removal of SO2 with high uptake capacity (1.55 mmol g-1 ) and record SO2 /CO2 selectivity (>5000) at ultra-low pressure of 0.002 bar, using ionic ultramicroporous polymers (IUPs) with high density of basic anions. The successful construction of uniform ultramicropores via polymerizing ionic monomers into IUPs enables the fully exploitation of the selective anionic sites. Notably, the aperture size and surface chemistry of IUPs can be finely tuned by adjusting the branched structure of ionic monomers, which play critical roles in excluding CH4 and N2 , as well as reducing the coadsorption of CO2 . The swelling property of IUPs with adsorption of SO2 contributed to the high SO2 uptake capacity and high separation selectivity. Systematic investigations including static gas adsorption, dynamic breakthrough experiments, stability tests and modeling studies confirmed the efficient performance of IUPs for trace SO2 capture.

Perovskite Oxide-Halide Solid Solutions: A Platform for Electrocatalysts.

The successful integration or hybridization of perovskite oxides with their halide cousins would enable the formation of both multi-anionic and multi-cationic solid solutions with unique metal-ion sites and synergistic properties that could potentially surpass the performance of classic perovskites. However, such solid solutions had not been produced previously owing to their distinct formation energies and different synthesis conditions. Solid solutions combining perovskite oxides with fluorides were produced in this study by mechanochemical synthesis. The obtained perovskite oxide-halide solid solutions had highly mixed elements and valences, uniform element distributions, and single-phase crystalline structures. The solid solution with an optimized combination of oxides and fluorides exhibited enhanced catalytic performance in the oxygen evolution reaction.

Highly Perfluorinated Covalent Triazine Frameworks Derived from a Low-Temperature Ionothermal Approach Towards Enhanced CO2 Electroreduction.

Perfluorinated covalent triazine frameworks (F-CTFs) have shown unique features and attractive performance in separation and catalysis. However, state-of-the-art F-CTFs synthesized via the ZnCl2 -promoted procedure have quite low fluorine contents due to C-F bond cleavage induced by chloride (a Lewis base) and the harsh conditions deployed (400-700 °C). Fabricating F-CTFs with high fluorine contents (>30 wt %) remains challenging. Herein, we present a low-temperature ionothermal approach (275 °C) to prepare F-CTFs, which is achieved via polymerization of tetrafluoroterephthalonitrile (TFPN) over the Lewis superacids, e.g., zinc triflimide [Zn(NTf2 )2 ] without side reactions. With low catalyst loading (equimolar), F-CTFs are afforded with high fluorine content (31 wt %), surface area up to 367 m2 g-1 , and micropores around 1.1 nm. The highly hydrophobic F-CTF-1 exhibits good capability to boost electroreduction of CO2 to CO, with faradaic efficiency of 95.7 % at -0.8 V and high current density (-141 mA cm-2 ) surpassing most of the metal-free electrocatalysts.

Transformation Strategy for Highly Crystalline Covalent Triazine Frameworks: From Staggered AB to Eclipsed AA Stacking.

Fabrication of crystalline covalent triazine frameworks (CTFs) under mild conditions without introduction of carbonization is a long-term challenging subject. Herein, a tandem transformation strategy was demonstrated for the preparation of highly crystalline CTFs with high surface areas under mild and metal- and solvent-free conditions. CTF-1 with a staggered AB stacking order (orange powder) obtained in the presence of a catalytic amount of superacid at 250 °C was transformed to highly crystalline CTF-1 with an eclipsed AA stacking order (greenish powder) and surface area of 646 m2 g-1 through annealing at 350 °C under nitrogen. The strategy can be extended to the production of crystalline fluorinated CTFs with controllable fluorine content. This finding unlocks opportunities to design crystalline CTFs with tunable photoelectric properties.

ß-Cyclodextrin-derived Room Temperature Macromolecular Ionic Liquids by PEGylated Anions.

A series of cyclodextrin-derived room temperature macromolecular ionic liquids carrying rather low glass transition temperatures of -20 to -40 °C are synthesized via sequential esterification, quaternization, and anion metathesis reactions. In addition to being ionic in nature, they are viscous liquids at room temperature with more fluidic behavior at elevated temperatures. They serve as a solvent for organic dyes or iodine separation via a liquid-liquid extraction approach. This strategy is useful for the development of various sugar (macro)molecule-based functional ionic liquids as well as macromolecular ionic liquids.

Selective sorting of hexane isomers by anion-functionalized metal-organic frameworks with optimal energy regulation.

Extensive efforts have been made to improve the separation selectivity of hydrocarbon isomers with nearly distinguishable boiling points; however, how to balance the high regeneration energy consumption remains a daunting challenge. Here we describe the efficient separation of hexane isomers by constructing and exploiting the rotational freedom of organic linkers and inorganic SnF62- anions within adaptive frameworks, and reveal the nature of flexible host-guest interactions to maximize the gas-framework interactions while achieving potential energy storage. This approach enables the discrimination of hexane isomers according to the degree of branching along with high capacity and record mono-/di-branched selectivity (6.97), di-branched isomers selectivity (22.16), and upgrades the gasoline to a maximum RON (Research Octane Number) of 105. Benefitting from the energy regulation of the flexible pore space, the material can be easily regenerated only through a simple vacuum treatment for 15 minutes at 25 °C with no temperature fluctuation, saving almost 45% energy compared to the commercialized zeolite 5 A. This approach could potentially revolutionize the whole scenario of alkane isomer separation processes.

Direct prediction of gas adsorption via spatial atom interaction learning.

Physisorption relying on crystalline porous materials offers prospective avenues for sustainable separation processes, greenhouse gas capture, and energy storage. However, the lack of end-to-end deep learning model for adsorption prediction confines the rapid and precise screen of crystalline porous materials. Here, we present DeepSorption, a spatial atom interaction learning network that realizes accurate, fast, and direct structure-adsorption prediction with only information of atomic coordinate and chemical element types. The breakthrough in prediction is attributed to the awareness of global structure and local spatial atom interactions endowed by the developed Matformer, which provides the intuitive visualization of atomic-level thinking and executing trajectory in crystalline porous materials prediction. Complete adsorption curves prediction could be performed using DeepSorption with a higher accuracy than Grand canonical Monte Carlo simulation and other machine learning models, a 20-35% decline in the mean absolute error compared to graph neural network CGCNN and machine learning models based on descriptors. Since the established direct associations between raw structure and target functions are based on the understanding of the fundamental chemistry of interatomic interactions, the deep learning network is rationally universal in predicting the different physicochemical properties of various crystalline materials.

Graphitic Aza-Fused π-Conjugated Networks: Construction, Engineering, and Task-Specific Applications.

2D π-conjugated networks linked by aza-fused units represent a pivotal category of graphitic materials with stacked nanosheet architectures. Extensive efforts have been directed at their fabrication and application since the discovery of covalent triazine frameworks (CTFs). Besides the triazine cores, tricycloquinazoline and hexaazatriphenylene linkages are further introduced to tailor the structures and properties. Diverse related materials have been developed rapidly, and a thorough outlook is necessitated to unveil the structure-property-application relationships across multiple subcategories, which is pivotal to guide the design and fabrication toward enhanced task-specific performance. Herein, the structure types and development of related materials including CTFs, covalent quinazoline networks, and hexaazatriphenylene networks, are introduced. Advanced synthetic strategies coupled with characterization techniques provide powerful tools to engineer the properties and tune the associated behaviors in corresponding applications. Case studies in the areas of gas adsorption, membrane-based separation, thermo-/electro-/photocatalysis, and energy storage are then addressed, focusing on the correlation between structure/property engineering and optimization of the corresponding performance, particularly the preferred features and strategies in each specific field. In the last section, the underlying challenges and opportunities in construction and application of this emerging and promising material category are discussed.

Computational Insights into Malononitrile-Based Carbanions for CO2 Capture.

Although anionic N and O sites have been widely used in chemisorption of CO2, carbanions are much less explored for CO2 capture. Here we employ ab initio calculations and quantum mechanical/molecular mechanical (QM/MM) molecular dynamics (MD) simulations to examine the interaction between CO2 and the malononitrile carbanion, [CH(CN)2]-. We have explored the potential energy surface of CO2 binding by scanning the C-C distance between CO2 and the central C site of the carbanion. We find that CO2 prefers to bind to the nitrile group physically rather than to form a C-C bond via the carboxylation reaction at the sp2 C site. Moreover, the two -CN groups can attract two CO2 molecules at equal strength. The presence of an alkali metal ion enhances both physical and chemical interactions of CO2 with the malononitrile carbanion. QM/MM MD simulations further confirm the preference of physical interaction in the condensed ionic liquid phase with a phosphonium cation. Our findings suggest that ionic liquids based on the malononitrile carbanion may have a high CO2 solubility for carbon capture.

Ultramicroporous material based parallel and extended paraffin nano-trap for benchmark olefin purification.

Selective paraffin capture from olefin/paraffin mixtures could afford high-purity olefins directly, but suffers from the issues of low separation selectivity and olefin productivity. Herein, we report an ultramicroporous material (PCP-IPA) with parallel-aligned linearly extending isophthalic acid units along the one-dimensional channel, realizing the efficient production of ultra-high purity C2H4 and C3H6 (99.99%). The periodically expanded and parallel-aligned aromatic-based units served as a paraffin nano-trap to contact with the exposed hydrogen atoms of both C2H6 and C3H8, as demonstrated by the simulation studies. PCP-IPA exhibits record separation selectivity of 2.48 and separation potential of 1.20 mol/L for C3H8/C3H6 (50/50) mixture, meanwhile the excellent C2H6/C2H4 mixture separation performance. Ultra-high purity C3H6 (99.99%) and C2H4 (99.99%) can be directly obtained through fixed-bed column from C3H8/C3H6 and C2H6/C2H4 mixtures, respectively. The record C3H6 productivity is up to 15.23 L/kg from the equimolar of C3H8/C3H6, which is 3.85 times of the previous benchmark material, demonstrating its great potential for those important industrial separations.

New-Generation Carbon-Capture Ionic Liquids Regulated by Metal-Ion Coordination.

Development of efficient carbon capture-and-release technologies with minimal energy input is a long-term challenge in mitigating CO2 emissions, especially via CO2 chemisorption driven by engineered chemical bond construction. Herein, taking advantage of the structural diversity of ionic liquids (ILs) in tuning their physical and chemical properties, precise reaction energy regulation of CO2 chemisorption was demonstrated deploying metal-ion-amino-based ionic liquids (MAILs) as absorbents. The coordination ability of different metal sites (Cu, Zn, Co, Ni, and Mg) to amines was harnessed to achieve fine-tuning on stability constants of the metal ion-amine complexes, acting as the corresponding cations in the construction of diverse ILs coupled with CO2 -philic anions. The as-afforded MAILs exhibited efficient and controllable CO2 release behavior with great reduction in energy input and minimal sacrifice on CO2 uptake capacity. This coordination-regulated approach offers new prospects for the development of ILs-based systems and beyond towards energy-efficient carbon capture technologies.

Control of Functionalized Pore Environment in Robust Ionic Ultramicroporous Polymers for Efficient Removal of Trace Propyne from Propylene.

Separating trace propyne from propylene is of great importance in the petrochemical industry but difficult because of very close molecular sizes and physicochemical properties, which promotes the development of high-performance porous materials with great stability in practical adsorptive separation; however, a limited number of efficient adsorbents have been reported. Here, a class of robust functionalized ionic ultramicroporous polymers (IUPs) with different branched structures that feature high-density preferential anionic binding sites and outstanding thermal and water stability is systematically studied for the separation of propyne and propylene for the first time. The functionalized pore environment of IUPs achieves the highest selectivity of propyne and propylene (126.5) for the 1/99 (v/v) mixture among porous organic polymers, as well as excellent and recyclable dynamic separation performance. Modeling studies reveal that strong basic sites of IUPs with abundant ultramicroporosity facilitate the efficient removal of propyne from propylene. This study provides important clues for the design of robust functionalized adsorbents and thus expands the currently limited dictionary of adsorbents for the separation of important gas mixtures.

Benzene Ring Knitting Achieved by Ambient-Temperature Dehalogenation via Mechanochemical Ullmann-Type Reductive Coupling.

The current approaches capable of affording conjugated porous networks (CPNs) still rely on solution-based coupling reactions promoted by noble metal complexes or Lewis acids, on-surface polymerization conducted in ultrahigh-vacuum environment at very high temperatures (>200 °C), or mechanochemical Scholl-type reactions limited to electron-rich substrates. To develop simple and scalable approaches capable of making CPNs under neat and ambient conditions, herein, a novel and complementary method to the current oxidative Scholl coupling processes is demonstrated to afford CPNs via direct aromatic ring knitting promoted by mechanochemical Ullmann-type reactions. The key to this strategy lies in the dehalogenation of aromatic halides in the presence of Mg involving the formation of Grignard reagent intermediates. Products (Ph-CPN-1) obtained via direct CC bond formation between 1,2,4,5-tetrabromobenzene (TBB) monomer feature high surface areas together with mesoporous architecture. The versatility of this approach is confirmed by the successful construction of various CPNs via knitting of the corresponding aromatic rings (e.g., pyrene and triphenylene), and even highly crystalline graphite product was obtained. The CPNs exhibit good electrochemical performance as the anode material in lithium-ion batteries (LIBs). This approach expands the frontiers of CPN synthesis and provides new opportunities to their scalable applications.

CO2 Chemisorption Behavior of Coordination-Derived Phenolate Sorbents.

Invited for this month's cover is the group of Sheng Dai at the Oak Ridge National Laboratory. The image shows the CO2 chemisorption behavior of coordination-derived phenolate sorbents. The Communication itself is available at 10.1002/cssc.202100666.