Crystalline porous organic salts.

Crystalline porous organic salts (CPOSs), formed by the self-assembly of organic acids and organic bases through ionic bonding, possess definite structures and permanent porosity and have rapidly emerged as an important class of porous organic materials in recent years. By rationally designing and controlling tectons, acidity/basicity (pKa), and topology, stable CPOSs with permanent porosity can be efficiently constructed. The characteristics of ionic bonds, charge-separated highly polar nano-confined channels, and permanent porosity endow CPOSs with unique physicochemical properties, offering extensive research opportunities for exploring their functionalities and application scenarios. In this review, we systematically summarize the latest progress in CPOS research, describe the synthetic strategies for synthesizing CPOSs, delineate their structural characteristics, and highlight the differences between CPOSs and hydrogen-bonded organic frameworks (HOFs). Furthermore, we provide an overview of the potential applications of CPOSs in areas such as negative linear compression (NLC), proton conduction, rapid transport of CO2, selective and rapid transport of K+ ions, atmospheric water harvesting (AWH), gas sorption, molecular rotors, fluorescence modulation, room-temperature phosphorescence (RTP) and catalysis. Finally, the challenges and future perspectives of CPOSs are presented.

Metal-Organic Framework with Space-Partition Pores by Fluorinated Anions for Benchmark C2H2/CO2 Separation.

The efficient separation of C2H2 from C2H2/CO2 or C2H2/CO2/CH4 mixtures is crucial for achieving high-purity C2H2 (>99%), essential in producing contemporary commodity chemicals. In this report, we present ZNU-12, a metal-organic framework with space-partitioned pores formed by inorganic fluorinated anions, for highly efficient C2H2/CO2 and C2H2/CO2/CH4 separation. The framework, partitioned by fluorinated SiF62- anions into three distinct cages, enables both a high C2H2 capacity (176.5 cm3/g at 298 K and 1.0 bar) and outstanding C2H2 selectivity over CO2 (13.4) and CH4 (233.5) simultaneously. Notably, we achieve a record-high C2H2 productivity (132.7, 105.9, 98.8, and 80.0 L/kg with 99.5% purity) from C2H2/CO2 (v/v = 50/50) and C2H2/CO2/CH4 (v/v = 1/1/1, 1/1/2, or 1/1/8) mixtures through a cycle of adsorption-desorption breakthrough experiments with high recovery rates. Theoretical calculations suggest the presence of potent "2 + 2" collaborative hydrogen bonds between C2H2 and two hexafluorosilicate (SiF62-) anions in the confined cavities.

3D Covalent Organic Framework with "the" Topology.

Discovery of new topology covalent organic frameworks (COFs) is a mainstay in reticular chemistry and materials research because it not only serves as a stepwise guide to the designed construction of covalent-organic architectures but also helps to comprehend function from structural design point-of-view. Proceeding on this track, the first 3D COF, TUS-38, with the topology is constructed by reticulating a planar triangular 3-c node of D3h symmetry with a tetragonal prism 8-c node of D2h symmetry via [3 + 8] reversible imine condensation reaction. TUS-38 represents a twofold interpenetrated multidirectional pore network with a high degree of crystallinity and structural integrity. Interestingly, stemming from the nitrogen-rich s-triazine rings with electron-deficient character and ─C â• N─ linkages composing the TUS-38 framework that benefit to the charge-transfer and hence dipole-dipole electrostatic interactions between the framework and iodine in addition to exclusive topological characteristics of the exotic the net, TUS-38 achieves an exemplary capacity for iodine vapor uptake reaching 6.3 g g-1. Recyclability studies evidence that TUS-38 can be reused at least five times retaining 95% of its initial adsorption capacity; while density functional theory (DFT) calculations have heightened the understanding of the interactions between iodine molecules and the framework.

Anhydrous Proton Conduction Through a Chemically Robust Electrolyte Enabling a High-Temperature Non-Precious Metal Catalyzed Fuel Cell.

Fuel cells offer great promise for portable electricity generation, but their use is currently limited by their low durability, excessive operating temperatures, and expensive precious metal electrodes. It is therefore essential to develop fuel cell systems that can perform effectively using more robust electrolyte materials, at reasonable temperatures, with lower-cost electrodes. Recently, proton exchange membrane fuel cells have attracted attention due to their generally favorable chemical stability and quick start-up times. However, in most membrane materials, water is required for proton conduction, severely limiting operational temperatures. Here, for the first time it is demonstrated that when acidified, PAF-1 can conduct protons at high temperatures, via a unique framework diffusion mechanism. It shows that this acidified PAF-1 material can be pressed into pellets with high proton conduction properties even at high temperatures and pellet thickness, highlighting the processibility, and ease of use of this material. Furthermore, a fuel cell is shown with high power density output is possible using a non-precious metal copper electrode. Acid-doped PAF-1 therefore represents a significant step forward in the potential for a broad-purpose fuel cell due to it being cheap, robust, efficient, and easily processible.

Reply to the Correspondence on "Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System".

White et al., in a recent Correspondence, provided additional structural data to illustrate that CPOS-6 undergoes a single-crystal-to-single-crystal transformation during water adsorption/desorption. This finding gave a better understanding of the relevant experimental phenomena from the perspective of structural transformation and is a good complement to our previous results. However, we wish to emphasize that our research focuses on the kinetic behavior of water during ultrafast adsorption/desorption in nano-confined channels. Herein, we further interpret the rapid transport of water molecules in the nano-confined channels from the perspective of superfluidity.

Record Ultralarge-Pores, Low Density Three-Dimensional Covalent Organic Framework for Controlled Drug Delivery.

The unique structural characteristics of three-dimensional (3D) covalent organic frameworks (COFs) like high surface areas, interconnected pore system and readily accessible active sites render them promising platforms for a wide set of functional applications. Albeit promising, the reticular construction of 3D COFs with large pores is a very demanding task owing to the formation of interpenetrated frameworks. Herein we report the designed synthesis of a 3D non-interpenetrated stp net COF, namely TUS-64, with the largest pore size of all 3D COFs (47 Å) and record-low density (0.106 g cm-3 ) by reticulating a 6-connected triptycene-based linker with a 4-connected porphyrin-based linker. Characterized with a highly interconnected mesoporous scaffold and good stability, TUS-64 shows efficient drug loading and controlled release for five different drugs in simulated body fluid environment, demonstrating the competency of TUS-64 as drug nanocarriers.

Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System.

In recent years, the porous sorbent-assisted atmospheric water harvesting (AWH) method has emerged as an effective approach for solving water crises without geographical restrictions. However, there is a limited array of porous adsorbent materials that can be used for AWH, which are inadequate to meet the needs under different climatic conditions. In light of this, herein, we synthesize a new crystalline porous organic salt (CPOS; denoted as CPOS-6) possessing a dual hydrogen bond system and verify its applicability toward AWH for the first time. Unlike other reported CPOSs, CPOS-6 displays an S-shaped water sorption isotherm owing to the presence of the dual hydrogen bond system. Under simulated drought conditions in Xinjiang Uygur Autonomous Region, CPOS-6 exhibits long-term water adsorption-desorption cycling stability, low water desorption temperature, and ultrarapid adsorption-desorption kinetics. The results confirm that CPOS-6 is an effective sorbent material for AWH.

Colossal Negative Linear Compressibility in Porous Organic Salts.

Negative linear compressibility (NLC) is a common sense violation (that is, crystal phases expand in one or more directions under hydrostatic compression). The excellent NLC performance of crystal materials is intrinsically related to the geometric structure of its skeleton. Here, we discovered a crystalline porous organic salt (CPOS-1); high-pressure X-ray diffraction experiments reveal that the CPOS-1 shows colossal NLC (Kc = -90.7 T Pa-1) behavior along the c axis. This incredible performance arises from the flexible "supramolecular spring" formed by the charge-enhanced N-H+···-O-S hydrogen bond interaction between the anionic sulfonate and the cationic ammonium ion. Furthermore, we reveal the relationship between this rare NLC behavior and single crystal proton conductivity using high-pressure electrochemical impedance spectroscopy (EIS) method. We believe that NLC behavior research on such inexpensive and readily available porous organic materials is of great significance for accelerating the research and application of NLC materials, especially in organic system.

High Uptake and Fast Transportation of LiPF6 in a Porous Aromatic Framework for Solid-State Li-Ion Batteries.

Solid-state Li-ion batteries (SSLIBs) have recently attracted substantial attention from scientists for the advantages of better safety performance. However, there are still several key challenges in SSLIBs that need to be addressed, such as low energy density, poor thermal stability or cycle stability, and large interface resistance. This contribution introduces a novel SSLIB with a porous aromatic framework (PAF-1) accommodating LiPF6 that was used as the solid-state electrolyte (SSE) replacing the liquid electrolyte and diaphragm of traditional Li-ion batteries. The charge, discharge capacity, rate performance and cycle stability of the SSLIB were remarkably enhanced.

Porous Organic Materials: Strategic Design and Structure-Function Correlation.

Porous organic materials have garnered colossal interest with the scientific fraternity due to their excellent gas sorption performances, catalytic abilities, energy storage capacities, and other intriguing applications. This review encompasses the recent significant breakthroughs and the conventional functions and practices in the field of porous organic materials to find useful applications and imparts a comprehensive understanding of the strategic evolution of the design and synthetic approaches of porous organic materials with tunable characteristics. We present an exhaustive analysis of the design strategies with special emphasis on the topologies of crystalline and amorphous porous organic materials. In addition to elucidating the structure-function correlation and state-of-the-art applications of porous organic materials, we address the challenges and restrictions that prevent us from realizing porous organic materials with tailored structures and properties for useful applications.

Synthesis of Crystalline Porous Organic Salts with High Proton Conductivity.

Self-assembled crystalline porous organic salts (CPOSs) formed by an acid-base combination and with one-dimensional polar channels containing water molecules have been synthesized. The water content in the channels of the porous salts plays an important role in the proton conduction performance of the materials. The porous salts described in this study feature high proton conductivity at ambient conditions and can reach as high as 2.2×10-2  S cm-1 at 333 K and under high humid conditions. This is among the best conductivity values reported to date for porous materials, for example, metal-organic frameworks and hydrogen-bonded organic frameworks. These materials exhibiting permanent porosity represent a group of porous materials and may find interesting applications in proton-exchange membrane fuel cells.

Chiral Recognition and Separation by Chirality-Enriched Metal-Organic Frameworks.

Endowed with chiral channels and pores, chiral metal-organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality-enriched MOFs with accessible pores. The ability of the materials to form host-guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed-matrix membranes (MMMs) composed of chirality-enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation.

A 3D Organically Synthesized Porous Carbon Material for Lithium-Ion Batteries.

We report the first organically synthesized sp-sp3 hybridized porous carbon, OSPC-1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to-date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium-ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.

Fabrication of COF-MOF Composite Membranes and Their Highly Selective Separation of H2/CO2.

The search for new types of membrane materials has been of continuous interest in both academia and industry, given their importance in a plethora of applications, particularly for energy-efficient separation technology. In this contribution, we demonstrate for the first time that a metal-organic framework (MOF) can be grown on the covalent-organic framework (COF) membrane to fabricate COF-MOF composite membranes. The resultant COF-MOF composite membranes demonstrate higher separation selectivity of H2/CO2 gas mixtures than the individual COF and MOF membranes. A sound proof for the synergy between two porous materials is the fact that the COF-MOF composite membranes surpass the Robeson upper bound of polymer membranes for mixture separation of a H2/CO2 gas pair and are among the best gas separation MOF membranes reported thus far.

Micropore engineering of carbonized porous aromatic framework (PAF-1) for supercapacitors application.

Micropore engineering of porous carbons on the effect of capacitance was explored using a carbonized porous aromatic framework (PAF-1). The porous carbons obtained through different carbonization methods show different pore structures enabling us to do this. The capacitance was measured both in aqueous electrolyte and different organic electrolytes. The porous carbons prepared by KOH activation show both high microporous volume, which is beneficial for charge storage, and mesoporous volume, which is devoted to fast ion diffusion in the pores; properties which are highly desirable. It shows a capacitance as high as 280 F g(-1) and 203 F g(-1) at a current density of 1 A g(-1) in 6.0 M KOH and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI), respectively. We also demonstrate the effect of diffusion and that of geometric packing of the electrolyte ions in the pores, where a commensurate match of the electrolyte ions with the pores of carbonized materials control and influence significantly the capacitance of these materials.

Electrochemical synthesis of a microporous conductive polymer based on a metal-organic framework thin film.

A new approach to preparing 3D microporous conductive polymer has been demonstrated in the electrochemical synthesis of a porous polyaniline network with the utilization of a MOF thin film supported on a conducting substrate. The prepared porous polyaniline with well-defined uniform micropores of 0.84 nm exhibits a high BET surface area of 986 m(2) g(-1) and a high electric conductivity of 0.125 S cm(-1) when doped with I2, which is superior to existing porous conducting materials of porous MOFs, CMPs, and COFs.

Molecular rotors in porous organic frameworks.

Porous organic frameworks perform a variety of functions, owing to their extremely large surface areas, but the dynamics of the structural elements have never been explored. Our discovery of ultra-fast molecular rotors (10(6)  Hz at 225 K) in their architectures allows us to look at them from a new perspective. The constructive elements are robust struts and rapid rotors, resulting in a dynamic material whose motion can be frozen or released at will. The rotational motion can be actively regulated in response to guests. As the temperature is increased, the rotors spin ever faster, approaching free-rotational diffusion at 550 K. The unusual combination of remarkable nanoporosity with fast dynamics is intriguing for engineering oscillating dipoles and producing responsive materials with switchable ferroelectricity, and for applications spanning from sensors to actuators, which capture and release chemicals on command.

Topochemical cross-linking of diacetylene in a highly interpenetrated three-dimensional covalent organic framework.

Topochemical polymerization is a highly promising and effective method for constructing complex three-dimensional structures and functionalized polymers. Herein, we present for the first time a topochemical reaction of diacetylene within a meticulously designed covalent organic framework (ZNUC-1). Our experimental results revealed that ZNUC-1 underwent a 1,4-addition reaction under thermal induction, forming an ene-yne-conjugated structure.

Lipocalin-2-mediated intestinal epithelial cells pyroptosis via NF-κB/NLRP3/GSDMD signaling axis adversely affects inflammation in colitis.

Ulcerative colitis (UC) is a major inflammatory bowel disease (IBD) characterized by intestinal epithelium damage. Recently, Lipocalin-2 (LCN2) has been identified as a potential fecal biomarker for patients with UC. However, further investigation is required to explore its pro-inflammatory role in UC and the underlying mechanism. The biological analysis revealed that Lcn2 serves as a putative signature gene in the colon mucosa of patients with UC and its association with the capsase/pyroptosis signaling pathway in UC. In wild-type mice with DSS-induced colitis, LCN2 overexpression in colon mucosa via in vivo administration of Lcn2 overexpression plasmid resulted in exacerbation of colitis symptoms and epithelium damage, as well as increased expression levels of pyroptosis markers (cleaved caspase1, GSDMD, IL-1ß, HMGB1 and IL-18). Additionally, we observed downregulation in the expression levels of pyroptosis markers following in vivo silencing of LCN2. However, the pro-inflammatory effect of LCN2 overexpression was effectively restrained in GSDMD-KO mice. Moreover, single-cell RNA-sequencing analysis revealed that Lcn2 was predominantly expressed in the intestinal epithelial cells (IECs) within the colon mucosa of patients with UC. We found that LCN2 effectively regulated pyroptosis events by modulating the NF-κB/NLRP3/GSDMD signaling axis in NCM460 cells stimulated by LPS and ATP. These findings demonstrate the pro-inflammatory role of LCN2 in colon epithelium and provide a potential target for inhibiting pyroptosis in UC.

A novel hydrophobic carborane-hybrid microporous material for reversed C2H6 adsorption and efficient C2H4/C2H6 separation under humid conditions.

Since ethylene (C2H4) is important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (C2H6)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display C2H4-selective features, we herein reported that the incorporation of a neutral para-carborane backbone and aliphatic 1,4-diazabicyclo[2.2.2]octane (DABCO) enables the reversed adsorption of C2H6 over C2H4. The generated carborane-hybrid microporous material ZNU-10 (ZNU = Zhejiang Normal University) is highly stable in humid air and maintains good C2H6/C2H4 separation performance under high humidity. Gas loaded single crystal structure and density-functional theory (DFT) calculations revealed that the weakly polarized carborane and DABCO within ZNU-10 induce more specific C-Hδ+⋯Hδ--B dihydrogen bonds and other van der Waals interactions with C2H6, while the suitable pore space allows the high C2H6 uptake. Approximately 14.5 L kg-1 of polymer grade C2H4 can be produced from simulated C2H6/C2H4 (v/v 10/90) mixtures under ambient conditions in a single step, comparable to those of many popular materials.