Porous Cyclodextrin Polymer Enables Dendrite-Free and Ultra-Long Life Solid-State Zn-I2 Batteries

Zn-I₂ batteries have attracted attention due to their low cost, safety, and environmental friendliness. However, their performance is still limited by the irreversible growth of Zn dendrites, hydrogen evolution reactions, corrosion, and shuttle effect of polyiodide. In this work, we have prepared a new porous polymer (CD-Si) by nucleophilic reaction of β-cyclodextrin with SiCl₄, and CD-Si is applied to the solid polymer electrolyte (denoted PEO/PVDF/CD-Si) to solve above-mentioned problems. Through the anchoring of the CD-Si, a conductive network with dual transmission channels was successfully constructed. Due to the non-covalent anchoring effect, the ionic conductivity of the solid polymer electrolytes (SPE) can reach 1.64×10⁻³ S cm⁻¹ at 25 °C. The assembled symmetrical batteries can achieve highly reversible dendrite-free galvanizing/stripping (stable cycling for 7500 h at 5 mA cm⁻² and 1200 h at 20 mA cm⁻²). The solid-state Zn-I₂ battery shows an ultra-long life of over 35,000 cycles at 2 A g⁻¹. Molecular dynamics simulations are performed to elucidate the working mechanism of CD-Si in the polymer matrix. This work provides a novel strategy towards solid electrolytes for Zn-I₂ batteries.     

Absolute CO2/Xenon Separation in Ultramicropore MOF for Anesthetic Gases Regeneration

Xe is an ideal anesthetic gas, but it has not been widely used in practice due to its high cost and low output. Closed-circuit Xe recovery and recycling is an economically viable method to ensure adequate supply in medical use. Herein, we design an innovative way to recover Xe by using a stable fluorinated metal-organic framework (MOF) NbOFFIVE-1-Ni to eliminate CO₂ from moist exhaled anesthetic gases. Unlike other Xe recovery MOFs with low Xe/CO₂ selectivity (less than 10), NbOFFIVE-1-Ni could achieve absolute molecular sieve separation of CO₂/Xe with excellent CO₂ selectivity (825). Mixed-gas breakthrough experiments assert the potential of NbOFFIVE-1-Ni as a molecular sieve adsorbent for the effective and energy-efficient removal of carbon dioxide with 99.16 % Xe recovery. Absolute CO₂/Xe separation in NbOFFIVE-1-Ni makes closed-circuit Xe recovery and recycling can be easily realized, demonstrating the potential of NbOFFIVE-1-Ni for important anesthetic gas regeneration under ambient conditions.     

Fluorine-Boosted Kinetic and Selective Molecular Sieving of C6 Derivatives

Porous molecular sorbents have excellent selectivity towards hydrocarbon separation with energy saving techniques. However, to realize commercialization, molecular sieving processes should be faster and more efficient compared to extended frameworks. In this work, we show that utilizing fluorine to improve the hydrophobic profile of leaning pillararenes affords a substantial kinetic selective adsorption of benzene over cyclohexane (20 : 1 for benzene). The crystal structure shows a porous macrocycle that acts as a perfect match for benzene in both the intrinsic and extrinsic cavities with strong interactions in the solid state. The fluorinated leaning pillararene surpasses all reported organic molecular sieves and is comparable to the extended metal–organic frameworks that were previously employed for this separation such as UIO-66. Most importantly, this sieving system outperformed the well-known zeolitic imidazolate frameworks under low pressure, which opens the door to new generations of molecular sieves that can compete with extended frameworks for more sustainable hydrocarbon separation.     

Selective Encapsulation and Chiral Induction of C60 and C70 Fullerenes by Axially Chiral Porous Aromatic Cages

Chiral induction has been an important topic in chemistry, not only for its relevance in understanding the mysterious phenomenon of spontaneous symmetry breaking in nature but also due to its critical implications in medicine and the chiral industry. The induced chirality of fullerenes by host–guest interactions has been rarely reported, mainly attributed to their chiral resistance from high symmetry and challenges in their accessibility. Herein, we report two new pairs of chiral porous aromatic cages (PAC), R- PAC-2 , S- PAC-2 (with Br substituents) and R- PAC-3 , S- PAC-3 (with CH₃ substituents) enantiomers. PAC-2 , rather than PAC-3 , achieves fullerene encapsulation and selective binding of C₇₀ over C₆₀ in fullerene carbon soot. More significantly, the occurrence of chiral induction between R- PAC-2 , S- PAC-2 and fullerenes is confirmed by single-crystal X-ray diffraction and the intense CD signal within the absorption region of fullerenes. DFT calculations reveal the contribution of electrostatic effects originating from face-to-face arene-fullerene interactions dominate C₇₀ selectivity and elucidate the substituent effect on fullerene encapsulation. The disturbance from the differential interactions between fullerene and surrounding chiral cages on the intrinsic highly symmetric electronic structure of fullerene could be the primary reason accounting for the induced chirality of fullerene.     

Functional Dithienopyrazines: Structure-Property Relationships**

Dithienopyrazines are only scarcely used as building blocks in organic electronic materials. Here, we report efficient preparation and investigation of syn- and anti-dithienopyrazines, which were functionalized with triaraylamine units to provide different series of donor-acceptor-donor-type materials. The characterization of the optoelectronic properties resulted in valuable structure-property relationships and allowed for the elucidation of the influence of structural effects such as core structure (syn vs anti), type of substituents (directly arylated vs ethynylated aryl), and substitution pattern (α,α’- vs β,β’- vs fourfold substitution). Finally, first application of a dithienopyrazine derivative as model for hole-transport materials tailored for organic electronic devices has been realized.     

Simple high-performance liquid chromatography-ultraviolet method for simultaneous separation and detection of 14 bisphenol pollutants in building materials

A high-performance liquid chromatography-ultraviolet method was developed for rapidly and simultaneously analyzing novel and typical bisphenols in building materials, including bisphenol S, diphenolic acid, bisphenol F, bisphenol E, bisphenol A, bisphenol B, bisphenol AF, bisphenol AP, bisphenol C, bisphenol FL, bisphenol Z, bisphenol BP, bisphenol M, and bisphenol P. By using a Kromasil 100–5 C18 column, these bisphenols were completely separated in 40 min via gradually increasing the concentration of methanol in the mobile phase from 45 to 80% during the elution process. In particular, this method achieved the synchronous analysis of bisphenol S, diphenolic acid, bisphenol FL, bisphenol BP, and bisphenol M through HPLC, which were difficult to separate and had to be identified and detected through mass spectrometry. The limits of detection of the method ranged from 0.002 to 0.040 mg/L for these 14 bisphenols, with a precision of less than 4.9% (n = 7, c = 0.05 mg/L). The analytical results for five types of building materials (phenolic, epoxy, polycarbonate, polyester, and polysulfone resins) indicated that the proposed method is appropriated for the rapid measurement of bisphenols in real samples.     

Surface modification of date palm activated carbonaceous materials for heavy metal removal and CO2 adsorption

In this study, high surface area activated carbon (AC) was prepared from a local palm tree (Phoenix Dactylifera) using a variety of metal carbonates activators and finally achieved an excellent S_BET of 2700 m²/g when Cs₂CO₃ was used as an activating agent at a temperature of 600 °C. Surface modification of AC was carried out using various nitrogen transporting agents, resulting in N-doped ACs with nitrogen content varying from 4.0 to 11.4 %, depending on the functionalizing agents and activators used. The bimodal (presence of micro- as well as meso-porosity) ACs with such excellent surface properties were studied for their CO₂ uptake capacity at two different temperatures (0 and 25 °C) by isotherms recorded at pressure 1 bar and showed a remarkable uptake ability of 3.52 mmol/g (at 25 °C) and 5.6 mmol/g (at 0 °C), respectively. Also, batch experiments with variable pH, contact time, adsorbate concentrations, adsorbent dose, and temperatures were evaluated to understand the mechanism of sorption phenomena of Cr(VI) and Pb(II) achieving > 99.9 % removal capacity by the prepared ACs. Depending on the heavy metal ions being investigated, it was revealed that the pH of the solution and the amount of adsorbent had a direct impact on the total adsorption ability. Nitrogen atoms doped into the carbon frameworks were found to enhance the adsorption in the case of Pb(II) while the removal of Cr(VI) appeared to be unaffected. Maximum adsorption for Cr(VI) was observed at pH 2 and was determined to follow Freundlich isotherm while that of Pb(II) was observed at pH 7 and follows Langmuir isotherm. Best adsorption was found at an adsorbate concentration of 10 ppm and an adsorbent dose of 10 g/L. Kinetic modeling parameters showed the applicability of pseudo-second-order model perfectly.     

The role of Carica papaya latex bio-catalyst and thermal shock in water on synthesizing rice husk

A bio-catalyst made of natural resources, such as Carica papaya latex, is very challenging for nanoparticle separation. In addition, differences in thermal conditions between nanoparticles affect the movement of substances in the separation process. The study experimentally investigated the role of Carica papaya latex bio-catalyst and thermal shock in water on synthesizing rice husk (RH). The synthesis retained the Mg and C elements attached to SiO₂, which were generally neglected during the process. The study's objective was to evaluate the effectiveness of biocatalysts and thermal effects on the separation of Mg-SiO₂-C from rice husk carbon nanoparticles (CNPs-RH). The research involved various treatment processes, such as RH pyrolysis in obtaining charcoal, High energy milling (HEM) to have carbon particles, and washing to get nano-sized carbon particles. The bonding of elemental compounds to rice husk carbon particles (CPs-RH) was released using NaOH and coagulation using a bio-catalyst. Coagulated CPs-RH was injected into water at a temperature of 60–70 °C to have a thermal shock effect for H₂O clusters in Na⁺ and Mg²⁺ ions attached to the surface of the nanoparticles. Several tests were carried out, such as the SEM-EDX, TEM, XRD, and FTIR tests, to investigate the two nanoparticle clusters formed up to the nanometer scale. The results indicated that CNPs-RH nanoparticles consist of spherical particles with a diameter of 1.2 nm, while Mg-SiO₂-C nanoparticles have a diameter of 0.6 nm. Both are classified as amorphous. Based on the FTIR test, CNPs-RH is hydrophilic, while Mg-SiO₂-C is hydrophobic. Thermal shock in water strengthens the ion's mobility, increasing the interfacial dipole forces between nanoparticles and accelerating the separation process.     

Three-Dimensional Covalent Organic Frameworks: From Synthesis to Applications

Three-dimensional covalent organic frameworks (3D COFs) with spatially periodic networks demonstrate significant advantages over their 2D counterparts, including enhanced specific surface areas, interconnected channels, and more sufficiently exposed active sites. Nevertheless, research on these materials has met an impasse due to serious problems in crystallization and stability, which must be solved for practical applications. In this Minireview, we first summarize some strategies for preparing functional 3D COFs, including crystallization techniques and functionalization methods. Hereafter, applications of these functional materials are presented, covering adsorption, separation, catalysis, fluorescence, sensing, and batteries. Finally, the future challenges and perspectives for the development of 3D COFs are discussed.     

In Situ Enzyme Immobilization by Covalent Organic Frameworks

Enzyme immobilization is a widely reported method to favor the applicability of enzymes by enhancing their stability and re-usability. Among the various existing solid supports and immobilization strategies, the in situ encapsulation of enzymes within crystalline porous matrices is a powerful tool to design biohybrids with a stable and protected catalytic activity. However, to date, only a few metal–organic frameworks (MOFs) and hydrogen-bonded organic frameworks (HOFs) have been reported. Excitingly, for the first time, Y. Chen and co-workers expanded the in situ bio-encapsulation to a new class of crystalline porous materials, namely covalent organic frameworks (COFs). The enzyme@COF materials not only exhibited high enzyme loading with minimal leaching, high catalytic activity and selectivity, chemical and long-term stability and recyclability but could also be scaled up to a few grams. Undoubtedly, this work opens new striking opportunities for enzymatic immobilization and will stimulate new research on COF-based matrices.