Impact of defects on the decomposition of chemical warfare agent simulants in Zr-based metal organic frameworks

Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.     

High-Performance Solution-Processed Nondoped Circularly Polarized OLEDs with Chiral Triptycene Scaffold-Based TADF Emitters Realizing Over 20% External Quantum Efficiency

Recently, circularly polarized organic light-emitting diodes (CP-OLEDs) fabricated with thermally activated delayed fluorescence (TADF) emitters are developed rapidly. However, most devices are fabricated by vacuum deposition technology, and developing efficient solution-processed CP-OLEDs, especially nondoped devices, is still a challenge. Herein, a pair of triptycene-based enantiomers, (S,S)-/(R,R)-TpAc-TRZ, are synthesized. The novel chiral triptycene scaffold of enantiomers avoids their intermolecular π–π stacking, which is conducive to their aggregation-induced emission characteristics and high photoluminescence quantum yield of 85% in the solid state. Moreover, the triptycene-based enantiomers exhibit efficient TADF activities with a small singlet-triplet energy gap (ΔE_ST) of 0.03 eV and delayed fluorescence lifetime of 1.1 µs, as well as intense circularly polarized luminescence with dissymmetry factors (|g_PL|) of about 1.9 × 10⁻³. The solution-processed nondoped CP-OLEDs based on (S,S)-/(R,R)-TpAc-TRZ not only display obvious circularly polarized electroluminescence signals with g_EL values of +1.5 × 10⁻³ and −2.0 × 10⁻³, respectively, but also achieve high efficiencies with external quantum, current, and power efficiency up to 25.5%, 88.6 cd A⁻¹, and 95.9 lm W⁻¹, respectively.     

The Chemistry of DPPH· Free Radical and Congeners

Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH^·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.     

State-of-the-art technology: Recent investigations on laser-mediated synthesis of nanocomposites for environmental remediation

In both developing and industrialized/developed countries, various hazardous/toxic environmental pollutants are entering water bodies from organic and inorganic compounds (heavy metals and specifically dyes). The global population is growing whereas the accessibility of clean, potable and safe drinking water is decreasing, leading to world deterioration in human health and limitation of agricultural and/or economic development. Treatment of water/wastewater (mainly industrial water) via catalytic reduction/degradation of environmental pollutants is extremely critical and is a major concern/issue for public health. Light and/or laser ablation induced photocatalytic processes have attracted much attention during recent years for water treatment due to their good (photo)catalytic efficiencies in the reduction/degradation of organic/inorganic pollutants. Pulsed laser ablation (PLA) is a rather novel catalyst fabrication approach for the generation of nanostructures with special morphologies (nanoparticles (NPs), nanocrystals, nanocomposites, nanowires, etc.) and different compositions (metals, alloys, oxides, core-shell, etc.). Laser ablation in liquid (LAL) is generally considered a quickly growing approach for the synthesis and modification of nanomaterials for practical applications in diverse fields. LAL-synthesized nanomaterials have been identified as attractive nanocatalysts or valuable photocatalysts in (photo)catalytic reduction/degradation reactions. In this review, the laser ablation/irradiation strategies based on LAL are systematically described and the applications of LAL synthesized metal/metal oxide nanocatalysts with highly controlled nanostructures in the degradation/reduction of organic/inorganic water pollutants are highlighted along with their degradation/reduction mechanisms.     

Photocatalytic degradation of methylene blue and sulfisoxazole from water using biosynthesized zinc ferrite nanoparticles

The extensive occurrence of textile and pharmaceutical contaminants and their metabolites in water systems has posed significant concerns regarding their possible threat to human health and the environmental system. As a result, herein ZnFe₂O₄ nanoparticles were synthesized through the use of Monsonia burkeana plant extract. The synthesized nanoparticles were characterized using XRD, FTIR, UV–vis, SEM, EDS, TGA, BET, PL, EPR and VSM. XRD showed that the crystalline structure of ZnFe₂O₄ nanoparticles with a calculated crystal size of 25.03 nm was formed. FT-IR confirmed the characteristic functional groups contained within the M. burkeana plant were deposited on the formed ferrite nanoparticles. BET analysis confirmed the mesoporous nature of ZnFe₂O₄ with an average pore diameter of 31.6 nm. Morphological studies demonstrated that the formed nanoparticles had spherical as well as rod-like shapes. ZnFe₂O₄ photocatalyst illustrated that it may be effortlessly detached by an external magnetic field. The optimum conditions for the 99.8% removal of Methylene Blue was obtained at pH12, within 45min and at the optimum dosage of 25 mg of the catalyst. The as-prepared ZnFe₂O₄ nanoparticles proved to be easily separated and recycled, and remained efficient even after 5 reuses, proving that the material is highly stable. The ROS studies also demonstrated that electrons are the main factors contributing to the degradation of MB. Upon testing the photocatalytic performance of the sulfonamide antibiotic, sulfisoxazole in water showed a degradation of 67%. This study has shown that these materials can be used in targeting textile and pharmaceutically polluted water.     

Synthesis of magnetically recyclable porous CoFe2O4/Rh composites with large BET surface area for enhanced photocatalytic degradation of organic pollutant

The organic pollutants in water have been a great environment challenges to human beings, and photocatalytic degradation is an effective method to solve this problem. In this paper, the Rh-loaded cobalt ferrite CoFe₂O₄ (CFO) nanoparticles have been successfully synthesized by in situ photodeposition of Rh nanoparticles onto the porous CFO particles as the photocatalysts. After incorporating Rh nanoparticles, the CFO/Rh composite has a higher specific surface area and is more efficient in charge separation than the bare CFO. The photocatalytic efficiency of decomposing Malachite Green (MG) is improved from 70% over the bare CFO to 97% over the optimized CFO/Rh in 60 min. The CFO/Rh sample also demonstrates its durability for the degradation of MG in 5 photocatalytic reaction cycles. Additionally, hydroxyl radicals (?OH) and superoxide radicals (?O₂^?) are proved to be the crucial reactive species during the photocatalytic degradation of MG with CFO/Rh, evidenced by the active species capture experiments. This work provides a useful approach to enhance the photocatalytic activity of semiconductors for degrading organic dyes.     

Facile Fabrication of Luminescent Eu(III) Functionalized HOF Hydrogel Film with Multifunctionailities: Quinolones Fluorescent Sensor and Anticounterfeiting Platform

The luminescent hydrogen-bonded organic framework (HOF) based films have become one of the most remarkable materials for optical application, thus, developing facile synthesis methods and establishing multifunctional applications for HOF-based luminescent materials are essential. Herein, a dual-emitting Eu³⁺-functionalized HOF hydrogel film ( 1 ) is fabricated successfully. 1 emits a blue-green long afterglow when turning off the UV lamp, and the long afterglow lifetime gets to 1.99 s. 1 performs great selectivity, high sensitivity, and low detection limit toward ofloxacin and flumequine, and the sensing toward ofloxacin and flumequine is in accord with the chroma and ratio modes. The fluorescent response mechanisms of 1  toward ofloxacin and flumequine are investigated in depth, which are further utilized to build an anticounterfeiting platform with high-level security. The film-based anticounterfeiting platform can conduct information encryption on demand inline with different fluorescent responses and can also fetch specific information by controlling the long afterglow intensity and excited light. This study not only provides a representative case of the fabrication of dual-emitting Eu³⁺-functionalized HOF-based hydrogel film but also opens the possibility of HOF-based film as intelligent luminescent materials with multifunctionalities.     

Flexible,Mechanically Stable,Porous Self-Standing Microfiber Network Membranes of Covalent Organic Frameworks: Preparation Method and Characterization

Covalent organic frameworks (COFs) show advantageous characteristics, such as an ordered pore structure and a large surface area for gas storage and separation, energy storage, catalysis, and molecular separation. However, COFs usually exist as difficult-to-process powders, and preparing continuous, robust, flexible, foldable, and rollable COF membranes is still a challenge. Herein, such COF membranes with fiber morphology for the first time prepared via a newly introduced template-assisted framework process are reported. This method uses electrospun porous polymer membranes as a sacrificial large dimension template for making self-standing COF membranes. The porous COF fiber membranes, besides having high crystallinity, also show a large surface area (1153 m² g⁻¹), good mechanical stability, excellent thermal stability, and flexibility. This study opens up the possibility of preparation of large dimension COF membranes and their derivatives in a simple way and hence shows promise in technical applications in separation, catalysis, and energy in the future.     

Enhanced the photocatalytic activity of B–C–N–TiO2 under visible light:Synergistic effect of element doping and Z-scheme interface heterojunction constructed with Ag nanoparticles

In order to enhance the photocatalytic activity of TiO₂ under visible light, Ag nanoparticles were introduced into tridoped B–C–N–TiO₂ (TT) catalyst by photoreduction deposition. Ag/B–C–N–TiO₂ (ATT) catalysts with the functions of reducing band gap and carrier recombination were prepared. At the same time, the effect of the amount of Ag on the photocatalytic performance of ATT catalyst was investigated. Through XRD, XPS, PL and other characterization methods, the (211)/(101)/Ag interface heterojunction mechanism similar to the traditional Z-scheme heterojunction was proposed. The intervention of Ag nanoparticles changed the P–N interface heterojunction between (211)/(101) to the (211)/(101)/Ag Z-scheme interface heterojunction. The results show that ATT catalyst exhibits the highest photocatalytic activity when the molar amount of Ag is 0.005% with the MB degradation rate of the ATT catalyst (0.01707 min^?1), which is 14.59 times of TiO₂ (0.00117 min^?1) and 2.02 times of TT (0.00847 min^?1). In addition, the four cycles efficiencies of ATT for MB degradation were all above 94.00%.This study reveals the possibility of construction of Z-scheme heterojunctions between precious metal nanoparticles and different interfaces of TiO₂, and provides a reference for the construction of Z-scheme interface heterojunctions.     

Construction,structure and photocatalysis of janus nanofiber modified by g-C3N4 nanosheets heterostructure photocatalysts

The construction of photocatalyst with gradient band structure is guided by the principle of band gap engineering. Rational structural design is advanced and applied to construct a new-typed peculiarly structural and functional carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber modified by g-C₃N₄ nanosheets heterostructure photocatalyst (denoted as TB-JgHP). The flexible carbon-based [TiO₂/C]//[Bi₂WO₆/C] Janus nanofiber with one side responding to ultraviolet light and the other capturing visible light is fabricated by conjugate electrospinning, and then g-C₃N₄ nanosheets are uniformly grown in-situ on the surface of the Janus nanofibers by using gas-solid reaction via gasification of urea. The optimized TB-JgHP possesses remarkable hydrogen evolution efficiency (17.48 mmol h⁻¹ g⁻¹) and methylene blue degradation rate (99.2%) under simulated sunlight illumination for 100 min, demonstrating prominent dual-functional characteristics. The enhanced photocatalytic performance benefits from the unique Janus structure as well as the synergistic effects among the triple heterostructures of TiO₂ and Bi₂WO₆, g-C₃N₄ and TiO₂, g-C₃N₄ and Bi₂WO₆. The formation of gradient band structure among heterostructures is more conducive to the multi-step separation of photo-induced electron-hole pairs and more effective absorption of light. Further, flexible self-standing carbon-based photocatalysts not only have outstanding electron transport performance, but also are easy to separate from solution with preeminent recyclable stability. Based on a series of characterization techniques, it is further proved that TB-JgHP has higher carrier separation efficiency than the counterpart contrast samples. The formation mechanism of TB-JgHP is proposed, and the construction technique is established. The design philosophy and construction technique presented in this work pave a new avenue for research and development of other heterostructure photocatalysts.