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.     

Evidence of fluid evolution of Baoshan Cu−Pb−Zn polymetallic deposit: Constraints from in-situ sulfur isotope and trace element compositions of pyrite

In-situ LA-ICP-MS and S isotopes of pyrite from the Baoshan Cu polymetallic deposit were conducted to investigate the ore-forming process and the enrichment mechanism of elements. Three generations of pyrite (Py I, Py II, and Py III) in the skarn-type ores and pyrite in the carbonate-hosted sulfide ores from central, western, and northern (C_Py, W_Py, and N_Py) mining districts are selected for comparison. Compared with Py I and Py III, the contents of most elements in Py II are apparently higher. The As and Se contents are high within a wide range and are decoupled in the growth band of the C_Py. The highest As, Se, and Pb contents were found in W_Py and N_Py. These results indicate the drastic changes in the temperature and fluid mixing during the mineralization. The occurrence of fluctuation and change in temperature and f(O₂) was triggered by intermittent pulses of magmatic-hydrothermal fluids, mixing with meteoric water, and water−rock interactions. The sulfur isotopes of all species of pyrite indicated the magmatic source. The change in the f(O₂) conditions caused slight differences in the sulfur isotope compositions. Consequently, a metallogenic model was proposed to explain the ore-forming processes.     

Computational Fluid Dynamics versus Experiment: An Investigation on Liquid Weeping of Nye Trays

The weeping phenomenon was investigated using some experimental tests and a numerical model. The tests were performed within a 1.22‐m‐diameter pilot‐scale column including two chimney trays and two Nye test trays with an air‐water system. The rates of weeping were measured in the Nye trays with two heights of the weir and a hole area of 5 %. Moreover, the weeping rates in the outlet and inlet halves of the Nye tray and the total weeping rate were calculated. In the next step, an Eulerian‐Eulerian computational fluid dynamics (CFD) technique was used. The results show good agreement between the attained CFD findings and the experimental data.     

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.     

FE-SEA方法在平台支持船噪声预报中的应用

平台支持船由于作业需要通常配备有动力定位系统,其在侧推工况下舱室噪声超标较为严重。针对这个问题采用计算流体力学(CFD)方法,得到侧推螺旋桨作用在导管上的脉动压力,并将时域计算结果转换成噪声计算的激励条件。采用有限元(FE)与统计能量分析(SEA)混合方法建立船体中频段FE-SEA耦合模型并建立船体高频段SEA模型,对某65 m AHTS船侧推工况下全频段(63 Hz~8000 Hz)舱室噪声进行预报,分析该船噪声分布规律及主要影响因素。并建立起全船的SEA模型,在中频段对比SEA与FE-SEA两种方法得到的舱室声压级频谱曲线,验证了使用混合模型的必要性。     

High-Efficiency Organic Solar Cells Based on a Low-Cost Fully Non-Fused Electron Acceptor

A series of tetrathiophene-based fully non-fused ring acceptors (4T-1, 4T-2, 4T-3, and 4T-4), which can be paired with the star donor polymer PBDB-T to fabricate highly efficient organic solar cells are developed. Tailoring the size of lateral chains can tune the solubility and packing mode of acceptor molecules in neat and blend films. It is found that the incorporation of 2-ethylhexyl chains can effectively change the compatibility with the donor polymer PBDB-T, and an encouraging power conversion efficiency of 10.15% is accomplished by 4T-3-based organic solar cells. It also presents good compatibility with the other polymer donor and an even higher power conversion efficiency (PCE) of 12.04% is achieved based on D18:4T-3 blend, which is the champion PCE for the fully non-fused acceptors. Importantly, these inexpensive tetrathiophene fully non-fused ring acceptors provide cost-effective photovoltaic performance. The results demonstrate a high photovoltaic performance from synthetically inexpensive materials could be achieved by the rational design of non-fused ring acceptor molecules.     

Non-Halogenated-Solvent Processed and Additive-Free Tandem Organic Solar Cell with Efficiency Reaching 16.67%

Organic solar cells (OSCs) have recently reached a remarkably high efficiency and become a promising technology for commercial application. However, OSCs with top efficiency are mostly processed by halogenated solvents and with additives that are not environmentally friendly, which hinders large-scale manufacture. In this study, high-performance tandem OSCs, based on polymer donors and two small-molecule acceptors with different bandgaps, are fabricated by solution processing with non-halogenated solvents without additive. Importantly, the two active layers developed from non-halogenated solvents show better phase segregation and charge transport properties, leading to superior performance than halogenated ones. As a result, a tandem OSC with high efficiency of up to 16.67% is obtained, showing unique advantages in future massive production.