Interaction of moderately reactive molecules with organic superhalogens: a theoretical perspective

The interaction of four moderately reactive molecules (MRMs), benzene (BZ), water, ammonia and silicon dioxide, with three aromatic organic superhalogens (OSHs) has been investigated at the density functional theory (DFT) level. The strength of the interaction is analysed from the distortions in the structures of both the MRMs and OSHs after complexation and the calculated binding energy (BE) values between the two interacting moieties. The interaction becomes stronger as we move from BZ to H₂O to NH₃ and strongest for SiO₂ molecule. Contributions from different terms in total interaction energy have been examined by energy decomposition analysis (EDA). The charge flow values between MRMs and OSHs, and Mulliken spin density localised on the moderately reactive molecules have been evaluated to ensure whether the interaction is ionic or not. Atoms in Molecules (AIM) analysis has been performed to characterise the bonds formed between the two. Overall, our study gives a comprehensive account of the interaction between the moderately reactive molecules and three theoretically designed aromatic organic superhalogens, which will further motivate researchers in the field of superhalogen chemistry.     

Structural-Deformation-Energy-Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular-recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest-triggered structural-transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def-modulation strategy via encoding inter-framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate-opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption-energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

Interfacial Engineering FeOOH/CoO Nanoneedle Array for Efficient Overall Water Splitting Driven by Solar Energy

Interface engineering has been applied as an effective strategy to boost the electrocatalytic performance because of the strong coupling and synergistic effects between individual components. Here, we engineered vertically aligned FeOOH/CoO nanoneedle array with a synergistic interface between FeOOH and CoO on Ni foam (NF) by a simple impregnation method. The synthesized FeOOH/CoO exhibits outstanding electrocatalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline medium. For the overall water splitting, the bifunctional FeOOH/CoO nanoneedle catalyst requires only a cell voltage of 1.58 V to achieve a current density of 10 mA cm⁻², which is much lower than that required for IrO₂//Pt/C (1.68 V). The FeOOH/CoO catalyst has been successfully applied for solar cell-driven water electrolysis, revealing its great potential for commercial hydrogen production and solar energy storage.     

Bromine-Functionalized Covalent Organic Frameworks for Efficient Triboelectric Nanogenerator

Covalent organic frameworks (COFs) enable precise integration of various organic building blocks into porous skeletons through topology predesign. Here, we report the first example of COFs by integrating electron withdrawing bromine group onto the skeletons for triboelectric nanogenerators (TENG). The resulting framework exhibits high surface area and good crystallinity. Thus, the bromine functionalized COF has more regular aligned π columns and arrays over the skeleton than bare COFs, which in turn significantly enhances charge transport ability. As a result, bromine functionalized COFs showed higher electrical output performance at 5 Hz with a peak value of short circuit current density of 43.6 μA and output voltage of 416 V, which is 2 and 1.3 times higher than those of bare COFs (21.6 μA and 318 V), respectively. These results demonstrated that this strategy for engineering electron withdrawing groups on the skeleton could open a new aspect of COFs for developing TENG devices.     

Gas-Sensing Activity of Amorphous Copper Oxide Porous Nanosheets

In this paper, the gas-sensing properties of copper oxide porous nanosheets in amorphous and highly crystalline states were comparatively investigated on the premise of almost the same specific surface area, morphology and size. Unexpectedly, the results show that amorphous copper oxide porous nanosheets have much better gas sensing properties than highly crystalline copper oxide to a serious of volatile organic compounds, and the lowest detection limit (LOD) of the amorphous copper oxide porous nanosheets to methanal is even up to 10 ppb. By contrast, the LOD of the highly crystalline copper oxide porous nanosheets to methanal is 95 ppb. Experiments prove that the oxygen vacancies contained in the amorphous copper oxide porous nanosheets play a key role in improving gas sensitivity, which greatly improve the chemical activity of the materials, especially for the adsorption of molecules containing oxygen-groups such as methanal and oxygen.     

强流电子束泵浦XeCl准分子激光动力学模型

强流电子束泵浦XeCl准分子激光动力学模型由三部分组成,即电子束能量沉积的计算;电子温度、电子反应速率的计算和化学/激光动力学。这个模型可以准确地预报小信号增益、吸收等激光特征量的时间变化规律。 该模型是在文献[1]、[2]、[3]报导的动力学模型的基础上提出的。采用四阶龙格_库塔法在VAX—11/780机器上进行数值求解。 计算给出XeCl准分子激光反应过程中各种粒子浓度、小信号增益、吸收、输出光强、激发速率以及平均电子能量随时间的变化规律。计算结果表明本征效率是激发速率,电流密度和工作气体(Ne/Xe/HCl)的各分压比的函数。 该模型可为高功率准分子激光器的研制提供设计参数和最佳实验条件。     

On the summation of the Brillouin-Wigner type perturbation series

It is shown that if the ‘mean excitation energy’ assumption is introduced in the Brillouin-Wigner perturbation series, then the resulting series can be exactly summed. The implications of the result for calculating energy shift and for constructing trial functions are examined with special reference to the ground state of the helium atom.     

Thermoluminescence kinetic study of binary lead-silicate glasses

This paper describes a detailed experimental study of the thermoluminescence (TL) properties of four binary lead-silicate glasses, with PbO concentrations ranging from 32% to 62% in mole percent. The TL glow peaks between room temperature and 300 °C were analyzed using a systematic thermal cleaning technique. The T_max-T_stop and E-T_stop methods of analysis were used to identify the number of peaks under the glow curves, and to obtain the activation energy E for each TL trap. A computerized glow curve fitting analysis is used to fit the experimental data to four first-order peaks with maxima at temperatures of 54, 80, 110 and 210 °C, as measured with a heating rate of 2 °C/s. The kinetic parameters of the glow-peak at 210 °C were confirmed by using phosphorescence decay methods of analysis. The TL traps associated with the low-temperature TL peak at 54 °C are found to depend strongly on the PbO concentration of the samples, while the higher-temperature TL peaks show a behavior independent of the PbO concentration. The activation energy E and frequency factor s of the low-temperature TL trap associated with the peak at 54 °C are consistent with a trap involving a delocalized transition through the conduction band. However, the activation energies and frequency factors for the higher-temperature TL traps are consistent with traps involving localized transitions via an excited state below the conduction band. The data suggest that these higher-temperature TL traps are associated with the common silicate matrix in these binary silicate glasses.