Computational Study of spx(x=1–3)-Hybridized Be−Be Bonds Stabilized by Amidinate Ligands

Complexes containing odd-electron Be−Be bonds are still rare until now. Hereby, a series of neutral di-beryllium amidinate complexes containing a Be−Be bond were explored theoretically. The complexes with direct chelation with the Be₂ dimer by the bidentate amidinate (AMD) ligands are always corresponding to their global minimum structures. The detailed bonding analyses reveal that the localized electrons of the Be−Be fragment can be adjusted by the amount of AMD ligands because each AMD ligand only takes one electron from the Be₂ fragment. Meanwhile, the hybridization of the central Be atom also changes as the number of AMD ligands increases. In particular, the sp³-hybridized single-electron Be−Be bond is firstly identified in the tri-AMD-ligands-chelated neutral D_3h- Be₂(AMD)₃ complex, which also possesses the higher stability compared to its monoanionic D_3h- Be₂(AMD)₃ ⁻ and monocationic C₃- Be₂(AMD)₃ ⁺ analogues. Importantly, our study provides a new approach to obtain a neutral odd-electron Be−Be bond, namely by the use of radical ligands through side-on chelation.     

Evidence of Kinetically Relevant Consistency in Thermal and Photo-Thermal HCOOH Decomposition over Pd/LaCrO3/C3N4 Composite

Photo-thermal catalysis has been an attractive alternative strategy to promote chemical reactions for years, however, how light cooperates with thermal energy is still unclear. We meet this demand by exploring reaction mechanism via pressure dependency studies as well as H/D exchange experiments with HCOOH decomposition as a probe over a palladium nanoparticle (Pd_n) and isolated Pd (Pd₁) decorated LaCrO₃/C₃N₄ composite catalyst, in which the H₂ formation rate shows a first-order dependence on HCOOH and inverse first-order dependence on CO partial pressures no matter the reaction was driven by thermal or photo-thermal energy. Additionally, negligible kinetic isotopic effects (KIEs: k_H/k_D) were determined under both dark and light conditions at 1.04 and 1.18 when the HCOOH was replaced by HCOOD. Besides, when the reactant HCOOH was further replaced by DCOOD, the KIE values of 1.55 (dark) and 1.92 (light) were obtained, which indicates that the HCOOH decomposition follows kinetically relevant (KR) of C−H bond rupture within HCOOH molecule under both thermal and photo-thermal reaction conditions and the catalytic surface was found to be densely covered by CO based on the pressure dependency studies as well as the in situ Fourier transform infrared spectroscopy (FTIR) analysis. Clearly, the HCOOH decomposition driven by thermal and photo-thermal energy follows the same reaction mechanism. Nevertheless, light induced hot electrons and the derived thermal effect do cause the enhancement of the reaction activity in some circumstances compared with bare thermal catalysis, which clarifies the confusion on cooperation mechanism of photo and thermal energies from the kinetic perspective. Hot electrons induced by photo-illumination was confirmed by in situ FTIR CO chemisorption with ∼10 cm⁻¹ redshift identified of the CO feature once light was introduced. Meanwhile, the photo thermal reaction system suffers from severe electron-hole re-combination at high reaction temperatures and make the thermal effect of photo irradiation dominant with respect to the effect at low reaction temperatures. This research provides insight to the mechanism on how photo-thermal reaction works and draws attention to the photo-thermal reaction process in boosting catalytic activity.     

Atomic magnetometer with microfabricated vapor cells based on coherent population trapping

An atomic magnetometer based on coherent population trapping(CPT) resonances in microfabricated vapor cells is demonstrated. Fabricated by the micro-electro-mechanical-system(MEMS) technology, the cells are filled with Rb and Ne at a controlled pressure. An experimental apparatus is built for characterizing properties of microfabricated vapor cells via the CPT effects. The typical CPT linewidth is measured to be about 3 k Hz(1.46 k Hz with approximately zero laser intensity) for the rubidium D1 line at about 90℃. The effects of pressure, temperature and laser intensity on CPT linewidth are studied experimentally. A closed-loop atomic magnetometer is finally finished with a sensitivity of 210.5 p T/Hz1/2 at 1 Hz bandwidth. This work paves the way for developing an integrated chip-scale atomic magnetometer in the future.     

Controlling water temperature for efficient coal/gangue recognition

Coal and gangue (black-gray solid wastes in coal) recognition is vital to avoid waste of resources and pollution of the environment during the coal production. Considering their color/temperature is very close to each other, the traditional visible image and infrared image analyzing method is hard to obtain satisfied recognition efficiency. Therefore, a new idea of the ‘liquid intervention + infrared monitoring’ method was proposed to improve the recognition efficiency. In this article, the coal/gangue recognition experiments with different water temperatures were conducted, and the infrared thermal imager was used to record temperature variation after water intervention. The results show that when the water temperature is lower than the ambient temperature, the temperature difference between coal and gangue reaches the maximum value within 10 s, which is five times that without water intervention. The mean value of temperature difference between coal and gangue shows an approximate linear downward trend with the increasing of water temperature. The results indicate that under the condition of water intervention, it is recommended to choose water with a temperature below the ambient air, which may be a new approach to improve the coal/gangue recognition efficiency under different complex environments in underground coal mines.     

Polymerization Effects on the Decomposition of a Pyrazolo-Triazine at high Temperatures and Pressures

4-amino-3-aminopyrazole-8-trinitropyrazolo-[5, 1-c] [1, 2, 4]triazine (PTX, C₅H₂N₈O₆) has good detonation performance, thermal stability and low mechanical sensitivity, which endow it with good development prospects in insensitive ammunition applications. To study the effects of polymerization on the decomposition of PTX, the reaction processes of PTX at different conditions were simulated by quantum chemistry and molecular dynamics methods. In this paper, the effects of polymerization on the decomposition of PTX were studied in terms of species information, reaction path of PTX, bond formation and bond cleavage, evolution of small molecules and clusters, and kinetic parameters at different stages. The results show that under the high-temperature and high-pressure conditions, the initial reaction path of unimolecular PTX in the thermal decomposition is mainly the cleavage of C−NO₂ bonds. At the same time, there are many polymerization reactions in thermal decomposition process, which may greatly affect the reaction rate and path. The higher the degree of polymerization, the larger equilibrium value of potential energy, the less energy release of thermal decomposition. Compared with the activation energy of other explosives, the activation energy of PTX is higher than that of β-HMX and lower than that of TNT.     

Thermal behavior and thermal stabilization of guanidine hydrochloride-modified acrylic fiber for preparation of low-cost carbon fiber

Journal of Thermal Analysis and Calorimetry - A commercial textile-grade acrylic fiber was modified with guanidine hydrochloride for the preparation of low-cost carbon fibers. Thermal behavior of...     

A new phase-shifted long-period fiber grating for simultaneous measurement of torsion and temperature

A novel phase-shifted long-period fiber grating(PS-LPFG)for the simultaneous measurement of torsion and temperature is described and experimentally demonstrated.The PS-LPFG is fabricated by inserting a pretwisted structure into the long-period fiber grating(LPFG)written in single-mode fiber(SMF).Experimental results show that the torsion sensitivities of the two dips are?0.114 nm/(rad/m)and?0.069 nm/(rad/m)in the clockwise direction,and?0.087 nm/(rad/m)and?0.048 nm/(rad/m)in the counterclockwise direction,respectively.The temperature sensitivities of the two dips are 0.057 nm/℃ and 0.051 nm/℃,respectively.The two dips of the PS-LPFG exhibit different responses to torsion and temperature.Simultaneous measurement of torsion and temperature can be implemented using a sensor.The feasibility and stabilization of simultaneous torsion and temperature measurement have been confirmed,and hence this novel PS-LPFG demonstrates potential for fiber sensing and engineering applications.     

Polarization Behaviours at 2, 5 and 60 GHz for Indoor Mobile Communications

The behaviours of linear polarizations at 2.15, 5.3 and 61.7 GHz in corridors are studied in this paper. It shows that there is no significant difference between the received powers for vertical and horizontal polarizations. Depolarization is obvious at 2.15 GHz due to different antenna type is applied at the receiver, and it is more serious in non-line-of-sight (NLOS) cases.     

发射可见光多孔硅的拉曼光谱

本文报导了多孔硅的拉曼散射和光致发光的研究。给出了多孔硅的拉曼和光致发光谱之间的对应关系,根据拉曼峰的移动,估算了多孔硅量子线横截面的平均尺度为2.1～4.2nm。