Single Atoms of Iron on MoS2 Nanosheets for N2 Electroreduction into Ammonia

Efforts have been devoted to achieving a highly efficient artificial synthesis of ammonia (NH₃). Reported herein is a novel Fe-MoS₂ catalyst with Fe atomically dispersed onto MoS₂ nanosheets, imitating natural nitrogenase, to boost N₂ electroreduction into NH₃ at room temperature. The Fe-MoS₂ nanosheets exhibited a faradic efficiency of 18.8 % with a yield rate of 8.63 μg mg_cat.⁻¹ h⁻¹ for NH₃ at −0.3 V versus the reversible hydrogen electrode. The mechanism study revealed that the electroreduction of N₂ was promoted and the competing hydrogen evolution reaction was suppressed by decorating the edge sites of S in MoS₂ with the atomically dispersed Fe, resulting in high catalytic performance for the electroreduction of N₂ into NH₃. This work provides new ideas for the design of catalysts for N₂ electroreduction and strengthens the understanding about N₂ activation over Mo-based catalysts.     

Novel synthesis of 1,4-thiazin-2-one O-(tert-butyl) oximes and benzo[b][1,4]thiazin-2-one O-(tert-butyl) oximes in the presence of K2CO3/SiO2

A simple and efficient method was developed for the synthesis of 1,4-thiazin-2-one O-(tert-butyl) oximes and benzo[b][1,4]thiazin-2-one O-(tert-butyl) oximes from N-tert-butoxy acyl imidoyl bromides and 2-aminothiols in the presence of K₂CO₃/SiO₂. Twenty five novel compounds were readily synthesized in excellent yields using this procedure. The products possessed Z-stereochemistry with regard to the CN double bond. The reaction proceeded with initial substitution of bromine in the N-tert-butoxy acyl imidoyl bromides by mercapto groups in the presence of K₂CO₃/SiO₂, and subsequent intramolecular Schiff base formation.     

Theoretical insights into the mechanism of photocatalytic reduction of CO2 over semiconductor catalysts

Photocatalytic reduction of CO₂ is one important approach to alleviate greenhouse gas emission and energy crisis, which has gained huge attention in the past decades. However, the lack of understanding complex reaction mechanism impedes new catalysts design. It is also very difficult to understand the mechanism by using only experimental approaches. For this concern, theoretical calculations can effectively supplement the experimental deficiency and thus play an important role. Recently theoretical calculations have been performed on adsorption, migration and reduction of CO₂ molecule on the photocatalyst surface, leading to useful information that have contributed greatly to this field. This review summarizes recent advances in first-principles calculations about CO₂ photoreduction over various semiconductor photocatalysts like metal oxides, sulfides and g-C₃N₄. The methods, models, adsorption and reaction pathways have been discussed in detail. The perspective about future investigation on the photocatalytic reduction of CO₂ using first principles calculations is also presented.     

Three-dimensional Octameric Assembly of Icosahedral M13 Units in [Au8Ag57(Dppp)4(C6H11S)32Cl2]Cl and its [Au8Ag55(Dppp)4(C6H11S)34][BPh4]2 Derivative

The high-dimensional (that is, three-dimensional (3D)) assembly of nanomaterials is an effective means of improving their properties; however, achieving this assembly at the atomic level remains challenging. Herein, we obtained a novel nanocluster, [Au₈Ag₅₇(Dppp)₄(C₆H₁₁S)₃₂C_l2]Cl (Dppp=1,3-bis(diphenylphosphino)propane) showing a 3D octameric assembly mode involving the kernel penetration of eight complete icosahedral Au@Ag₁₀Au₂ units for the first time. The atomically precise structure was determined by single-crystal X-ray diffraction, and further confirmed by thermogravimetric analysis, X-ray photoelectron spectroscopy, and electrospray ionization mass spectrometry measurements. Furthermore, ligand-induced transformation prompted the conversion of [Au₈Ag₅₇(Dppp)₄(C₆H₁₁S)₃₂Cl₂]Cl, with complete octameric fusion into [Au₈Ag₅₅(Dppp)₄(C₆H₁₁S)₃₄][BPh₄]₂, with incomplete octameric fusion. These observations will hopefully facilitate further research on the assembly of M₁₃ nanobuilding blocks.     

Fixed-time disturbance observer-based robust fault-tolerant tracking control for uncertain quadrotor UAV subject to input delay

Nonlinear Dynamics - This study focuses on the design of a fixed-time disturbance observer-based robust fault-tolerant tracking control scheme for an uncertain quadrotor unmanned aerial vehicle...     

基于消失点检测算法的束靶红外图像畸变校正

传统的霍夫变换、Cannylines直线检测算法、霍夫概率变换方法在图像上的直线检测效果不佳,存在检测线段不连续不正确的问题,因而,利用Sobel滤波对红外图像横轴和纵轴两个方向分别进行锐化,通过线段检测(LSD)算法实现线段特征检测,进而经线段聚类拟合获得图像中完整的直线,通过对直线交点计算获得消失点,最后依据透视关系计算得到校正图像。实验结果表明,该方法可以实现对中性束红外图像的自动有效校正。     

Observation of multiferroic properties in a CdTe:Mn thin film grown by pulsed laser deposition techniques

We report multiferroic properties in a 3% Mn-doped CdTe (CdTe:Mn or CTM) thin film grown in a co-deposition system constituting pulsed laser deposition and radio frequency (RF) sputtering, in which the Mn concentration was tuned by the sputtering rate of Mn. We observed a clear ferroelectric hysteresis loop in the CTM thin film with remanent polarization of 3.5 μC/cm² and ferromagnetism in the film at a temperature lower than the Curie temperature of 15 K. Both features show direct evidence of multiferroics in the CTM thin film.     

Dielectric loss and electromagnetic absorption performance study of 1T/2H-MoS2/Mo2S3 nanocomposites with different ratios

High dielectric loss materials have an important application in electromagnetic (EM) absorption fields. In this paper, the ternary nanocomposites: 1T/2H-MoS₂/Mo₂S₃ with heterogeneous interfaces are synthesized by hydrothermal method. XRD, XPS, FTIR, SEM, and TEM measurements are applied to study the structure, morphology, and composition. The frequency spectra of complex permittivity (ε_r-f) are measured in 2–18 GHz by vector network analyzer. The results show that the nanocomposites have higher dielectric loss angle tangents than the reported 2H-MoS₂ absorbers. Based on the ε_r-f spectra, the reflection loss-frequency curves ($RL-f$) are simulated at given thicknesses. An effective absorption bandwidth of 5.2 GHz (12.8–18 GHz) and a $RL$ peak of −29.49 dB are achieved in a thin thickness of 1.62 mm, which are comparable to the reported 2H-MoS₂ absorbers with complex composition, showing that the 1T/2H-MoS₂/Mo₂S₃ nanocomposites have great application potential as an EM wave absorber in the K_u band.     

Direct synthesis of hyperbranched ethene oligomers and ethene-MA co-oligomers using iminopyridyl systems with weak neighboring group interactions

The synthesis of hyper-branched ethene oligomers through catalytic insertion reactions with late transition metal catalysts is unique in its synthetic and practical scope. In this study, a series of iminopyridyl Ni(II) and Pd(II) complexes with electron-rich distal aryl motifs were synthesized and characterized. These complexes were very efficient in ethene oligomerization and co-oligomerization with methyl acrylate (MA). Hyperbranched ethene oligomers with different microstructures were generated using different metal species in ethene oligomerization. More importantly, hyperbranched ethene-MA co-oligomers with varying incorporation ratios were generated via ethene and MA co-oligomerization using the Pd(II) complexes. Most notably, weak neighboring group interactions of distal aryl motifs in the nickel system are more effective in influencing the microstructure of ethene oligomers than the corresponding palladium system.     

Controllable Preparation of Branched Polyolefins with Various Microstructural Units via Chain-walking Ethylene and Pentene Polymerizations

Chinese Journal of Polymer Science - Branched polyolefins with controllable topology structures were generated from the chain-walking (co)polymerizations of ethylene, 1-pentene (1P) and 2-pentene...