Activating Bi p-orbitals in Dispersed Clusters of Amorphous BiOx for Electrocatalytic Nitrogen Reduction

Catalytic strategies based on main group metals are significantly less advanced than those of transition metal catalysis, leaving untapped areas of potentially fruitful research. We here demonstrate an effective approach for the modulation of Bi 6p energy levels during the construction of atomically dispersed clusters of amorphous BiO_x. Bi oxidation state is proposed to strongly affects the nitrogen fixation activity, with the half-occupied p_z orbitals of the Bi²⁺ ions being highly efficient toward electron injection into the inert N₂ molecule. With sufficient catalytic sites to adsorb and activate N₂, the bonding between N₂ and catalyst is able to be in situ identified. The catalyst shows an outstanding Faraday efficiency (≈30 %) and high yield (≈113 μg h⁻¹ mg⁻¹_cat) in NH₃ production, outperforming most of the existing catalysts in aqueous solution. These results lay the basis for developing the potential of p-block elements for catalysis of multi-electron reactions.     

Correlating Polysulfide Solvation Structure with Electrode Kinetics towards Long-Cycling Lithium–Sulfur Batteries

Lithium–sulfur (Li−S) batteries are promising due to ultrahigh theoretical energy density. However, their cycling lifespan is crucially affected by the electrode kinetics of lithium polysulfides. Herein, the polysulfide solvation structure is correlated with polysulfide electrode kinetics towards long-cycling Li−S batteries. The solvation structure derived from strong solvating power electrolyte induces fast anode kinetics and rapid anode failure, while that derived from weak solvating power electrolyte causes sluggish cathode kinetics and rapid capacity loss. By contrast, the solvation structure derived from medium solvating power electrolyte balances cathode and anode kinetics and improves the cycling performance of Li−S batteries. Li−S coin cells with ultra-thin Li anodes and high-S-loading cathodes deliver 146 cycles and a 338 Wh kg⁻¹ pouch cell undergoes stable 30 cycles. This work clarifies the relationship between polysulfide solvation structure and electrode kinetics and inspires rational electrolyte design for long-cycling Li−S batteries.     

Symmetry-Broken Intermolecular Charge Separation of Cationic Radicals

A quadrupolar compound Pyr-BA with two pyrrole-type nitrogen atoms doped externally was prepared in this work. In high contrast with other π ionic radicals, its cationic radical Pyr-BA ⋅ ⁺ undergoes unusual symmetry-broken charge separation (SB-CS), generating the mixed valence complex of Pyr-BA^+1−q ⋅⋅⋅ Pyr-BA^+1+q , where q is the degree of charge transfer. Variable-temperature (VT) single-crystal analysis, absorption and EPR experiments all confirmed that aggregation and lower temperature would help to facilitate this SB-CS process. Gibbs energy calculations and gauge-including magnetically induced current simulation both validate that, for Pyr-BA ⋅ ⁺ , SB-CS behavior is more favorable than the conventional dimerization mode. To the best of our knowledge, this is the first study that shows solid single-crystal evidence for spontaneous SB-CS between identical ionic radicals. Such a unique phenomenon is of great significance both in terms of fundamental aspects and uncharted material science.     

Spin-Distribution-Directed Regioselective Substitution Strategy for Highly Stable Olympicenyl Radicals

The synthesis of bench-stable conjugated π-radicals is challenging owing to the lack of modular approaches, which greatly hampers their practical material screens and applications. Here, we demonstrate a spin-distribution-directed regioselective substitution strategy to introduce substituents into the specific positions of an olympicenyl radical in a stepwise manner, resulting in a series of highly stable radical species. The substituents can also adjust the crystal packing by means of steric and electronic factors, enabling the changing from a π-dimer to a pseudo-one-dimensional chain. The first single crystal organic field-effect transistor device based on a graphenic radical is fabricated in air, showing a hole mobility of up to 0.021 cm² V⁻¹ s⁻¹ and excellent device stability. This approach may be generalized to diverse spin-delocalized open-shell organic radicals.     

State-constrained bipartite tracking of interconnected robotic systems via hierarchical prescribed-performance control

This paper investigates the collaborative design problem aiming to achieve state-constrained bipartite tracking of the interconnected robotic systems (IRSs) with prescribed performance. In practical applications, the physical limitations of the robots are inevitable. Besides, it is difficult to ensure that the target trajectory is known for each robot of the IRSs in advance. Thus, it is important to follow the target trajectory and meanwhile obey the state constraint being generated from the physical limitations and the external environment of the IRSs. To this end, we propose a new hierarchical state-constrained estimator-based control framework with the characteristics of low computation complexity and high task adaptability. With limited accessibility of the target trajectory, we newly present the estimator to observe it at each time interval through the interconnections among the robots. The state constraint is never violated throughout the convergence process by using the presented control algorithm. The theoretical proof and simulation results are presented to validate the feasibility of the control framework.

     

部分相干光学成像系统的光学传递函数和像质评价准则

根据光学成像理论，建立了部分相干成像光学系统的光学传递函数。该函数与非相干成像光学系统传递函数相同，因而部分相干成像和非相干成像两者的光学系统波面像差公差标准也是相同的。这一点解释了显微镜光学系统的光学设计惯用法则：镜头像差公差标准的选择，并不因为采用成像照明方式的不同而有所差异。     

以酚醛树脂为碳源合成锂离子电池正极材料Li3V2 (PO4)3/C

以酚醛树脂为碳源,分别采用了固相法和溶胶凝胶法合成了锂离子电池正极材料Li3V2(PO4)3/C.结果表明,高分子材料酚醛树脂是一种优良的碳源材料,其热解后得到的导电网络能够有效的提高Li3V2(PO4)3的电化学性能;两种试样的充放电曲线和交流阻抗图谱体现出了试样良好的可逆性,其极化程度很低,电荷转移电阻小;而相对于固相法来讲,溶胶凝胶法和表面活性剂CTAB(十六烷基三甲基溴化铵)的共同作用能够有效的将颗粒粒径控制在纳米级别.用这种方法合成的试样在15 C下充放电比容量也能高于90 mAh/g,5C倍率下循环50次比容量无衰减,证明了以酚醛树脂为碳源并采用溶胶凝胶法合成的试样具有很好的倍率性能与循环性能.     

基于高速图像分析的激光器光束稳定性及光斑质量评价方法研究

机载激光器的光束稳定性及光斑质量是关系到该武器系统毁伤效率的关键性因素。本文基于棱镜分光及数字图像处理技术,发展了能够在实验室实验中同时获取激光光斑位置和光强分布信息且不会对系统自身工作产生影响的方法及系统,实现了对激光光束稳定性及光斑质量的评价。该方法利用数字相机采集光斑图像,并根据像素灰度值计算光斑位置和光强分布。标定实验结果表明,该方法对光斑位置的测量误差可控制在1%以内,对光斑质量也可以实现很好的评价。     

基于高光谱技术的玉米种子可视化鉴别研究

种子纯度是衡量种子品质的重要指标。提出一种基于近红外(874～1 734 nm)高光谱技术实现玉米种子可视化鉴别的方法。采集4个品种共384个玉米种子样本的高光谱图像数据,随机选择288个样本作为建模集,剩余96个样本作为预测集。对玉米种子光谱曲线进行分析后,通过连续投影算法（SPA）选取7个特征波段作为输入,结合偏最小二乘法判别分析(PLS-DA)模型,对预测集进行预测,获得较好的分类效果,其中R_C=0.917 7,RMSECV=0.444 2; R_CV=0.911 5,RMSECV=0.459 9,建模集和预测集的总体鉴别率分别为78.5%和70.8%。通过图像处理技术提取高光谱图像中每个玉米颗粒的平均光谱数据,输入建立的SPA-PLS-DA模型,在计算生成的鉴别图中以不同颜色标识不同类别,实现了混杂玉米种子样本的可视化鉴别。对3份不同组成的混杂种子样本进行鉴别,达到了较好的可视化效果。结果表明,通过可视化鉴别技术,可以直观方便地观察混杂种子样本中不同品种种子的分布和数量,为农业生产中种子的纯度鉴别和筛选提供了帮助。     

Physical insight of superconductivity of Nb2AlC: in situ Raman spectrometry investigation

Superconductivity of Nb₂AlC has been previously reported, but the origin is not clear. In this paper, in situ Raman spectra of Nb₂AlC are measured in the temperature range from 80 to 380 K at ambient pressure. The line‐width of E_2g (ω₁) mode increases with temperature which originates from the anharmonic phonon–phonon scattering. On the contrary the line‐widths of E_2g (ω₂) and A_1g (ω₄) modes decrease continuously at elevated temperature. The phenomenon is explained by the electron–phonon coupling. The origin of superconductivity is therefore interpreted by the coupling of Nb 4d electrons with E_2g (ω₂) and A_1g (ω₄) phonon modes. Copyright © 2013 John Wiley & Sons, Ltd.