Sulfur Chemistry for Stable and Electroactive Metal-Organic Frameworks: The Crosslinking Story

The versatile sulfur chemistry, as exemplified by the reactive yet tractable thiol group (-SH), offers unique opportunities for bypassing the obstacles in accessing stable and electroactive metal-organic frameworks. Of particular interest are recent advances in assembling MOF materials equipped with free-standing thiol functions: metal guests can be conveniently inserted to install electroactive metal-sulfur bonds, which, as crosslinks, also stabilize the host coordination net. Here the historical development of the bifunctional, two-step design embodied by the thiol-tagged MOF solids is traced, in order to highlight the underlying spirit that has driven research efforts in the past two decades. Going forward, broad new horizons are foreseen in solid-state materials synthesis, for example, arising from various sulfur-based hard-and-soft combinations, in synergy with the crystalline and modular MOF structural platform.     

Prediction of the cross-sections of isotopes produced in deuteron-induced spallation of long-lived fission products

The spallation cross-section data for the long-lived fission products(LLFPs) are scarce but required for the design of accelerator driven systems. In this paper, the isospin dependent quantum molecular dynamics model and the statistical code GEMINI are applied to simulate deuteron-induced spallation in the energy region of GeV/nucleon. By comparing the calculations with the experimental data, the applicability of the model is verified. The model is then applied to simulate the spallation of 90 Sr, 93 Zr, 107 Pd, and 137 Cs induced by deuterons at 200, 500 and 1000 MeV/nucleon. The cross-sections of isotopes, the cross-sections of long-lived nuclei, and the reaction energy are presented.Using the above observables, the feasibility of LLFP transmutation by spallation is discussed.     

Coupling effect-triggered control strategy for hypersonic flight vehicles with finite-time convergence

Nonlinear Dynamics - This paper investigates a novel control strategy of addressing coupling issue for attitude tracking control of hypersonic flight vehicle. By using a defined coupling effect...     

Highly efficient and thermal stable guanidinium-based two-dimensional perovskite solar cells via partial substitution with hydrophobic ammonium

Layered two-dimensional(2D)perovskite solar cells(PVSCs)with a chemical formula of C(NH_2)_3(CH_3NH_3)_3Pb_3I_(10)(n=3)have been fabricated through additive engineering,wherein stoichiometrically equivalent guanidinium(GA~+)and methylammonium(MA~+)serve as spacer cations.The crystallinity of the perovskite films is dramatically enhanced with proper amount of methylammonium thiocyanate(MASCN)added into the precursor solution.In addition,we substitute a small amount of MA~+with hydrophobic phenylethylammonium(PEA~+),which can passivate trap states of the perovskite films.As a result,the open circuit voltage increases to 1.1 V and the best power conversion efficiency(PCE)of 10.12%is yielded.Furthermore,superior thermal stability and balanced moisture stability of the PEA-substituted GA-based PVSCs are demonstrated,compared to the popular 3D MAPbI_3and 2D PEA-based PVSCs.They retain approximately 80%of the original PCE after 30 d at 20%relative humidity(RH),and 50%of the original PCE after 3200 min at 85°C without any encapsulation.This work suggests a new route to achieve both heat and humidity stable PVSCs by simply mixing different spacer cations.     

Porphyrin‐containing Polyimide with Enhanced Light Absorption and Photocatalysis Activity

A series of porphyrin‐containing polyimide (PI) photocatalysts were synthesized by a one‐step solvothermal method. Characterization results revealed that porphyrin was uniformly coupled into the PI framework through covalent bonding and the visible‐light absorption was greatly improved. The photodegradation activity of porphyrin‐containing PIs for methyl orange (MO) under visible light was enhanced significantly, with the highest pseudo‐first‐order rate constant 35 times higher than that of neat porphyrin and 10 times higher than that of porphyrin‐free PI. The enhancement is mainly attributed to an increased light harvesting accompanied by a varied HOMO level, which was clarified by control experiments, characterizations and theoretical calculations. This work provides an insight into multiple effects of dye molecules in dye‐containing heterogeneous photocatalysts.     

Selective Excitation of Band Extrema in Valley Photonic Crystals

Flexible control of building blocks of photonic crystals enables achieving desirable band structures. Exploration of photonic band extrema has brought many fantastic features to design artificial optical materials, such as Brillouin‐zone‐corner extrema for valley photonic materials and zone‐center extremum for zero‐index metamaterials. However, two such kinds of extrema are always found independently in different photonic crystals. In this work, a kind of valley photonic crystals possessing both zone‐center and zone‐corner band extrema almost at the same frequency is proposed. Inspired by antennas theory, a three‐antenna array (TAA) source is devoted to individually manipulate each extremum. The correlation coefficient is given to determine the coupling efficiency between the TAA source and extrema eigenmodes. By using a source with a high correlation coefficient, these extrema bulk states are selectively excited consistent with their eigenfields. Furthermore, three control cases are shown that multiple extrema points are simultaneously excited, in order to confirm the validity of the correlation coefficient. Finally, a potential application of a beam‐steering device is proposed through selective excitation of ternary extrema. This work develops binary valley states into ternary mix states, rendering more degrees of freedom for on‐chip optical information transport, particularly for beam steering and mode division multiplexing.     

新郑西亚斯东周玉器材料属性与加工工艺的科技分析

中国玉文化源远流长,治玉工艺经过各个时代的不断发展和完善,在一定程度上能反映古代社会生产力发展水平及文化、贸易、技术交流等信息。利用能量色散型X射线荧光光谱（EDXRF）、激光拉曼光谱（LRS）、超景深光学显微系统（OM）等分析技术,结合硅胶覆膜微痕复制技术,对河南省新郑西亚斯东周墓地出土的一批玉器进行科技分析。首先利用化学成分和物相结构分析技术确定了玉器材质的矿物属性,其次利用显微分析技术表征了玉器表面及穿孔内部和印模的加工痕迹,特别是阴刻纹饰和穿孔微痕特征,最后探讨了玉器样品的材料属性和加工工艺两者之间的联系。化学成分和物相结构分析结果表明,所分析的西亚斯东周玉器材质丰富,主要矿物组成有滑石、透闪石、水晶、云母等。玉器表面纹饰微痕特征分析表明,所分析玉器阴刻工艺采用了两种加工工具,分别是砣具和手持硬质工具。穿孔微痕分析特征表明,钻孔包括单面钻孔和双面/多面钻孔两种方式,钻孔工艺则有实心钻、管钻等。部分玉器钻孔形状和内部微痕特征表明,尽管均采用了实心钻工艺,但所采用的实心钻头在形状上存在差异,同时,也存在是否配合解玉砂进行钻孔的差异。不同材料属性的玉器采用了不同的加工工艺。滑石质玉器,莫氏硬度1,器型主要为玉片饰,其表面阴刻纹饰主要采用手持硬质工具进行刻画,钻孔主要采用了双面钻孔方式,并使用了实心钻头未添加解玉砂进行加工,钻头形状可能为圆锥状;云母质玉器,莫氏硬度2~3,器型主要为玉玦片饰,纹饰采用了砣具添加解玉砂的加工工艺,钻孔方式为单面钻孔,采用了管钻工艺。透闪石型玉器,莫氏硬度5~6,器型主要为玉片饰,表面纹饰采用砣具配合解玉砂砣刻,以双面钻孔的方式为主,钻孔工艺为实心钻头配合解玉砂工艺,钻头形状与滑石类样品一致,为圆锥状。水晶质玉器,莫氏硬度7,均为珠饰,表面无纹饰,钻孔方式为双面/多面钻孔,钻孔工艺为实心钻配合解玉砂工艺,且钻头可能为圆柱形。研究结果表明,玉器表面纹饰所采用的阴刻工艺和钻孔工艺,与玉器本身的材料属性、器型等存在密切关系。