Controllably asymmetric beam splitting via gap-induced diffraction channel transition in dual-layer binary metagratings

In this work, we designed and studied a feasible dual-layer binary metagrating, which can realize controllable asymmetric transmission and beam splitting with nearly perfect performance. Owing to ingenious geometry configuration, only one meta-atom is required to design for the metagrating system. By simply controlling air gap between dual-layer metagratings, high-efficiency beam splitting can be well switched from asymmetric transmission to symmetric transmission. The working principle lies on gap-induced diffraction channel transition for incident waves from opposite directions. The asymmetric/symmetric transmission can work in a certain frequency band and a wide incident range. Compared with previous methods using acoustic metasurfaces, our approach has the advantages of simple design and tunable property and shows promise for applications in wavefront manipulation, noise control and one-way propagation.     

Separation,Quantification and Structural Study of (+)‐Catechin and (–)‐Epicatechin by Ion Mobility Mass Spectrometry Combined with Theoretical Algorithms

Two catechin epimers and their non‐covalent complexes with γ‐cyclodextrin were studied by using ion mobility coupled with mass spectrometry (IM‐MS). Rapid separation of complexes was achieved with the peak‐to‐peak resolution reaching 0.86 after optimization of IM condition. Collision cross section (CCS) was measured to explore the structural difference of complexes. A gap of 11.75 Ų between two complexes was found. Molecular modeling and theoretical CCS calculation were adopted to explain the measurement results. Two binding ways of both complexes were found and the calculated CCS corresponds accurately to the measured CCS. Quantification of catechins in mixtures was performed and the relative error was less than 15%, indicating the effectiveness of quantification by IM‐MS.     

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。     

含酰胺结构超低膨胀聚酰亚胺薄膜的热膨胀行为

采用联苯二酐与3种含酰胺结构二胺制备了具有不同取代基团的聚酰胺-酰亚胺薄膜, 考察了酰胺结构对薄膜力学、 耐热及尺寸稳定性的影响, 研究了聚集态结构与薄膜热膨胀行为的关系和规律. 该系列薄膜具有超高强度和优异的耐热性能, 拉伸强度高达280.5 MPa, 玻璃化转变温度在389~409 ℃, 并在30~300 ℃温度范围内表现出超低负膨胀, 热膨胀系数(CTE, ppm/℃, 即10 ⁶ cm·cm ^-1·℃ ^-1)在-3.05~-1.74 ppm/℃之间. 聚集态分析结果表明, 酰胺结构使分子链间形成了强氢键相互作用, 分子链在薄膜面内方向高度有序取向, 并在膜厚方向堆积更为紧密, 使薄膜表现出热收缩现象. 通过不同体积大小的取代基团进一步调控分子链间相互作用及排列堆积, 可实现薄膜在高温下近乎零尺寸形变, 为设计制备超低膨胀聚合物基板材料提供了新思路.     

Ni单原子催化剂表面CO2电还原动力学的电化学谱学解析

针对Ni单原子催化剂表面的CO₂电还原反应(CO₂RR), 提出了以Ni为活性位点的“单中心”机理以及同时借助Ni位点还原和碳氮锚定位水解的“双功能”机理. 依据稳态极化的实验结果, 开展了CO₂RR的动力学解析与模型参数的敏感性分析; 借助暂态模型方程, 分别获取可表达CO₂RR线性与非线性频响特征的电化学阻抗谱(EIS)与总谐波失真(THD)谱. 研究结果表明, CO₂的溶解分压对CO₂RR活性影响最显著. 若CO₂RR遵循“单中心”机理, Ni位点COOH_ads的形成为速率控制步骤; 但若为“双功能”机理, 碳氮锚定位的水解与Ni位点的CO_2,ads还原同为速率控制步骤. EIS理论上可用于区分CO₂RR的“单中心”机理与“双功能”机理; 与之相比, THD谱在CO₂RR的机理识别中并无优势.     

Integrating Biomass into the Organonitrogen Chemical Supply Chain: Production of Pyrrole and d-Proline from Furfural

Production of renewable, high-value N-containing chemicals from lignocellulose will expand product diversity and increase the economic competitiveness of the biorefinery. Herein, we report a single-step conversion of furfural to pyrrole in 75 % yield as a key N-containing building block, achieved via tandem decarbonylation–amination reactions over tailor-designed Pd@S-1 and H-beta zeolite catalytic system. Pyrrole was further transformed into dl -proline in two steps following carboxylation with CO₂ and hydrogenation over Rh/C catalyst. After treating with Escherichia coli, valuable d -proline was obtained in theoretically maximum yield (50 %) bearing 99 % ee. The report here establishes a route bridging commercial commodity feedstock from biomass with high-value organonitrogen chemicals through pyrrole as a hub molecule.     

Reverse Thinking of the Aggregation-Induced Emission Principle: Amplifying Molecular Motions to Boost Photothermal Efficiency of Nanofibers**

Using reverse thinking of the aggregation-induced emission (AIE) principle, we demonstrate an ingenious and universal protocol for amplifying molecular motions to boost photothermal efficiency of fibers. Core–shell nanofibers having the olive oil solution of AIE-active molecules as the core surrounded by PVDF-HFP shell were constructed by coaxial electrospinning. The molecularly dissolved state of AIE-active molecules allows them to freely rotate and/or vibrate in nanofibers upon photoexcitation and thus significantly elevates the proportion of non-radiative energy dissipation, affording impressive heat-generating efficiency. Photothermal evaluation shows that the core–shell nanofibers with excellent durability can reach up to 22.36 % of photothermal conversion efficiency, which is 26-fold as the non-core–shell counterpart. Such a core–shell fiber can be used for photothermal textiles and solar steam generation induced by natural sunlight with green and carbon-zero emission.     

Direct Intermediate Regulation Enabled by Sulfur Containers in Working Lithium–Sulfur Batteries

Polysulfide intermediates (PSs), the liquid-phase species of active materials in lithium–sulfur (Li-S) batteries, connect the electrochemical reactions between insulative solid sulfur and lithium sulfide and are key to full exertion of the high-energy-density Li-S system. Herein, the concept of sulfur container additives is proposed for the direct modification on the PSs species. By reversible storage and release of the sulfur species, the container molecule converts small PSs into large organosulfur species. The prototype di(tri)sulfide-polyethylene glycol sulfur container is highly efficient in the reversible PS transformation to multiply affect electrochemical behaviors of sulfur cathodes in terms of liquid-species clustering, reaction kinetics, and solid deposition. The stability and capacity of Li-S cells was thereby enhanced. The sulfur container is a strategy to directly modify PSs, enlightening the precise regulation on Li-S batteries and multi-phase electrochemical systems.     

Cooperative effect of Fe and Ti species over Fe–Ti–Ox catalysts on the catalytic hydrolysis performance of hydrogen cyanide

FeO_x, TiO₂, and Fe–Ti–O_x catalysts were synthesized and used in the catalytic hydrolysis of hydrogen cyanide (HCN). Nearly 100% HCN conversion was achieved at 250 °C over the Fe–Ti–O_x catalyst. TiO₂ rutile was detected over TiO₂, but not over Fe–Ti–O_x, which suggested that the interaction between Fe and Ti species could inhibit the TiO₂ phase transition. Furthermore, the interaction between Fe and Ti species over Fe–Ti–O_x could promote the selectivity of NH₃ and CO. The mechanism of hydrolysis of HCN over FeO_x, TiO₂, and Fe–Ti–O_x can be given as follows: HCN + H₂O → methanamide → ammonium formate → formic acid → H₂O + CO.     

Effectively promoted catalytic activity by adjusting calcination temperature of Ce-Fe-Ox catalyst for NH3-SCR

A series of Ce-Fe-O_x catalysts prepared by the different calcination temperatures (marked as CF-X, where X represented calcination temperature) were used to the selectivity catalytic reduction of NO_x by NH₃. The results explained the relationship between calcination temperature and the sulfate species over Ce-Fe-O_x, and then investigated the surface acidity and catalytic performance. The large amounts of sulfate species were formed over CF-450 and CF-550 while it was decomposed with further the increasing of calcination temperature, which resulted in the loss of surface acidity, causing a decrease in the catalytic activity over Ce-Fe-O_x. Thereby, the CF-450 catalyst showed the best catalytic activity and over 90% NO_x conversion was obtained at 244–450 °C. Besides, the favored pore structure, more Fe³⁺ active species, higher Ce³⁺ concentration and the abundance of chemical adsorbed oxygen species, as well as the surface acid sites, would together contribute to the excellent catalytic activity of CF-450 catalyst.