Vertically Grown Few-Layer MoS2 Nanosheets on Hierarchical Carbon Nanocages for Pseudocapacitive Lithium Storage with Ultrahigh-Rate Capability and Long-Term Recyclability

Molybdenum disulfide (MoS₂) is an intensively studied anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity, but it is still confronted by severe challenges of unsatisfactory rate capability and cycle life. Herein, few-layer MoS₂ nanosheets, vertically grown on hierarchical carbon nanocages (hCNC) by a facile hydrothermal method, introduce pseudocapacitive lithium storage owing to the highly exposed MoS₂ basal planes, enhanced conductivity, and facilitated electrolyte access arising from good hybridization with hCNC. Thus, the optimized MoS₂/hCNC exhibits reversible capacities of 1670 mAh g⁻¹ at 0.1 A g⁻¹ after 50 cycles, 621 mAh g⁻¹ at 5.0 A g⁻¹ after 500 cycles, and 196 mAh g⁻¹ at 50 A g⁻¹ after 2500 cycles, which are among the best for MoS₂-based anode materials. The specific power and specific energy, which can reach 16.1 kW and 252.8 Wh after 3000 cycles, respectively, indicate great potential in high-power and long-life LIBs. These findings suggest a promising strategy for exploring advanced anode materials with high reversible capacity, high-rate capability, and long-term recyclability.     

Proton conductivity study on three CS/IL@fle-MOF membranes

The low-cost, high specific surface area and porosity, controlled pore size, and chemical properties of metal–organic framework (MOF) materials have attracted much attention in the exploration of proton conduction. The method of chemically modifying MOF structures or introducing conductive medium into the holes can effectively improve the proton conductivities of the materials. Here, the structural tunability of ionic liquid (IL) and flexible MOF (fle-MOF) materials are matched to give full play to the conductivity of IL, the framework support, and the microporous effect of MOFs, which achieves the synergistic effect of performance and expands the temperature range of proton transfer. Three kinds of CS/IL@fle-MOF membranes were prepared by combining three fle-MOFs with 1-carboxymethyl-3-methylimidazole (CMMIM) in different proportions to obtain 15 pieces of membranes. The comparative analyses show that CS/IL@fle-MOF membranes have excellent proton conduction performance at a wider temperature range (263–353 K) and lower relative humidity (75% RH). Among them, the proton conductivities of CS/CMMIM@MIL-88A-25% and CS/CMMIM@MIL-88B-125% are up to 1.33 and 1.42 S cm⁻¹ at 75% RH and 353 K, respectively; whereas those of CS/CMMIM@MIL-53(Fe)-75% and CS/CMMIM@MIL-88B-125% reach up to 2.1 × 10⁻³ and 1.28 × 10⁻³ S cm⁻¹ at 75% RH and 263 K, respectively. The E_a of CS/CMMIM@fle-MOFs is in the range of 0.1–0.5 eV, suggesting that the proton transport follows predominantly the typical Grotthuss transfer mechanism. The results of this study indicate that the CS/CMMIM@fle-MOF membranes combinations offer great potential for the design of composite porous proton-conducting materials.     

Mechanism and Stereoselectivity of the Elementometalation Process of Activated Alkyne RCCR(RCO2Me) by Cp2TaH3

The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO₂Me) by Cp₂TaH₃ and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η²-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η²-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc.     

基于混合空穴注入层的湿法制备高效蓝光热激活延迟有机发光二极管

在溶液法制备有机电致发光器件(OLEDs)的研究中, PEDOT∶PSS由于具有较好的成膜性与高透光性而常被用作器件的空穴注入层。但相关研究表明, PEDOT∶PSS本身稳定性较差以及功函数较低,这使得溶液法制备OLEDs的性能差且不稳定。蓝色作为全彩色的三基色之一,制备高效的蓝光器件对于实现高质量显示器件和固态照明装置必不可少。而目前溶液法制备蓝光OLEDs的器件效率普遍较差,针对此问题,本文利用传统的蓝光热激活延迟荧光发光(TADF)材料DMAC-DPS作为发光层,用溶液法制备了蓝光TADF OLEDs,通过在PEDOT∶PSS中掺杂PSS-Na制备混合空穴注入层(mix-HIL)来提高空穴注入层的功函数,研究其对于蓝光TADF OLEDs器件性能的影响。首先在PEDOT∶PSS水溶液中掺入不同体积的PSS-Na溶液,在相同条件下旋涂制膜,进行器件制备。通过观测各个实验组器件的电致发光(EL)光谱,发现掺入PSS-Na后器件EL谱存在光谱蓝移的现象,这是由于掺入PSS-Na水溶液后, mix-HIL层的厚度有所降低,使得在微腔效应作用下, EL光谱发生蓝移。通过对比各组器件的电流密度-电压-亮度(J-V-L)曲线及其计算所得器件的电流效率,结果显示随着PSS-Na的掺入,器件的亮度和电流都有所增大,器件的电流效率也得到了提升,当掺杂比例为0.5∶0.5(PEDOT∶PSS/PSS-Na)时提升幅度最大(亮度提升86.7%,电流效率提升34.3%)。通过在瞬态电致发光测试过程中施加或撤去驱动电压观测了器件EL强度的变化,分析了在混合空穴注入层/发光层(mix-HIL/EML)界面处的电荷积累情况。实验证明,通过在PEDOT∶PSS中掺杂PSS-Na制备mix-HIL获得了蓝光TADF OLEDs器件性能的提升,这是一个获得高效率溶液法制备OLEDs的可行方法。     

On-chip multiphoton Greenberger–Horne–Zeilinger state based on integrated frequency combs

One of the most important multipartite entangled states, Greenberger–Horne–Zeilinger state (GHZ), serves as a fundamental resource for quantum foundation test, quantum communication and quantum computation. To increase the number of entangled particles, significant experimental efforts should been invested due to the complexity of optical setup and the difficulty in maintaining the coherence condition for high-fidelity GHZ state. Here, we propose an ultra-integrated scalable on-chip GHZ state generation scheme based on frequency combs. By designing several microrings pumped by different lasers, multiple partially overlapped quantum frequency combs are generated to supply as the basis for on-chip polarization-encoded GHZ state with each qubit occupying a certain spectral mode. Both even and odd numbers of GHZ states can be engineered with constant small number of integrated components and easily scaled up on the same chip by only adjusting one of the pump wavelengths. In addition, we give the on-chip design of projection measurement for characterizing GHZ states and show the reconfigurability of the state. Our proposal is rather simple and feasible within the existing fabrication technologies and we believe it will boost the development of multiphoton technologies.     

TADF激基复合物主体材料提升溶液法制备蓝色荧光有机发光二极管的效率

为了提升溶液法制备的蓝色荧光有机发光二极管(OLEDs)的效率,采用了基于热激活延迟发光(TADF)的激基复合物作为主体材料。TADF激基复合物主体可以利用反向系间窜跃上转换形成单线态激子并将能量传递到客体,从而可以同时利用发光层中的三线态激子和单线态激子,以提升蓝色荧光器件的效率。选择蓝色荧光材料1-4-Di-[4-(N,N-diphenyl)amino]styryl-benzene(DSA-ph)作为客体发光材料,4,4′,4″-T-ris(carbazol-9-yl)triphenylamine(TCTA)掺杂1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)(TPBi)作为热激活延迟荧光激基复合物主体,通过溶液法制备了蓝色荧光OLEDs。通过测试TCTA,TPBi以及TCTA掺杂TPBi的光致发光光谱发现,与TCTA和TPBi相比,TCTA掺杂TPBi的光致发光谱(PL)发生了明显的红移(峰值波长变为437 nm),而且光谱变宽,证明了TCTA∶TPBi激基复合物的形成。通过对于DSA-ph掺杂激基复合物主体的薄膜与DSA-ph掺杂poly(methyl methacrylate)(PMMA)的薄膜进行PL测试发现,两者发光峰相同,都是来自DSA-ph的发光,说明激基复合物主体将能量传递到了DSA-ph;DSA-ph的吸收光谱与激基复合物主体的PL光谱存在很大重叠,说明激基复合物主体与DSA-ph的能量传递非常有效;通过对激基复合物主体掺杂不同浓度客体的薄膜进行瞬态PL衰减测试发现,与纯DSA-ph的寿命相比,DSA-ph掺杂激基复合物主体之后其寿命会延长,纯DSA-ph的寿命只有1.19 ns,DSA-ph掺杂激基复合物主体的荧光衰减曲线与激基复合物主体的荧光衰减曲线相似,这进一步证明了激基复合物主体将能量传递到了DSA-ph。研究了主体引入以及DSA-ph掺杂浓度对器件性能的影响。对于器件的亮度、电流密度、电压、电流效率、电致发光光谱等参数进行了测试,与不采用激基复合物主体的器件相比,采用激基复合物主体的器件性能明显改善,在DSA-ph掺杂浓度为10%时,器件亮度从2133.6 cd·m^-2提升到了3597.6 cd·m^-2,器件效率从1.44 cd·A-1提升到了3.15 cd·A-1,发光峰只有来自DSA-ph的发光。采用TADF激基复合物主体的方法有潜力实现溶液法制备的高效蓝色荧光OLEDs。     

Modeling and simulation of weld line location and properties during injection molding based on viscoelastic constitutive equation

Rheologica Acta - Weld lines are one of the typical quality issues of injection molded parts. They are unavoidable even for moderate complex products. To explore the formation of weld lines in...     

基于平面度的燃料电池电化学性能模拟

 固体氧化物燃料电池的翘曲会影响电极-盖板界面的接触情况，从而影响电化学性能，对相关制造工艺提出了很大的挑战．为了分析燃料电池平面度对放电过程的影响，揭示其潜在的风险，我们建立了两个基于有限元法的仿真模型，对考虑平面度缺陷的燃料电池封装和放电进行分析．在对固体氧化物燃料电池进行平面度测量的基础上，首先建立了具有真实燃料电池翘曲特性的几何模型，分析封装过程中接触压力的分布情况．然后将接触电阻的仿真结果导入到三维多物理场耦合模型中，模拟具有平面度缺陷的燃料电池电化学性能．计算结果展示了燃料电池两侧封装过程中接触压力的分布情况．通过对比有接触电阻和无接触电阻的燃料电池电流密度，分析了电池与盖板的接触对放电过程的影响．结果表明，燃料电池的凹陷面较难达到满意的接触状态，需要比凸起面更大的封装压力．燃料电池表面接触电阻的变化将引起电流传导路径的变化，产生局部高电流或低电流．这项工作强调了在燃料电池中保持均匀分布的接触电阻的重要性，为今后的优化工作奠定了基础．