Growth and characterization of two-dimensional crystals for communication and energy applications

This review article covers the growth and characterization of two-dimensional (2D) crystals of transition metal chalcogenides, h-BN, graphene, etc. The chemical vapor transport method for bulk single crystal growth is discussed in detail. Top-down methods like mechanical and liquid exfoliation and bottom-up methods like chemical vapor deposition and molecular beam epitaxy for mono/few-layer growth are described. The optimal characterization techniques such as optical, atomic force, scanning electron, and Raman spectroscopy for identification of mono/few-layer(s) of the 2D crystals are discussed. In addition, a survey was done for the application of 2D crystals for both creation and deterministic transfer of single-photon sources and photovoltaic systems. Finally, the application of plasmonic nanoantenna was proposed for enhanced solar-to-electrical energy conversion and faster/brighter quantum communication devices.     

Barriers to internal rotation and tunnelling splittings of the torsional states in the HO(CH2)OH,DO(CH2)OH and DO(CH2)OD molecules

Torsional states caused by vibrations of hydroxyl groups in the methanediol molecule and its two deuterated analogues – DO(CH₂)OH and DO(CH₂)OD were analysed at MP2/cc-pVTZ and CCSD(T)/cc-pVQZ levels of theory. In the first case, 2D PES and 2D surfaces of kinematic coefficients were calculated with geometry optimisation for all other geometric parameters, and in the second case, only the energy of optimised configurations at the MP2/cc-pVTZ level of theory was determined. Then 2D PES was recounted to the complete basis set (CBS) limit by extrapolating the results of calculations at the MP2/cc-pVTZ and MP2/cc-pVQZ levels of theory The calculated values were then averaged over four equivalent points on the coordinate plane. Hamiltonian matrices were constructed using DVR and Fourier methods. After their subsequent diagonalization, the energies of the stationary torsional states were computed. Their classification by C_2V(M) and C_S(M) molecular symmetry groups has been performed. The splitting values due to the tunnelling of the thirty most deeply located torsional states in the three studied molecules were also determined. The torsional states, internal rotation barriers, and tunnelling frequencies in the molecules of methanediol and hydrogen trioxide were compared.     

Influence of the torsional vibration of the periodically attached perpendicular beam resonator on the flexural band of a Euler-Bernoulli beam

The bending and torsional vibration of the periodic perpendicular cantilever beam-mass resonators (PCBMR) is idealized as translational and rotational oscillators attached to the main beam. In this paper, the effect of that torsional vibration of the PCBMR on the dynamics of an infinitely long Euler-Bernoulli beam is evaluated. The band-structure is explored by implementing the transfer matrix method in conjunction with Bloch-Floquet's theorem. The combination of the translational and rotational oscillator modifies the relative position of the coupling coefficient in the transfer matrix, which plays a pivotal role in the band-gap formation. The flexural band-structure is highly sensitive to the torsional vibration while the radius of gyration of the tip mass is considerably higher than the length of the PCBMR. Ill-tuning leads to split and reduction of attenuation band to 50%; whereas, around 38% elongation of the attenuation band in the low frequency regime can be achieved by proper tuning.     

Wall shear stress modified by bubbles in a horizontal channel flow of silicone oil in the transition region

We performed laboratory experiments on bubbly channel flows using silicone oil, which has a low surface tension and clean interface to bubbles, as a test fluid to evaluate the wall shear stress modification for different regimes of bubble migration status. The channel Reynolds numbers of the flow ranged from 1000 to 5000, covering laminar, transition and turbulent flow regimes. The bubble deformation and swarms were classified as packing, film, foam, dispersed, and stretched states based on visualization of bubbles as a bulk void fraction changed. In the dispersed and film states, the wall shear stress reduced by 9% from that in the single-phase condition; by contrast, the wall shear stress increased in the stretched, packing, and foam states. We carried out statistical analysis of the time-series of the wall shear stress in the transition and turbulent-flow regimes. Variations of the PDF of the shear stress and the higher order moments in the statistic indicated that the injection of bubbles generated pseudo-turbulence in the transition regime and suppressed drag-inducing events in the turbulent regime. Bubble images and measurements of shear stress revealed a correlated wave with a time lag, for which we discuss associated to the bubble dynamics and effective viscosity of the bubble mixture in wall proximity.     

Facile non‐lithographic route to highly aligned silica nanopatterns using unidirectionally aligned polystyrene‐block‐polydimethylsiloxane films

Thin films (monolayer and bilayer) of cylinder forming polystyrene‐block‐polydimethylsiloxane (PS‐b‐PDMS) were shear aligned by the swelling and deswelling of a crosslinked PDMS pad that was physically adhered to the film during solvent vapor annealing. The nanostructures formed by self‐assembly were exposed to ultraviolet‐ozone to partially oxidize the PDMS, followed by calcination in air at 500 °C. In this process, the PS segments were fully decomposed, while the PDMS yielded silica nanostructures. The highly aligned PDMS cylinders were thus deposited as silica nanolines on the silicon substrate. Using a bilayer film, the center‐to‐center distance of these features were effectively halved from 38 to 19 nm. Similarly, by sequential shear‐alignment of two distinct layers, a rhombic array of silica nanolines was fabricated. This methodology provides a facile route to fabricating complex topographically patterned nanostructures. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1058–1064     

Extended Open-Chain Polyenides as Versatile Delocalized Anion Ligands for Metal Chain Clusters

Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd₄]⁴⁺ chain.     

Ligand Taxonomy for Bioinorganic Modeling of Dioxygen-Activating Non-Heme Iron Enzymes

Novel functions emerge from novel structures. To develop efficient catalytic systems for challenging chemical transformations, chemists often seek inspirations from enzymatic catalysis. A large number of iron complexes supported by nitrogen-rich multidentate ligands have thus been developed to mimic oxo-transfer reactivity of dioxygen-activating metalloenzymes. Such efforts have significantly advanced our understanding of the reaction mechanisms by trapping key intermediates and elucidating their geometric and electronic properties. Critical to the success of this biomimetic approach is the design and synthesis of elaborate ligand systems to balance the thermodynamic stability, structural adaptability, and chemical reactivity. In this Concept article, representative design strategies for biomimetic atom-transfer chemistry are discussed from the perspectives of “ligand builders”. Emphasis is placed on how the primary coordination sphere is constructed, and how it can be elaborated further by rational design for desired functions.     

简支及悬臂箱梁在角隅轴向荷载作用下的翼板纵向应力

基于能量变分原理，拟定轴向荷载作用下箱梁的纵向位移函数，得到关于翼板剪切变形引起的位移差函数的基本微分方程，继而推导出箱梁翼板纵向应力表达式，并首次得出角隅轴向荷载作用下翼板出现应力不均匀分布的荷载及边界条件。通过对一模型箱梁进行计算，并与通用有限元软件ANSYS壳单元计算结果进行比较，验证了该方法和所推导公式的正确性。研究结果表明，当作用于简支箱梁截面角隅处的轴向荷载（合力无偏心）为集中或分布荷载时，翼板不产生纵向应力不均匀现象；当作用于悬臂箱梁截面角隅处的轴向荷载（合力无偏心）为集中荷载时，翼板不产生纵向应力不均匀现象，而当荷载轴向分布时，翼板将产生纵向应力不均匀现象。实际工程中，横力弯曲使悬臂箱梁产生剪力滞效应，这种效应会与轴向分布荷载产生的效应叠加，设计时对此应予以充分考虑。     

政府奖励对报废汽车回收模式选择的作用机制研究——基于企业社会责任视角

随着我国报废汽车数量的增多,由其造成的交通隐患、环境污染和资源浪费已成为重要社会问题,而如何设计合理可行的回收模式成为解决问题的关键。以制造商主导为前提,提出了基于企业社会责任的报废汽车回收模型,构建了制造商回收、销售商回收和第三方回收模式下的回收流程和数学模型,通过实例对考虑和不考虑企业社会责任两种情况下的回收模型进行了分析,探讨了不同政府奖励下报废汽车回收模式的策略选择。通过研究发现:(1)不论是否考虑企业社会责任,随着政府奖励的增加,制造商最终都会选择由自己进行回收;(2)当考虑企业社会责任时,政府奖励和决策者经济责任偏好都会导致决策的改变,随着政府奖励和赋予经济责任权重的同步增加,制造商的决策由第三方企业回收模式或销售商回收模式变成了制造商回收模式,表明政府奖励和企业社会责任对报废汽车回收模式选择具有显著影响。     

Reversible Activation of Water by an Air- and Moisture-Stable Frustrated Rhodium Nitrogen Lewis Pair

[Cp*Rh(κ³N,N′,P- L )][SbF₆] (Cp*=C₅Me₅), bearing a guanidine-derived phosphano ligand L , behaves as a “dormant” frustrated Lewis pair and activates H₂ and H₂O in a reversible manner. When D₂O is employed, a facile H/D exchange at the Cp* ring takes place through sequential C(sp³)−H bond activation.