Predictive association of metal–organic systems in the solid-state: the molecular electrostatic potential based approach

Designing crystalline solids with improved properties or performances remains a challenging task, despite great strides that have been made within the field of crystal engineering since its birth several decades ago. Herein, we are bringing examples that illustrate recent successes in taking supramolecular synthetic guidelines from the organic crystal engineering and adjusting those to metal-containing systems, particularly to the lower-dimensional ones. The versatility of calculated molecular electrostatic potential (MEP) as a new crystal engineering tool is demonstrated.     

Interactions between hydrogen and the (112¯1) twin boundary in hexagonal close-packed titanium

In hexagonal close-packed titanium, the interactions between the $\left(11\overline{2}1\right)$ twin boundary (TB) and hydrogen solute atoms with several different concentrations are investigated by using first-principles calculations. The preferential occupation sites of hydrogen atoms in the $\left(11\overline{2}1\right)$ TB region are searched and vary with the amount of hydrogen. Both the shift of the TB and the diffusion of hydrogen atoms, as well as the mutual effect on the movement of each other, are studied. The energy barriers of the TB shift increase with the hydrogen concentration. Additionally, the simulated tensile tests are applied for several systems with co-existing $\left(11\overline{2}1\right)$ TB and hydrogen atoms, and different geometry transformation behaviors at different hydrogen concentrations are found under the increasing tensile strain.     

Macroscale evaluation and testing of chemically hydrogenated graphene for hydrogen storage applications

The effective storage of H₂ gas represents one of the major challenges in the wide spread adoption of hydrogen powered fuel cells for light vehicle transportation. Here, we investigate the merits of chemically hydrogenated graphene (graphane) as a means to store high-density hydrogen fuel for on demand delivery. In order to evaluate hydrogen storage at the macroscale, 75 g of hydrogenated graphene was synthesized using a scaled up Birch reduction, representing the largest reported synthesis of this material to date. Covalent hydrogenation of the material was characterized via Raman spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis (TGA). We go on to demonstrate the controlled release of H₂ gas from the bulk material using a sealed pressure reactor heated to 600 °C, identifying a bulk hydrogen storage capacity of 3.2 wt%. Additionally, we demonstrate for the first time, the successful operation of a hydrogen fuel cell using chemically hydrogenated graphene as a power source. This work demonstrates the utility of chemically hydrogenated graphene as a high-density hydrogen storage medium, and will be useful in the design of prototype hydrogen storage systems moving forward.     

Investigation of the hydrogen induced cracking behaviour of API 5L X65 pipeline steel

The effect of microstructural features on the hydrogen induced cracking (HIC) susceptibility of two API 5L X65 pipeline steels were investigated by cathodic charging, hydrogen permeation and hydrogen microprint experiments. Microstructural evaluation after hydrogen charging revealed cracks at the mid-thickness (segregation zone) of both plates. However, more severe cracks were observed in the plate with higher dislocation density and residual stresses. The plate with lower plastic strain and more {111}-oriented grains had less severe cracks. Inclusions found along the crack path, comprising of Si-enriched oxides and carbides contributed to the initiation and propagation of cracks. The variation of the trapping behaviour and hydrogen diffusion through the plates were examined. The results confirmed that a higher ratio of reversible to irreversible traps contributes to increasing HIC severity in steels. Additionally, hydrogen transport through the steels was most prominent along the grain boundaries, indicating the importance of grain boundary character to HIC.     

Structural Consequences of the 1,2,3-Triazole as an Amide Bioisostere in Analogues of the Cystic Fibrosis Drugs VX-809 and VX-770

Although the 1,2,3-triazole is a commonly used amide bioisostere in medicinal chemistry, the structural implications of this replacement have not been fully studied. Employing X-ray crystallography and computational studies, we report the spatial and electronic consequences of replacing an amide with the triazole in analogues of cystic fibrosis drugs in the VX-770 and VX-809 series. Crystallographic analyses quantify subtle differences in the relative positions and conformational preferences of the R¹ and R² substituents attached to the amide and triazole bioisosteres. Computational studies derived from the X-ray data highlight the improved hydrogen bonding donor and acceptor capabilities of the amide in comparison to the triazole. This analysis of the spatial and electronic differences between the amide and 1,2,3-triazole will inform medicinal chemists as they consider using the triazole as an amide bioisostere.     

煤制天然气中氢对X80钢螺旋焊管力学性能的影响

近年来,我国多项煤制天然气示范工程投入运行,X80钢螺旋焊管常用于天然气长输管道建设,其与煤制天然气的相容性直接影响了长输管道的服役寿命和安全可靠性。为研究煤制天然气对国产X80钢螺旋焊管的力学性能影响,分别从埋弧螺旋焊管的母材和螺旋焊缝处取样,在总压为12 MPa,氢气分数为0,1vol%,2.2vol%,5vol%的模拟环境中分别进行慢应变速率拉伸试验和疲劳裂纹扩展速率试验。试验结果表明:含氢量5vol%以下时,煤制天然气对国产X80管线钢强度性能影响很小,但对塑性性能有一定影响,对疲劳裂纹扩展性能影响很大,煤制天然气中氢对母材的疲劳裂纹扩展性能劣化影响比螺旋焊缝严重。     

离子液体的溶液热力学模型研究进展

离子液体是近年来发展起来的一种绿色介质，在化工反应和分离过程中具有广泛的应用前景。离子液体的溶液热力学性质和相平衡数据是其相关工艺过程设计的基础。本文从如下几个方面综述了离子液体溶液热力学模型的研究进展，即溶液热力学研究方法、溶液热力学模型的构建、离子液体的结构和分子间作用力、离子液体的溶液热力学模型及其在相平衡计算中的应用。重点分析了适用于离子液体溶液热力学性质计算的状态方程模型和过量Gibbs自由能模型或活度系数模型，离子液体的电解质和非电解质溶液模型，以及这些模型对ILs结构、氢键和静电作用的处理方法。分析了这些模型的优缺点，并对今后离子液体的溶液热力学研究提出了建议。     

How to accelerate green technology diffusion? Directed technological change in the presence of coevolving absorptive capacity

The time window for effective climate change mitigation is closing. Technological change needs to be accelerated to limit global warming to a manageable level. Path dependence of technological change is one explanation for sluggish diffusion of green technologies. Firms acquire capital that differs by technology type and build up type-specific technological know-how needed to use capital efficiently. Path dependence emerges from cumulative knowledge stocks manifested in the productivity of supplied capital and firms’ capabilities. Increasing returns arise from induced innovation feedbacks and learning by doing. Relatively lower endowments with technological knowledge are a barrier to diffusion for new technologies. This paper shows how the evolution of relative stocks of technological knowledge explains different shapes of diffusion curves. Using an eco-technology extension of the macroeconomic agent-based model Eurace@unibi, it is shown how the effectiveness of different climate policies depends on the type and strength of diffusion barriers. Environmental taxes can outweigh lower productivity and subsidies perform better if lacking capabilities hinder firms to adopt a sufficiently mature technology.     

方腔内耦合传热传质非对称流动数值模拟

对带有质热源的方腔内流体传热传质进行数值研究。针对不同Ra、Nc、Sr和Df，探究对称方腔内流体传热传质的分岔特性。结果表明：存在临界Ra_c使流体流动形态发生转变，当Ra<Ra_c时，流体流线、温度场和浓度场对称分布；当Ra>Ra_c时，流体发生偏斜。增大浮升力，流体更易发生分岔现象。增强Soret和Dufour效应可增强传热对称性并增大流体发生分岔的临界Rayleigh数。     

Optimization of self-regulated hydrogen production from photovoltaic energy

The use of photovoltaic energy (PV) for the production of hydrogen by using autonomous modular self-regulated systems is studied. Results are compared with those obtained for controlled systems. It was proved that for small and low-cost applications, it is possible to eliminate any control system with yields as high as 91.2% in the PV-electrolyzer interface for a sunny day. Self-regulated systems are thus an excellent, safe, cheap and environmentally friendly alternative for applications in isolated sites, especially in emerging countries.