Electrocatalysis as the Nexus for Sustainable Renewable Energy: The Gordian Knot of Activity,Stability, and Selectivity

The use of renewable energy by means of electrochemical techniques by converting H₂O, CO₂ and N₂ into chemical energy sources and raw materials, is the basis for securing a future sustainable “green” energy supply. Some weaknesses and inconsistencies in the practice of determining the electrocatalytic performance, which prevents a rational bottom‐up catalyst design, are discussed. Large discrepancies in material properties as well as in electrocatalytic activity and stability become obvious when materials are tested under the conditions of their intended use as opposed to the usual laboratory conditions. They advocate for uniform activity/stability correlations under application‐relevant conditions, and the need for a clear representation of electrocatalytic performance by contextualization in terms of functional investigation or progress towards application is emphasized.     

Photochromic reverse mode polymer dispersed liquid crystals

Control of light intensity and colour are two of the major features required in the realization of smart windows. We designed a bi‐functional polymer dispersed liquid crystal (PDLC) film in order to satisfy such requirements, i.e. it is able both to modulate the optical transmission, if an external electric field is applied, and to change colour if exposed to sunlight. A monomer/liquid crystal mixture was doped with a small amount of photochromic material and homeotropically aligned by means of rough surfaces. A transparent and pale pink coloured film was achieved after photopolymerization. Such a film changes colour upon exposure for some seconds to sunlight or ultraviolet radiation in a persistent but reversible manner. In addition, the film appears transparent without the application of an electric field (OFF state) and becomes opaque on application of a driving voltage of about 75?V (ON state), and thus the film operates in reverse mode with respect to conventional PDLCs.     

Stabilities,electronic and magnetic properties of Cu-doped nickel clusters: a DFT investigation

In this paper, we investigate the electronic and magnetic properties of Cu-doped nickel clusters by means of density functional theory. The stabilities of these clusters have also been studied in terms of the binding energies, second-order difference of energies, fragmentation energies and HOMO–LUMO energy gaps. The obtained results reveal that the N₄Cu, N₅Cu and Ni₇Cu clusters are found to be more stable that than all other clusters. Higher HOMO–LUMO gap was observed for Ni₅Cu cluster (2.265 eV), indicating its higher chemical stability. A half-metallic behaviour has also been observed for the Ni_nCu clusters, which suggests that these clusters can be employed as nanocatalysts for several catalytic processes, particularly for hydrogenation and dehydrogenation reactions. The magnetism calculations show that the magnetic moment is mostly located on the Ni atoms, and the contribution of the Cu atom to the total magnetic moment in the Ni_nCu clusters is very small. Furthermore, partial density of states analysis indicates that the 3d orbitals in Ni atoms are mostly responsible for the magnetic behaviour of these clusters, and the s orbitals have a very little contribution to the total magnetic moment.     

Structures,stabilities and adsorption mechanisms of nitrogen adsorbed on Mon (n = 1–8) clusters

Configurations, stabilities and adsorption mechanisms of ground-state Mo_nN and Mo_nN₂ (n?=?1–8) clusters are calculated by using the density functional method within the PBE level. Evidently, N atoms tend to approach more Mo atoms. Doping with two N impurity prefers to occupy symmetrical position of the host Mo_n (n?=?1–8) cluster except for Mo₂N₂ clusters. Mo₄N, Mo₆N, Mo₂N₂, Mo₄N₂ and Mo₆N₂ clusters have higher structural stabilities than their neighbors by the second derivative of total binding energy. Mo₂N, Mo₄N and Mo₇N, Mo₂N₂, Mo₅N₂ and Mo₇N₂ clusters have higher kinetic reactivity than their neighbors by the HOMO–LUMO gaps. The adsorption capacity of a N atom to Mo₄ cluster is stronger than the other Mo–N clusters.     

配体结构对含2-甲基咪唑及N-乙基咪唑的NAMI 衍生物水解及溶液稳定性的影响

制备并用UV、循环伏安(CV)和NMR 法研究了NAMI(新抗肿瘤转移抑制剂, trans-[RuCl₄(DMSO)(imidazole)]Na·2DMSO)衍生物trans-[RuCl₄(DMSO)(2-MeIm)]Na·2DMSO (2-MeIm＝2-甲基咪唑, 化合物1)和trans-[RuCl₄(DMSO)-(N-EtIm)]Na·2DMSO (N-EtIm＝N-乙基咪唑, 化合物2)的水解机理-动力学、溶液稳定性和电化学性质. 化合物1 和化合物2 与NAMI 相似, 在pH 7.40 的缓冲溶液中发生两步脱氯水解反应(I 氯水解及II 氯水解) (分步反应); 在酸性溶液(pH 5.00)中脱DMSO 水解. 通过线性拟合得到各水解反应速率常数k_obs 及半衰期t_1/2. 结果表明化合物在酸性溶液中的稳定性相对较高. 在NAMI 衍生物咪唑环的N 位引入乙基比在2 位引入甲基生成的化合物稳定. 含氮配体相同时,NAMI-A(新抗肿瘤转移抑制剂, A: 该系列中的第一个化合物, trans-[RuCl₄(DMSO)(imidazole)][Himidazole])衍生物略比相应的NAMI 衍生物稳定.     

二（2,6-二甲基-4-甲氧基）苯基卡宾的产生和反应

为了考察卡宾稳定性的电子效应,合成了对位具有强推电性甲氧基的二（2, 6-二甲基-4-甲氧基）苯基重氮甲烷(1c),通过光分解而产生了二（2,6-二甲基- 4-甲氧基）苯基卡宾(2c)。分别用电子顺磁共振（EPR）光谱,紫外可见(UV/vis) 光谱及激光闪光光分解法对二（2,6-二甲基-4-甲氧基）苯基卡宾(2c)的产生和衰 减过程进行了详细的观察。由于甲氧基的强推电子作用使二苯基卡宾的稳定性大大 降低,其二次动力学衰减速度常数为130s~(-1),是对位非取代二苯基卡宾(2b) (14s~(-1))的约9倍,且室温苯溶液中的寿命为20ms,仅为2b(180ms)的1/9。且通过 产物分析对二（2,6-二甲基-4-甲氧基）苯基卡宾(2c)的反应及甲氧基的取代基效 应进行了详细探讨。     

几种液体金属自由表面的MHD不稳定性实验研究

介绍了在核工业西南物理研究院的液态金属实验回路(LMEL)上获得的几种可供液态偏滤器-限制器系统选用的液体自由表面的磁流体动力学(MHD)效应不稳定性的实验结果。实验发现：自由表面射流在穿越梯度横磁场时射程变短、截面变扁平,但MHD效应稳定,调节射流与磁场的夹角可以控制射流的流动特性;自由表面膜流MHD效应存在三种现象,即层流、溪状流和湍流。层流是由多束射流打到固体表面产生的(简称“射-膜流”),从MHD效应角度考虑,“射-膜流”将是四种可选液态偏滤器-限制器系统的液体自由表面形式中最佳的选择。同时,探讨了从物理的角度来理解四种自由表面形式的MHD效应的现象。     

密度泛函理论研究簇合物(HFGaN3)n (n=1-6)：尺寸效应

用密度泛函理论DFT方法,计算研究不对称簇合物(HFGaN3)n (n=1-6)的几何构型、稳定性、IR谱和热力学性质。结果表明,簇合物(HFGaN3)n (n=2-6)的优化构型拥有一个Ga和α−N原子交替的2n元环状结构。通过计算研究(HFGaN3)n (n=1-6)的平均结合能、二阶能量差分和能隙与团簇尺寸关系,发现后两者表现出明显的“奇－偶”振荡现象。对计算获得的IR谱进行归属,获得四个特征区。讨论了团簇尺寸和温度对(HFGaN3)n (n=1-6)热力学函数的影响。由焓变和吉布斯自由能可知,200-800 K温度范围内由单体形成稳定的多聚体(HFGaN3)n (n=2-6)在热力学上有利。     

Relative Thermodynamic Stabilities of Isomeric Vinyl Ethers Derived from 2-Acetyland 2-Isobutyryltetrahydrofurans. An Experimental and DFT Study

The relative thermodynamic stabilities of four isomeric vinyl ethers obtained by acid-catalyzed cleavage of MeOH from the dimethyl acetals of both 2-acetyltetrahydrofuran and 2-isobutyryltetrahydrofuran have been determined by chemical equilibration in cyclohexane solution. In addition, the structures and relative energies of many of these compounds have also been studied theoretically by DFT calculations. In each series of compounds, the endocyclic isomers, 5-(1-methoxyethyl)-2,3-dihydrofuran and 5-(1-methoxy-2-methylpropyl)-2,3-dihydrofuran, respectively, show the highest thermodynamic stabilities. This is particularly prominent for the vinyl ethers derived from 2-isobutyryltetrahydrofuran in which the equilibrium mixture consists of 90% of the endocyclic isomer at room temperature. The geometrical (exocyclic) isomers of the latter series of compounds show unexpected relative thermodynamic stabilities, but on the basis of the geometry-optimized structures provided by the DFT calculations, a reasonable explanation can be found.