The uniform distribution and high density of ionic moieties in functional porous organic polymers are highly advantageous for carbon dioxide (CO2) capture and conversion. In this study, a series of functional poly(ionic liquid)s (FPILs) with hierarchical nanoporous structure bearing definite hydroxyl group were synthesized via ionothermal free-radical self-polymerization of hydroxyl-functionalized bis-vinylimidazolium monomer. The characterizations reflected that an improved surface area (up to 130.1 m(2) g(-1)), uniform chemical structure, and high-density ionic sites (up to 4.32 mmol g(-1)) and hydroxyl-based hydrogen bond donor (HBD) were achieved by optimizing synthetic parameters. After anion exchange to enrich active Br- anions, the resulting FPIL behaved as high-efficiency heterogeneous organocatalyst for solvent-additive-free CO2 cycloaddition at 90 degrees C and 1 MPa CO2. A high yield of 99.2 % with turnover frequency of 55.7 h(-1) over epichlorohydrin (ECH) was attained, much higher than most reported HBD-based heterogeneous catalysts, even surpassing homogeneous analogue. Furthermore, a wide range of epoxides including sterically hindered ones were transformed with high yields under atmospheric pressure. A possible synergistic effect involving Br- anions and HBDs dual active sites was proposed. This work highlights the significance of integrating hierarchical porosity, high-density and uniformly distributed active sites in the rational design of HBD-based heterogeneous organocatalysts for efficient CO2 fixation.

Separating acetonitrile-water azeotropic systems is challenging due to unclear molecular-level interaction mechanisms of ionic liquids (ILs). This study investigated ILs ([Emim]Br, [Bmim]Br, [Emim][BF4], and [Bmim][BF4]) as entrainers using experimental and theoretical approaches to elucidate the azeotropic point-breaking mechanism. Molecular dynamics (MD) simulations were employed to analyze binary and ternary solutions, while density functional theory (DFT) at B3LYP/6-311 + G(d) was used to refine the complexation energies and Boltzmann-averaged multiple isomers. Vapor-liquid equilibrium (VLE) data (T, x, and y) for the pseudobinary systems of acetonitrile, water, and ILs at 101.33 kPa were measured and correlated using the nonrandom two-liquid (NRTL) model. The results show that ILs exhibit a stronger salting-out effect than solvation, enhancing the relative volatility of acetonitrile and eliminating the azeotropic point. The salting-out efficacy followed the order [Emim]Br > [Bmim]Br > [Emim][BF4] > [Bmim][BF4], with [Emim](+) and Br- being the most effective. These findings highlight the ILs' potential for efficient, sustainable industrial azeotrope separation.

Metal halide perovskites have recently emerged as promising candidates for photothermal catalysis due to their tunable band gaps, high absorption coefficient, and long carrier diffusion length. Most studies have concentrated on 3D perovskite-based heterostructures, while studies on 0D perovskite materials remain largely underexplored, especially in the area of photothermal catalysis. Herein, 0D Cs2MoBr6 microcrystals (MCs) with an octahedral morphology are synthesized, demonstrating efficient photothermal activity for the conversion of benzyl alcohol to benzaldehyde with similar to 97 % selectivity within 270 min, under normal pressure, at room temperature and without the use of additives or additional oxidants. Mechanistic studies reveal that 0D Cs2MoBr6 MCs exhibit ultrafast hot-carrier relaxation (< 1 ps) and strong electron-phonon coupling, which facilitate the generation of thermal energy and enhance reaction activity. Surface potential measurements further demonstrate efficient charge separation in Cs2MoBr6, which could facilitate the generation of superoxide radicals. Multiple scavenging experiments confirmed that the photogenerated electrons, holes, O-2(-), and O-1(2) play crucial roles in efficient photothermal catalysis. Our work highlights that perovskite can serve as an ideal platform for further exploration of thermocatalysis and photothermal catalysis, opening a new avenue for the use of halide perovskites as photothermal converters.

TEMPO-functionalized porous poly(ionic liquid)s prepared via copolymerization exhibits high catalytic efficiency under solvent-metal-free conditions. This study provides a green and sustainable approach for the aerobic oxidation of alcohols.

It is a formidable dilemma for vapor-liquid equilibrium (VLE) association behavior in chemical separation procedures to correlate and predict binary and ternary mixtures containing associated components, since the form of components is completely unknown, such as monomers, homogeneous or heterogeneous dimers, trimers, and even polymers, and so on. Herein, the VLE data for the binary and ternary mixtures, including methanol, water, and ethanoic acid, were measured via the various liquid- and vapor-phase compositions using a Fisher ebulliometer at 101.33 kPa. The geometric configurations and distributions of diverse clusters in methanol, water, and ethanoic acid systems were wholly optimized at the B3LYP/6-31+G(d) level of theory using Gaussian 09. Then, we established a strategy for computing the liquid activity coefficients by pondering the various association species in the associating system. The approach is named the discrete clusters (DC) model, and the comparison is also provided between the calculating results for the binary systems of the DC model and the UNIQUAC, NRTL, and Wilson models. Moreover, the ternary system's phase behavior was investigated by using the DC, UNIQUAC, NRTL, and Wilson models without further adjusting model parameters. The DC model conveyed the number of various clusters, indicating better consistency and a smaller deviation from the measured data. These VLE data originating from the DC model can be applied to the design and simulation of the chemical separation process of the binary and ternary association systems.

Selective hydrodeoxygenation transformations constitute the most pivotal industrial processes in chemistry and catalysis. Herein, we have rationally designed a heterogeneous Co/CoOx catalytic system with metallic Co and oxygen vacancies in CoOx for selective hydrodeoxygenation of structurally diverse ketones and nitro compounds under mild conditions (80-100 degrees C and 10 bar H2), which shows a superior performance compared to state-of-the-art noble-metal catalysts. Experimental results and DFT calculation revealed that oxygen vacancies not only promote the adsorption and activation of substrates and the intermediates via electronic interactions, but also enable the hydrodeoxygenation reactions in a low-energy pathway via the direct hydrogenolysis process, instead of the dehydration-hydrogenation process. Given its generality and efficiency, it is believed that this method can serve as a practical, economically viable approach for selective hydrodeoxygenation reactions, which should impact both the chemical industry and scientific research. The Co/CoOx catalyst with rich oxygen vacancies was found to be robust for mild and selective hydrodeoxygenation reactions. The oxygen vacancies promote the activation of substrates, and enable the reactions in direct hydrogenolysis pathway.

Nanoporous poly(ionic liquid)s with both great porosities and high IL contents are prepared through a two-step synthetic strategy, serving as efficient heterogeneous catalysts for CO 2 cycloaddition with epoxides under mild conditions.

通过金相显微镜、扫描电镜和电化学工作站等设备,研究了固溶态和时效态无硼和含硼(质量分数0.004％)不锈钢的显微组织和耐蚀性.结果表明:固溶态无硼不锈钢和含硼不锈钢的组织都为单一奥氏体,时效态不锈钢中会析出σ相,硼的添加有助于改善不锈钢中富钼σ相的存在形式;相较于无硼不锈钢,含硼不锈钢的自腐蚀电位更正,腐蚀电流密度、点蚀电位和腐蚀速率更小,表明其具有更好的耐蚀性;与无硼不锈钢比,相同热处理条件下含硼不锈钢的容抗弧半径和相位角更大、钝化膜电阻更小;随着时效时间延长,无硼不锈钢与含硼不锈钢的电荷转移电阻和钝化膜电阻都逐渐减小,双电层电容和钝化膜电容都逐渐增大;含硼不锈钢的耐点蚀性能优于无硼不锈钢,这主要与硼加入后改善了不锈钢中σ相的存在形式,提高了钝化膜的致密度和稳定性有关.

Herein, a strategy for screening ionic liquids as entrainers to separate acetonitrile and water azeotropic systems was implemented by combining theoretical and experimental investigations on the breaking azeotropic-point principle. The measured VLE data (T, x, y) for the acetonitrile (1) + water (2) + ILs (3) pseudo-binary systems at 101.33 kPa were correlated by the nonrandom two-liquid (NRTL) model at the different ILs mole concentrations. 1:1 complexes of four kinds ILs including [Emim]Br, [Bmim]Br, [Emim][BF4], and [Bmim][BF4] with acetonitrile or water were calculated at the B3LYP/6-311+G(d) level of theory using Gaussian 16 package. The salt-out effect of ILs on acetonitrile is superior to their solvation effect by quantum chemistry and COSMO-RS simulations. The experimental results show that the VLE line deviates from the VLE line of the azeotropic system of acetonitrile and water with the addition of [Emim]Br, [Bmim]Br, [Emim][BF4], and [Bmim][BF4]. The bigger the mole fraction of ILs is, the greater the deviation from the VLE azeotropic line is. Therefore, the ILs can change the relative volatility of acetonitrile to the water and eliminate the azeotropic point of the acetonitrile and water system. The order of the salting-out effect of ILs on acetonitrile is as follows: [Emim]Br, [Bmim]Br, [Emim][BF4], and [Bmim][BF4]. Meantime, among them, the salting-out law of the cations on acetonitrile is in the order: [Emim]+ > [Bmim]+; and that of the anions on acetonitrile is Br ‑ > [BF4] ‑ .

The society’s evaluation of individual traditional martial arts people because of their defeat in modern martial arts competitions is more extreme,and some of the online criticisms that have lost their objective rationality are full of anti-intellectualism. Based on the literature and interview methods,the research has examined cultural phenomena and sociology of this social phenomenon,and believes that the traditional Wushu authority has the ideal characteristics of intellectuals,lacks the ability to keep pace with the times and is connected with reality;modern media methods have changed the communication expectations amplify the bad faith of the disorderly crowds;the lack of a public domain of mutual trust in modern society makes the general public unable to objectively and rationally recognize traditional Wushu authority and other factors are the main reasons for the traditional Wushu authority to be questioned. Taking this as a refracting point,we can also see the anxiety and suffering suffered by contemporary society in the modernization brought about by the development and prosperity of the media.

Selective hydrogenation of nitriles is a feasible route to synthesize primary amines. While highly desirable, conducting the synthesis under mild conditions is challenging. We report non-precious zinc and aluminum oxides supported Ni catalysts (Ni/ZnAlOx) facilely prepared by calcination and reduction of NiZnAl layered double hydroxide (LDH) precursors. The optimized Ni/ZnAlOx-600 catalyst demonstrates great activity towards the selective hydrogenation of nitriles to primary amines. Proper-size metallic nickel provides the hydrogenation centers, and the presence of Ni-Zn alloys indicates strong metal-support interactions, which can produce electron-deficient nickel species and enhances the chemisorption of the C---N bonds on the catalyst surface. The introduction of Zinc provides strong Lewis acid sites which also contribute to the catalytic activity. Based on the catalyst characterizations and control experiments, a plausible mechanism is proposed. This catalyst shows good stability and is conducive to the transformation of a variety of aromatic and aliphatic substrates, demonstrating potential application prospects.

在轨卫星数量呈爆发式增长.在应用方面,亟需提升海量卫星并行管理能力和自动化、智能化水平.设计并构建了一种基于知识和大数据的航天器在轨管理云平台,通过工程实际应用,验证了系统设计的可行性,实现了200余颗在轨航天器的并行管理,可以为我国未来复杂星座星群的高效运行管理提供参考.

为研究适用于露天煤矿爆破振动速度的计算公式,基于露天煤矿爆破的现场监测数据,通过回归分析对比了传统萨道夫斯基公式与考虑高程后改进公式的相对误差,并采用量纲分析法推导出适用于计算露天煤矿爆破振动速度的公式.基于量纲分析法的露天煤矿爆破振动速度计算公式,可表述露天煤矿爆破振动速度受高程差影响的缩放效应,当高程差为0时公式退化为萨道夫斯基公式;其计算误差低于传统萨道夫斯基公式误差和考虑高程的萨道夫斯基公式误差.研究结论对露天煤矿的爆破和爆破安全评价具有一定意义.

Biomass feedstocks are promising candidates of renewable clean energy. The development and utilization of biological energy is in line with the concept of sustainable development and circular economy. As an important platform chemical, γ-valerolactone (GVL) is often used as green solvent and biofuel additive. Regarding this, the efficient synthesis of GVL from biomass derivative furfural (FF) has attracted wide attention recently, However, suitable catalyst with appropriate acid-base sites is required due to the complex reaction progress. In this Mini Review, the research progress of catalytic synthesis of GVL from furfural by Zr/Hf-based catalysts was reviewed. The different effects of Lewis acid-base and Brønsted acid sites in the catalysts on each steps in the reaction process were discussed firstly. Then the effects of regulation of acid-base sites in the catalysts was also studied. Finally, the advantages and challenges of Zr/Hf-based catalysts in FF converted to GVL system were proposed.

Lithium-sulfur (Li-S) battery is now a promising technology for energy storage. However, rapid capacity decay due to sulfur dissolution and shutting effect severely limit its commercial development. In this work, a NH2-UIO-66 metal organic framework-derived porous composite (Co-ZrO2@NC) consists of nitrogen-doped carbon (NC) and zirconium oxide (ZrO2) loaded with cobalt nanoparticles was prepared. The porous NC component not only increases the accommodation of sulfur in the cathode, but also benefits the charge transfer in sulfur electrochemistry. The Co and ZrO2would act as active centers to enhance the adsorption/conversion of lithium polysulfide and improve its electrochemical utilization. When used in sulfur cathode, the Co-ZrO2@NC electrode shows excellent electrochemical performance with an initial specific capacity of 1073 mAh g-1at a rate of 0.2 C and a reversible capacity of 1015 mAh g-1after 100 cycles, corresponding to a capacity retention of 94.6%. Furthermore, after 300 cycles at 1.0 C, corresponding to a capacity retention of 75.4%. Moreover, the cell also exhibits good rate performance (640 mAh g-1at 3.0 C). Even at high sulfur loading of 4.0 mg cm-2, the S/Co-ZrO2@NC cathode is able to deliver an areal specific capacity of 4.8 mAh cm-2.

针对卫星静态仿真方法未实现故障时序发展过程及影响范围仿真的问题,在故障仿真方法进行分析的基础上,提出了一种基于层次模型的动态故障仿真方法,即通过建立不同层级的故障模型,利用动态仿真推进方法实现故障的时序发展过程仿真.此方法能够有效提高故障仿真的精细化程度,为故障处置提供支撑.通过某卫星能源安全模式故障仿真,对方法的有效性进行了验证,结果表明该方法能够满足故障仿真要求,可为卫星故障仿真系统设计提供参考.

自1957年第一颗人造地球卫星升空以来,空间目标的数量快速增加,直径1 cm以上的太空物体的数量已经达到数十万个.在这种形势下,已经多次发生在轨航天器与空间碎片相碰撞的情况.空间交通管理的目标是要保证空间系统的安全有效运行和空间资源的有效利用,这就需要进行空间目标探测、碰撞规避等.国外已经制定了相关法律法规,建立了相应的模型.基于以上情况,分析了我国空间交通管理在碎片监测、法律法规、空间碎片模型等方面的差距,提出了一种空间目标管理系统初步构架.

传统的航天器在轨监视体系为集中模式,应急处置时存在时效性低、对在岗值班人员专业要求高等问题.随着在轨航天器数量的急剧增加,亟需引入移动安全技术,支持在可信网络传输环境下移动终端的安全接入和快速响应,实现线上、线下的航天器设计、在轨管理技术力量的有效综合利用.设计了一种基于移动终端和云平台的航天器在轨监视系统,通过原型系统的实际测试,验证了系统在技术上成熟可行,能够实现航天器管理相关人员在远离任务中心的情况下,通过移动终端以安全可靠的方式便捷地接入后端云平台,及时掌握航天器在轨运行状况.