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1.
目的 提高缓蚀剂在酸溶液中的缓蚀性能.方法 构建含有2-巯基苯并噻唑(MBT)以及不同浓度Cl–的Fe表面溶液模型,并进行分子动力学计算.观察缓蚀剂分子在Fe表面的吸附构型,考察不同Cl–值下缓蚀剂膜的致密化行为.提取缓蚀剂分子的均方位移(MSD)曲线,评价缓蚀剂膜的稳定性.计算水分子的密度分布和扩散系数,考察不同Cl–值下MBT缓蚀剂膜的驱水能力和水分子的迁移能力.结果 当Cl–值从0增加到25时,MBT膜的厚度(0.42~1.51 nm)和致密度(占有面积0.33~1.31 nm2)增加,缓蚀剂分子的自扩散系数减小(从1.25×10–9 m2/s到接近0),水分子的吸附峰强度(相对密度为72.3~33.9 nm–3)和扩散系数(1.495×10–9~0.627×10–9 m2/s)降低.当Cl–值从25增加到36时,则出现了相反的趋势.结论 缓蚀剂分子与Cl–之间存在协同作用,适当浓度的KCl可以提高MBT缓蚀剂在H2SO4溶液中的缓蚀性能.Cl–值为25时,MBT缓蚀效率最高.  相似文献   
2.
Metal organic frameworks (MOFs) containing zirconium secondary building units (SBUs) in UiO-67 and related MOFs, are highly active for neutralizing both the chemical warfare agents and simulants, such as dimethyl methylphosphonate (DMMP). However, two recent publications gave conflicting reports of DMMP reaction with UiO-67 under ultra high vacuum (UHV) conditions, with one reporting chemisorption and reaction (Wang et al., J Phys Chem C, 2017, 121, 11261–11272) and the other reporting only physisorption and reversible desorption (Ruffley et al., J Phys Chem C, 2019, 123, 19748–19758) from very similar temperature programmed desorption experiments. We show that the discrepancy between these experiments may be explained by different levels of missing linker defects in the UiO-67 samples. We present density functional theory calculations showing that SBU sites having two-adjacent missing linkers exhibit reaction barriers that are about 30 kJ/mol lower than SBU sites having a single missing linker. We also show that topology of the undercoordinated sites plays an important role in the reaction barrier under UHV conditions.  相似文献   
3.
卢沛  罗向龙  陈健勇  杨智  梁颖宗  陈颖 《化工学报》2021,72(Z1):512-519
针对不同换热设备组合之间以及换热设备在系统中的分布情况进行了研究,建立了高级分析模型,将换热设备与系统的损进一步分割成不可避免性部分和可避免性部分,计算相应的损失和效率,确定换热设备与系统中能量损失的主要部位,并在有机朗肯循环(organic Rankine cycle,ORC)系统试验台中进行验证,为换热设备及其热力系统的运行优化提供科学依据。结果表明,不同的换热面积对换热设备的能效有着非常大的影响,同时常规分析和高级分析提出了不同的系统优化次序。高级分析表明,蒸发器可避免损占蒸发器损的41.2%~60.0%,冷凝器可避免损占冷凝器总损最高可达91%~97%,整个ORC系统有52.5%~66.3%的损可以避免,有很大的改造潜力,且发现不合理设计的管道也会影响ORC系统性能。  相似文献   
4.
Recently, circularly polarized organic light-emitting diodes (CP-OLEDs) fabricated with thermally activated delayed fluorescence (TADF) emitters are developed rapidly. However, most devices are fabricated by vacuum deposition technology, and developing efficient solution-processed CP-OLEDs, especially nondoped devices, is still a challenge. Herein, a pair of triptycene-based enantiomers, (S,S)-/(R,R)-TpAc-TRZ, are synthesized. The novel chiral triptycene scaffold of enantiomers avoids their intermolecular π–π stacking, which is conducive to their aggregation-induced emission characteristics and high photoluminescence quantum yield of 85% in the solid state. Moreover, the triptycene-based enantiomers exhibit efficient TADF activities with a small singlet-triplet energy gap (ΔEST) of 0.03 eV and delayed fluorescence lifetime of 1.1 µs, as well as intense circularly polarized luminescence with dissymmetry factors (|gPL|) of about 1.9 × 10−3. The solution-processed nondoped CP-OLEDs based on (S,S)-/(R,R)-TpAc-TRZ not only display obvious circularly polarized electroluminescence signals with gEL values of +1.5 × 10−3 and −2.0 × 10−3, respectively, but also achieve high efficiencies with external quantum, current, and power efficiency up to 25.5%, 88.6 cd A−1, and 95.9 lm W−1, respectively.  相似文献   
5.
Since the discovery in 1922 of 2,2-diphenyl-1-(2,4,6-trinitrophenyl) hydrazyl stable free radical (DPPH·), the chemistry of such open-shell compounds has developed continuously, allowing for both theoretical and practical advances in the free radical chemistry area. This review presents the important, general and modern aspects of the chemistry of hydrazyl free radicals and the science behind it.  相似文献   
6.
The low cost and highly efficient construction of electrocatalysts has attracted significant attention owing to the use of clean and sustainable energy technologies. In this work, cobalt nanoparticle decorated N-doped carbons (Co@NC) are synthesized by the pyrolysis of a cobalt covalent organic framework under an inert atmosphere. The Co@NC demonstrates improved electrocatalytic capabilities compared to N-doped carbon without the addition of Co nanoparticles, indicating the important role of cobalt. The well-dispersed active sites (Co–Nx) and the synergistic effect between the carbon matrix and Co nanoparticles greatly enhance the electrocatalytic activity for the oxygen reduction reaction. In addition, the Co content has a significant effect on the catalytic activity. The resulting Co@NC-0.86 exhibits a superb electrocatalytic activity for the oxygen reduction reaction in an alkaline electrolyte in terms of the onset potential (0.90 V), half-wave potential (0.80 V) and the limiting current density (4.84 mA·cm–2), and a high selectivity, as well as a strong methanol tolerance and superior durability, these results are comparable to those of the Pt/C catalyst. Furthermore, the superior bifunctional activity of Co@NC-0.86 was also confirmed in a home-built Zn-air battery, signifying the possibility for application in electrode materials and in current energy conversion and storage devices.  相似文献   
7.
芥子气(HD)是难降解可致死的最广泛使用的化学战剂,锆基金属有机框架材料(Zr-MOFs)MOF-808对其有很好的降解效果。但现阶段研究MOF-808对HD的降解多以粉末态使用,易团聚难回收,为解决此问题,研究使用静电纺聚丙烯腈(PAN)来固定回收MOF-808,并验证了MOF-808@PAN对芥子气有优异的降解效果。以ZrOCl2、均苯三甲酸为原料,三氟乙酸为调节剂,基于水为溶剂无模板的合成了MOF-808@PAN纳米纤维材料。采用SEM、XRD、FTIR、TG及氮气吸脱附对催化剂结构进行了表征。实验结果表明,MOF-808@PAN纳米纤维具有441.5m2/g的比表面积。在5μL芥子气模拟剂(CEES)下暴露20个小时,CEES的降解效率可达83.7%。为芥子气的降解提供另一解决思路。  相似文献   
8.
到目前为止TiO2是较为成熟的半导体光催化材料,但因TiO2分散性差、量子利用率低、比表面积小、难回收等问题难以工业化。多孔金属有机框架MOFs的引入可增强TiO2/MOFs复合材料的光吸收性能,提高电子-空穴对分离和提高回收率。基于TiO2/MOFs制备时前驱体添加顺序不同,综述了TiO2/MOFs的三种制备方法(即Ship-in-a-bottle法、Bottle-around-ship法、One-pot法)及TiO2/MOFs光催化机理与性能影响因素,并探讨不同MOFs与TiO2结合的作用机理。最后,对TiO2/MOFs存在的问题提出建议。  相似文献   
9.
Adsorption separation of olefin and paraffin can greatly lower the energy consumption associated with the currently utilized distillation technique but remains a great challenge. Herein, we report the efficient separation of propylene (C3H6) and propane (C3H8) in a phosphate anion-functionalized metal–organic framework (MOF) ZnAtzPO4 by synergetic effect of equilibrium and kinetics. The material features periodically expanded and contracted apertures decorated with electronegative groups, offering eligible pore shape and pore chemistry to effectively trap C3H6 under moderate isosteric heat of adsorption (27.5 kJ mol−1) while obstruct the diffusion of C3H8. It simultaneously combines excellent thermodynamic selectivity (uptake ratio of 1.71) and kinetic selectivity (~31) for C3H6/C3H8 separation, meanwhile can be easily regenerated. Breakthrough experiment for C3H6/C3H8 gas mixture was conducted and confirmed the outstanding separation capability of ZnAtzPO4. The equilibrium and kinetics cooperative C3H6/C3H8 adsorption separation was for the first time found in anion-functionalized MOFs, and further confirmed by computational studies.  相似文献   
10.
The luminescent hydrogen-bonded organic framework (HOF) based films have become one of the most remarkable materials for optical application, thus, developing facile synthesis methods and establishing multifunctional applications for HOF-based luminescent materials are essential. Herein, a dual-emitting Eu3+-functionalized HOF hydrogel film ( 1 ) is fabricated successfully. 1 emits a blue-green long afterglow when turning off the UV lamp, and the long afterglow lifetime gets to 1.99 s. 1 performs great selectivity, high sensitivity, and low detection limit toward ofloxacin and flumequine, and the sensing toward ofloxacin and flumequine is in accord with the chroma and ratio modes. The fluorescent response mechanisms of 1  toward ofloxacin and flumequine are investigated in depth, which are further utilized to build an anticounterfeiting platform with high-level security. The film-based anticounterfeiting platform can conduct information encryption on demand inline with different fluorescent responses and can also fetch specific information by controlling the long afterglow intensity and excited light. This study not only provides a representative case of the fabrication of dual-emitting Eu3+-functionalized HOF-based hydrogel film but also opens the possibility of HOF-based film as intelligent luminescent materials with multifunctionalities.  相似文献   
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