Metal chlorides-promoted ammonia absorption of deep eutectic solvent

Ammonia is considered as a promising hydrogen or energy carrier. Ammonia absorption or adsorption is an important aspect for both ammonia removal, storage and separation applications. To these ends, a wide range of solid and liquid sorbents have been investigated. Among these, the deep eutectic solvent (DES) is emerging as a promising class of ammonia absorbers. Herein, we report a novel type of DES, i.e., metal-containing DESs for ammonia absorption. Specifically, the NH₃ absorption capacity is enhanced by ca. 18.1–36.9% when a small amount of metal chlorides, such as MgCl₂, MnCl₂ etc., are added into a DES composed of resorcinol (Res) and ethylene glycol (EG). To our knowledge, the MgCl₂/Res/EG (0.1:1:2) DES outperforms most of the reported DESs. The excellent NH₃ absorption performances of metal–containing DESs have been attributed to the synergy of Lewis acid–base and hydrogen bonding interactions. Additionally, good reversibility and high NH₃/CO₂ selectivity are achieved over the MgCl₂/Res/EG (0.1:1:2) DES, which enables it to be a potential NH₃ absorber for further investigations.     

Lewis acid-oxygen vacancy interfacial synergistic catalysis over SO42−/Ce0.84Zr0.16O2–WO3–ZrO2 for N,N-diethylation of aniline with ethanol

Herein, a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis for aniline N,N-diethylation with ethanol was proposed, and the SO₄²⁻/Ce_0.84Zr_0.16O₂–WO₃–ZrO₂ catalyst (SCWZ) with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method, which shows better catalytic activity than the reported solid acidic catalysts. Besides, the SO₄²⁻/ZrO₂ (SZ) and SO₄²⁻/WO₃–ZrO₂ (SWZ) catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component. The SO₄²⁻ and WO₃ mainly generate Lewis acid by bonding with ZrO₂, which is beneficial for the fracture of the N–H bond in aniline. The Ce_0.84Zr_0.16O₂ solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species, which can participate in stripping –OH from ethanol, then the carbocation will also be released, which only needs 1.3805 kcal/mol energy, calculated by density functional theory (DFT), to be input. In comparison, the traditional reaction mechanism needs the Brønsted acidic sites to promote the protonation of ethanol, then dehydration and subsequent formation of carbocation followed, and 108.6846 kcal/mol energy needs to be input, which is far higher than that of the new mechanism. The apparent activation energy (E_a) over SCWZ was measured by experiment to be 34.09 kJ/mol, which is much lower than that of SWZ (47.10 kJ/mol) and SZ (54.37 kJ/mol), illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ. Besides, the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100% and 73%, respectively. The SCWZ can be renewed for 4 times without rapid deactivation, and the longevity of SCWZ is longer than that of SWZ and SZ, as the loaded SO₄²⁻ and tetragonal ZrO₂ are stabilized by Ce_0.84Zr_0.16O₂ and WO₃, respectively.     

Synthesis and characterization of MCM-41-supported nano zirconia catalysts

Series of MCM-41 supported sulfated Zirconia (SZ) catalysts with different loadings (2.5–7.5% wt.) were prepared using direct impregnation method. The acquired solid catalysts were characterized structurally and chemically using X-RD, HRTEM, BET, FT-IR, Raman spectroscopy and TPD analysis. The acidity of the solid catalysts was investigated through cumene cracking and isopropanol dehydration at different temperatures. As the SZ loading increases, the surface acidity of the mesoporous catalysts was enhanced, this was reflected by the higher catalytic activity toward cumene cracking and isopropanol dehydration.     

Topographies of the future: urban and suburban visions in Edward Bellamy’s utopian fiction

In Looking Backward (1888) and Equality (1897), Edward Bellamy offered two distinct but interrelated visions of a utopian future. The first and more famous book was set in a luxuriant, centralized metropolis. The sequel detailed decentralized, suburbanized infrastructures. Within the literature on Bellamy these emendations have been treated as evidence of regressive anti-urbanism. This paper argues instead that Bellamy used correlations between topography and technology to mediate an evolving approach to social reform. The discrepancies between the two texts did not represent abandonment of the city but rather an expansion of the scale and scope necessary to ensure social progress. While Looking Backward has often been invoked in relation the Garden City and City Beautiful movements, a new reading of Equality offers opportunities to rethink Bellamy’s relationship to planning history.     

Measurement of enthalpies of association between CO2 and polymers via in situ ATR-FTIR spectroscopy

Although the existence of Lewis acid–base interactions between CO₂ and electron donating functional groups in polymers can be determined from the vibrational spectra of the polymers in question, only a few quantitative estimates of the strength of such interactions have been reported. We have previously reported values of the enthalpy of association between CO₂ and the carbonyl group in polymers from the bending vibrations of CO₂. In the present work, we extend these measurements to other functional groups and relate the strength of these interactions to the structure of the polymer.     

18F-FDG对小鼠Lewis肺癌移植瘤抑制作用的实验研究

建立Lewis肺癌C57BL/6小鼠皮下移植瘤模型18只,按随机数字法分为高剂量18F-FDG治疗组、低剂量18F-FDG治疗组和对照组,每组6只,分别给予18F-FDG 18.5×107Bq、9.25×107Bq和0.2 mL等体积的生理盐水,于接种后第7天腹腔内一次给药,观察18F-FDG对Lewis肺癌移植瘤体积变化和瘤重的影响。22天后用流式细胞仪检测细胞凋亡,以免疫组化法检测bcl-2及Survivin基因的蛋白表达。发现18F-FDG高、低剂量组肿瘤抑瘤率及凋亡率明显高于对照组,Bcl-2及Survivin蛋白的表达明显低于对照组(P<0.05),与低剂量组相比,高剂量组与对照间差异更为显著(P<0.01)。这表明18F-FDG可明显抑制小鼠Lewis肺癌移植瘤生长,其机制可能与下调Bcl-2及Survivin蛋白的表达促进细胞凋亡有关。     

Assessment of the method for calculating the Lewis number of H2/CO/CH4 mixtures and comparison with experimental results

This paper investigates the various techniques used in the literature to calculate the effective Lewis number of two-component (H₂/CO and H₂/CH₄) and three-component fuels (H₂/CO/CH₄ and H₂/CO/CO₂) over a wide range of equivalence ratios (0.6 ≤ φ ≤ 1.4) under laminar flame conditions. The most appropriate effective Lewis number formulation is identified through comparison with experimentally extracted Lewis numbers (Le). The paper first identifies the proper methodology to extract the experimental Le from the burned Markstein length of an outwardly propagating flame. Second, the different methodologies for the calculation of the effective Le are presented and compared to experimental results for H₂/CH₄ and H₂/CO mixtures. Based on the experimental results, it is shown that the calculation of the effective Le of mixtures can be divided into a three-step procedure depending on the equivalence ratio: (1) calculation of the Le for each fuel and the oxidizer; (2) use of the Le mixing rule; and (3) assessment of the necessity or not of combining the fuel's and oxidizer's Lewis numbers. The paper shows that, in rich mixtures, the oxidizer Le needs to be taken into account. Lastly, the methodology is validated for H₂/CO/CH₄ and H₂/CO/CO₂ fuels.     

Study on the Mechanisms for Baeyer-Villiger Oxidation of Cyclohexanone with Hydrogen Peroxide in Different Systems

The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing ε-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H2O2 and H2O, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with ·OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Brnsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by Brnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*C=O orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H2O2 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O-O group highly electrophilic to attack the C=O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.     

我国PCB工业的发展趋势——调整结构、创新发展

文章概述了我国PCB工业的未来五年是战略的提升期.在这战略提升期中,要着重抓好"调整转变(整合提高)"、创新发展.实现这一目标的最好方法是"政产学研"结合形式.