Selective hydrogenation of benzene to cyclohexene over Ce-promoted Ru catalysts

Ru-Ce catalysts were prepared by a co-precipitation method.The effects of Ce precursors with different valences and Ce contents on the catalytic performance of Ru-Ce catalysts were investigated in the presence of ZnSO4.The Ce species in the catalysts prepared with different valences of the Ce precursors all exist as CeO2 on the Ru surface.The promoter CeO2alone could not improve the selectivity to cyclohexene of Ru catalysts.However,almost all the CeO2 in the catalysts could react with the reaction modifier ZnSO4 to form(Zn(OH)2)3(ZnSO4)(H2O)3 salt.The amount of the chemisorbed salt increased with the CeO2 loading,resulting in the decrease of the activity and the increase of the selectivity to cyclohexene of Ru catalyst.The Ru-Ce catalyst with the optimum Ce/Ru molar ratio of 0.19 gave a maximum cyclohexene yield of 57.4%.Moreover,this catalyst had good stability and excellent reusability.     

Enzyme-free amperometric sensing of hydrogen peroxide and glucose at a hierarchical Cu2O modified electrode

In this paper, an enzyme-free amperometric electrochemical sensor was fabricated by casting Nafion-impregnated Cu₂O particles onto a glassy carbon electrode. A dual dependence of peak current on sweeping rate, which can be attributed for the accumulation of reaction products, was observed on the sensor. Electrochemical analysis of the particulate Cu₂O for detecting H₂O₂ and glucose is described, showing remarkable sensitivity in both cases. The estimated detection limits and sensitivities for H₂O₂ (0.0039 μM, 52.3 mA mM⁻¹ cm⁻²) and glucose (47.2 μM, 0.19 mA mM⁻¹ cm⁻²) suggest that the response for H₂O₂ detection was much higher than for glucose detection. Electron microscopy observation suggested that the hierarchical structures of Cu₂O resulting from self-assembly of nanocrystals are responsible for the specific electrochemical properties.     

Iron phthalocyanine oligomer/Fe3O4 hybrid microspheres and their microwave absorption property

The novel nano-scale iron phthalocyanine oligomer/Fe₃O₄ (FePc/Fe₃O₄) hybrid microspheres were synthesized from iron phthalocyanine oligomer and FeCl₃·6H₂O via a solvent-thermal crystallization route. The morphology and structure of the hybrid microspheres were characterized by Fourier transform infrared spectrophotometer, X-ray diffraction, scanning electron microscopy and transmission electron microscopy. These results showed that the hybrids were monodisperse microspheres and the morphology can be adjusted by controlling pre-polymerization time. The saturation magnetization increased with increase in the pre-polymerization time, while the coercivities decreased. The FePc/Fe₃O₄ hybrid microspheres exhibited novel microwave electromagnetic properties: the dielectric loss was enhanced when the pre-polymerization time increased and a new microwave loss peak appeared at high frequency. The microwave absorbing properties enhanced with increase in the pre-polymerization time and a maximum reflection loss of −29.7 dB was obtained at 11.7 GHz with 6 h of pre-polymerization time when the matching thickness was 3.0 mm. The novel hybrid materials are believed to have potential applications as microwave absorbing materials.     

带宽对平顶高斯宽带激光传输特性的影响

研究了横向分布为平顶高斯模式的宽带激光在自由空间的传输特性,分析了频带宽度对其强度分布的影响。首先推导了平顶高斯模式宽带激光的每一频率分量在自由空间的传输公式,然后将频率域的传输公式通过傅里叶变换得到时间域的传输公式。基于推导的公式通过数值算例给出了不同频带宽度激光光束的强度分布结果,详细分析了空间模式的变化和时空耦合现象。研究结果表明:随着传输距离增大,平顶高斯空间模式趋于高斯分布。同时随着带宽增大,平顶高斯模式宽带激光表现出更强的时空耦合现象,并导致其空间横向分布发生明显变化。变化的主要特征为波前的强度分布随带宽增大而变窄,波后的强度分布则随带宽增大而远离轴中心向外扩展。     

带梯度项的椭圆型方程边界爆破解的高阶估计

In this paper,the higher order asymptotic behaviors of boundary blow-up solutions to the equation■in bounded smooth domain■are systematically investigated for p and q.The second and third order boundary behaviours of the equation are derived.The results show the role of the mean curvature of the boundary■and its gradient in the high order asymptotic expansions of the solutions.     

Transition-metal-free highly efficient synthesis of 2-pyridones from β-keto amides and ynals

A convenient and efficient annulation reaction was developed, affording 2-pyridones in good to excellent yields. A variety of substituted β-keto amides and ynals were well tolerated, and especially the transformation produced water as only by-product under transition-metal-free conditions. Furthermore, the conjugated enyneamides were achieved from β-cyano amides and ynals in high yields.     

Constructing amidoxime-modified porous adsorbents with open architecture for cost-effective and efficient uranium extraction

The dense structure of polymeric matrices exposes only 10–20% of adsorption (amidoxime) groups, thus detracting from the extraction efficiency of uranium from seawater. Herein, the amidoxime-modified building units were cross-linked via the Scholl reaction into porous aromatic frameworks (PAFs). Due to the formation of open architecture, PAF adsorbents reveal a larger utilization ratio (>60%) of amidoxime groups. Consequently, PAF samples enable an ultrahigh uranium capacity of 702 mg g⁻¹, which creates a 16-fold capacity enhancement and gains a 7-fold adsorption rate improvement compared with polymer-based adsorbents. Notably, PAF solids are able to be integrated into various devices, thus realizing versatile and efficacious uranium extraction from real seawater (meeting the commercial standard ∼6 mg g⁻¹ in 21 days). In addition, the final cost using our PAF-based adsorbent is US $189.77 per kg uranium, it is in accordance with the prevailing market cost ($100–335 per kg).

The dense structure of polymeric matrices exposes only 10–20% of adsorption (amidoxime) groups, thus detracting from the extraction efficiency of uranium from seawater.     

Insight into the origins of the reactivity and selectivity for the aminocatalytic [2+2] cycloaddition reaction

A density functional study of the [2 + 2] cycloaddition between methyleneindolinones and enals catalyzed by prolinol derivatives is presented here. The calculations show that dienamines could be generated under acid-free conditions, and the hydroxyl of the catalysts plays a key role in the formation of dienamines. The following cycloaddition process between methyleneindolinones and the new formed dienamines includes two-step intramolecular electron transfers. The stereoselectivity is mainly attributed to the charge distributions on the reaction centers and the H-bonding interaction between the catalysts and methyleneindolinones. The excellent 3,4-regioselectivity is largely ascribed to the fact that the pre-product of 1,2-reactivity is tough to hydrolyze, but could return to the precursor. Besides, the large steric hindrance of catalysts is not conducive to the 3,4-reactivity, while the H-bonding between the catalysts and methyleneindolinones has less effect on the regioselectivity.     

ESR Study on Scavenging Effect of Squalene on Free Radicals in Mainstream Cigarette Smoke

Radicals in mainstream cigarette smoke (MCS) have been proposed to contribute to the harm caused by cigarette smoking. In the present study, we used natural antioxidant, squalene, to treat cigarette filters and tobacco for scavenging gas- and particulate-phase free radicals in MCS. The scavenging activities of cigarette filter and tobacco containing squalene against gas and particulate-phase free radicals were detected and quantified using spin-trapping or directly electron spin resonance spectroscopy method. The results revealed that squalene could significantly scavenge gas- and particulate-phase free radicals in MCS in a dose-dependent manner. The radical-scavenging activity of cigarette filter treatment was higher than that of tobacco treatment, irrespective of either gas-phase free radicals, or particulate-phase free radicals in MCS. Among them, 3 mg squalene/filter treatment showed that the highest scavenging effects against gas- and particulate-phase free radicals were 35.9 and 35.4%, respectively. The use of squalene as potential scavenger for reducing free radicals in cigarette smoke is discussed.