丁烯在纳米H-ZSM-5催化剂上的催化裂解反应

在小型固定床反应器中考察了纳米H-ZSM-5催化剂(晶粒度为20～50nm)对丁烯催化裂解制丙烯反应的催化性能,并与两种微米H-ZSM-5催化剂样品(晶粒度分别为1～2和1～6μm)进行了比较.结果表明,在相同的反应条件下,纳米H-ZSM-5和微米H-ZSM-5催化剂上的初始丁烯转化率及丙烯收率相当,但纳米H-ZSM-5催化剂在反应中的抗积碳失活性能优于微米H-ZSM-5催化剂.在进料质量空速7h-1,常压和560℃的条件下反应,当丁烯转化率和丙烯收率下降50%时,两种微米催化剂上的反应时间仅为28h左右,而纳米催化剂上的反应时间为120h左右.积碳分析结果表明,纳米催化剂上的积碳速率明显低于微米催化剂.     

Thermal decomposition of 1-hexene by flash pyrolysis: A study of initial decomposition mechanism

Thermal decomposition of 1-hexene at temperatures 295-1410 K was conducted using a flash pyrolysis micro-reactor coupled to laser-based vacuum ultraviolet photoionization time-of-flight mass spectrometer (VUV-PI-TOFMS). The decomposition mechanism of 1-hexene was developed with the help of theoretical calculation performed at the MRCI/cc-pvtz//CASSCF/6–31+G(d,p) level. The γ-scission and diradical retro-ene reactions were determined as the main initial decomposition reactions in the temperature range 990-1240 K. Two diradical retro-ene reaction channels, 1,5-diradical and 1,6-diradical reactions, were proposed in order to interpret the appearance of the C₄H₈ species. The 1,5-diradical retro-ene reaction involved a 1,5-diradical intermediate that subsequently decomposed via CC β-scissions to the C2, C3 and C4 products. The 1,6-diradical retro-ene reaction proceeded via a 1,6-diradical intermediate and CC β-scissions to produce the C2 and C4 species. The proposed diradical retro-ene mechanism was evidenced indirectly by the early product distribution of 1-hexene pyrolysis in a flow reactor at 1173 K determined by synchrotron radiation VUV-PI-TOFMS. It was verified in the flash pyrolysis of 1-heptene as well.     

多偏振飞秒激光制备彩色铁

采用四个不同偏振方向的线偏振和圆偏振态飞秒激光扫描处理金属铁表面来制备不同的彩色铁。从不同角度观察被处理区域时,线偏振扫描处理的彩色区域呈现不同的色彩, 而圆偏振扫描处理的区域没有明显的颜色变化。扫描电子显微镜图片显示,线偏振激光扫描处理金属铁表面形成了nm量级的激光诱导周期表面结构,其方向始终与激光偏振方向垂直;圆偏振激光扫描处理金属铁表面形成的条纹结构不明显且有大量的纳米颗粒结构。     

Innentitelbild: Catalytic Asymmetric Functionalization of Aromatic C?H Bonds by Electrophilic Trapping of Metal‐Carbene‐Induced Zwitterionic Intermediates (Angew. Chem. 48/2014)

Asymmetric functionalization of aromatic C H bonds of N,N‐disubstituted anilines with diazo compounds and imines is reported for the efficient construction of α,α‐diaryl benzylic quaternary stereocenters in good yields with high diastereoselectivities and excellent enantioselectivities. This Rh^II/chiral phosphoric acid cocatalyzed transformation is proposed to proceed through a metal‐carbene‐induced zwitterionic intermediate which undergoes electrophilic trapping. To the best of our knowledge, this is the first asymmetric example of metal carbene‐induced intermolecular functionalization of aryl C H bonds.     

A Novel Aluminum-Based Metal-Organic Framework with Uniform Micropores for Trace BTEX Adsorption

Metal-organic frameworks (MOFs) are potential porous adsorbents for benzene, toluene, ethylbenzene and xylene (BTEX). A novel MOF, using low toxic aluminum (Al) as the metal, named as ZJU-620(Al), with uniform micropore size of 8.37±0.73 Å and specific surface area of 1347 m² g⁻¹, was synthesized. It is constructed by one-dimensional rod-shaped AlO₆ clusters, formate ligands and 4,4′,4′′-(2,4,6-trimethylbenzene-1,3,5-triyl) tribenzoic ligands. ZJU-620(Al) exhibits excellent chemical-thermal stability and adsorption for trace BTEX, e.g., benzene adsorption of 3.80 mmol g⁻¹ at P/P₀=0.01 and 298 K, which is the largest one reported. Using Grand Canonical Monte Carlo simulations and Single-crystal X-ray diffraction analyses, it was observed that the excellent adsorption could be attributed to the high affinity of BTEX molecules in ZJU-620(Al) micropores because the kinetic diameters of BTEX are close up to the pore size of ZJU-620(Al).     

A Sensitivity Result for Quadratic Second-Order Cone Programming and its Application

Applications of Mathematics - In this paper, we present a sensitivity result for quadratic second-order cone programming under the weak form of second-order sufficient condition. Based on this...     

Establishment of an LC-MS/MS Method for the Determination of 45 Pesticide Residues in Fruits and Vegetables from Fujian,China

Pesticide residues in food have become an important factor seriously threatening human health. Therefore, this study was conducted to determine the pesticide residues in fruits and vegetables commonly found in Fujian, China, with the aim of constructing a simple and rapid method for pesticide residue monitoring. We collected 5607 samples from local markets and analyzed them for the presence of 45 pesticide residues. A fast, easy, inexpensive, effective, robust, and safe (QuEChERS) multi-residue extraction method followed by liquid chromatography equipped with triple-quadrupole mass spectrometry (LC-MS/MS) was successfully established. This 12-min-long analytical method detects and quantifies pesticide residues with acceptable validation performance parameters in terms of sensitivity, selectivity, linearity, the limit of quantification, accuracy, and precision. The linear range of the calibration curves ranged from 5 to 200 mg/L, the limits of detection for all pesticides ranged from 0.02 to 1.90 μg/kg, and the limits of quantification for the pesticides were 10 μg/kg. The recovery rates for the three levels of fortification ranged from 72.0% to 118.0%, with precision values (expressed as RSD%) less than 20% for all of the investigated analytes. The results showed that 726 (12.95%) samples were contaminated with pesticide residues, 94 (1.68%) samples exceeded the maximum residue limit (MRL) of the national standard (GB 2763-2021, China), 632 (11.23%) samples were contaminated with residues below the MRL, and 4881 (87.05%) samples were pesticide residue-free. In addition, the highest number of multiple pesticide residues was observed in bananas and peppers, which were contaminated with acetamiprid, imidacloprid, pyraclostrobin, and thiacloprid.     

Diastereoselectivity switch in cooperatively catalyzed three-component reactions of an aryldiazoacetate, an alcohol, and a β,γ-unsaturated α-keto ester

A highly switchable,diastereoselectivity-controlled, three-component reaction of aryldiazoacetate, alcohol,and β,γ-unsaturated α-keto esters has been achieved through a dual-metal cooperative catalysis strategy.