Gaseous nitryl azide N4O2: A joint theoretical and experimental study

Gaseous nitryl azide N₄O₂ is generated by the heterogeneous reaction of gaseous ClNO₂ with freshly prepared AgN₃ at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N₄O₂ is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(π_{nb(N4–N5–N6)})}⁻¹. An apparent vibrational spacing of 1600 ± 60 cm⁻¹ (ν_asO1N2O3) on the second band at 12.52 eV (π_{nb(O1–N2–O3)}) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable.     

Using three major criteria to evaluate aromaticity of five-member C-containing rings and their Si-, N-, and P-substituted aromatic heterocyclics

In this paper, we used bond-length equalization, aromatic stabilization energies (ASE) and nucleus-independent chemical shifts (NICS), calculated with (density functional theory) B3LYP levels at the 6-311+G^** basis set, to evaluate the aromaticity of a set of 38 five-member planar π-electron aromatic systems: sila-, aza- and phospha- derivatives and their parent systems. The result revealed statistically significant correlations among the above three criteria, and the order of aromaticity of the whole set was: Aza- derivatives rings > Phospha- derivatives rings > Sila- derivatives rings > Carbon-containing rings; NICS(0.6) and NICS(0.8) had the same results in evaluating the order of aromaticity in our case.     

分子内环化对聚乙烯醇交联体系的影响

以聚乙烯醇(PVA)-戊二醛(GA)体系作为研究对象, 系统地研究了分子内环化对凝胶体系的影响, 为水凝胶体系的网络结构评价奠定了一定的实验基础.     

血清微量元素与儿童少年身高生长的相关研究

报道了6-18岁在校学生身高生长突增的情况以及身高突增期前后血清中Ca、Mg、Zn、Fe、Cu、Mn、Se、Pb8种元素含量的变化。结果表明，女生身高生长突增开始、达到高峰及突增结束年龄均早于男生约2年。在身高生长的三个阶段，血清Ga、Mn、Cu、Se、Pb含量都有显著或极显著差异。血清Ca在身高突增期以后水平较低，血清Mn在身高突增期以前水平较低，血清Cu在身高突增期以前水平较高，血清Se、Pb则呈渐减趋势。而两性间除血清Cu女生高于男生外，其它各元素均无显著性羌异。     

三唑类硫醚及二硫醚化合物的合成

以2-苯基-1，2，3-三唑-4-甲酰肼为原料，合成了6个新的含连三唑和均三唑的硫醚类化合物，并经IR、^1HNMR、MS和元素分析进行了结构表征。     

用EXAFS研究NiO在γ-Al2O3表面上的分散

本文使用EXAFS方法研究NiO在γ-Al_2O_3的表面上的分散情况。文章讨论了Ni含量为7%、13%、18%、26%、35%的NiO/γ-Al_2O_3体系的径向结构函数图以及Ni含量为13%、26%的NiO/α-Al_2O_3样品的径向结构函数图,认为NiO能在γ-Al_2O_3表面上成单层分散。分散后的Ni-O距离接近NiO晶体的Ni-O距离,表明Ni离子和γ-Al_2O_3表面上的氧有很强的相互作用。     

Modification of Cr/SiO2 for the dehydrogenation of propane to propylene in carbon dioxide

Summary Dehydrogenation of propane to propylene in carbon dioxide was investigated over promoted Cr/SiO2. The results showed that the catalysts were effective for the reaction and CO2 in the feed promoted the catalytic activity. XRD, TPR and microcalorimetric adsorption techniques were used to study the structure and surface acidity of the catalysts. It was found that the surface acidity decreased with the increase of K in the Cr/SiO2 and led to the increase of selectivity toward propylene. A propane conversion of 31% with 91% selectivity to propylene over the 5%Cr-0.4%K/SiO2 catalyst was observed at 923 K with CO2 /C3H8 molar ratio of 3.6.     

Mg/Zn/Al类水滑石的热分解和水化性能研究

采用共沉淀法制备了Mg2Al1、Zn2Al1和Mg1Zn1Al1LDHs,利用XRD和SEM表征手段,对它们的热分解及焙烧物在Na2CO3溶液中恢复层状结构的能力进行了对比研究。结果表明,在400～700℃温度范围内,Zn2Al1LDH和Mg2Al1LDH的焙烧物中均出现氧化物相(ZnO和MgO)和尖晶石相(ZnAl2O4和MgAl2O4相);而Mg1Zn1Al1LDH的焙烧物中始终以ZnO相为主,仅在700℃时出现微弱的MgAl2O4相。三种焙烧物恢复层状结构的能力为:Mg1Zn1Al1LDO>Mg2Al1LDO>Zn2Al1LDO,其与焙烧物组成有关。原始LDHs和水化LDHs均呈片状。     

活性位高度暴露的钴/氮/碳电催化剂的构建及氧还原性能研究

金属/氮/碳催化剂（M/N/C，M=Fe、Co等）是最有发展前景的非贵金属电催化剂之一，其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳（g-C₃N₄）富含类吡啶氮和亚纳米孔腔结构，将g-C₃N₄包覆在高导电性碳纳米笼（hCNC）表面，进而利用表层g-C₃N₄的配位和限域作用锚定大量Co²⁺离子，获得的Co/g-C₃N₄/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性，其起始电位（0.97 V）与商业Pt/C催化剂相当，且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略.