Cu-Fe-PILC催化C3H6选择性还原NO的性能

采用羟基铁离子柱撑Na-Mont制备出1.0Fe-PILC,通过超声浸渍法合成不同铜负载量的nCu-Fe-PILC,并测试了其在富氧条件下催化C_3H_6选择性催化还原NO的性能。通过N_2吸附脱附、XRD、UV-Vis、H_2-TPR、Py-FTIR等技术手段表征催化剂的微观结构和物化性质,进一步解释其催化反应机理。结果表明,Cu的引入提高了1.0Fe-PILC的中低温活性和抗水硫能力。其中9Cu-Fe-PILC在300℃时NO转化率可达69.8%以上,400℃后NO转化率保持在99%以上且水硫影响较小。XRD、N_2吸附脱附结果表明,催化剂的SCR活性与所负载的活性组分和催化剂的吸附能力有关。UV-Vis结果表明,9Cu-Fe-PILC具有较强的中低温活性,与其含有较多的游离态Cu~(2+)有关。H_2-TPR结果表明,与1.0Fe-PILC相比,经Cu修饰的nCu-Fe-PILC获得了中低温还原能力。Py-FTIR结果表明,nCu-Fe-PILC表面同时含有Lewis酸和Br?nsted酸,Lewis酸是影响催化剂SCR活性的主要因素。     

An unusual substitution reaction of an aromatic sulfonic group based on 3-carbonyl-4-phenolsulfonic acid

An unusual substitution reaction of an aromatic sulfonic group based on 3-carbonyl-4-phenolsulfonic acid was discovered in a diazo-coupling process.The reaction occurred under mild reaction conditions (pH 8.0-9.0.0-5 C,solvent:water) within a short reaction time(1h).A plausible substitution reaction mechanism by phenol-ketone resonance was proposed.     

基于密度泛函理论的CO2吸附微观机理比较研究

为探究吸附法捕获CO₂过程中的微观机理和吸附剂材料间的作用关系,基于密度泛函理论方法,综合比较了典型吸附剂包括煤基官能团、Fe、限域离子液体、Na₂CO₃、SrTiO₃与CO₂的吸附过程和差异性.根据不同计算策略,着重分析比较了吸附能、结构优化参数、吸附构型以及原子分布等参数.结果表明,化学吸附中CO₂分子与吸附面呈平行关系时通常吸附能最大;在一种材料的同类型官能团中,吸附能大小与氧原子的数量呈正相关关系;吸附过程中C-O键的伸长活化会生成一种重要的中间产物CO₂^-.提出在探寻CO₂吸附材料时可以在含氧原子较多的官能团、活性金属表面等方面进一步探究.最后对基于密度泛函理论的CO₂的吸附机理的进一步研究方向进行了展望.     

Rare-earth-catalyzed C-H bond addition of pyridines to olefins

An efficient and general protocol for the ortho-alkylation of pyridines via C-H addition to olefins has been developed, using cationic half-sandwich rare-earth catalysts, which provides an atom-economical method for the synthesis of alkylated pyridine derivatives. A wide range of pyridine and olefin substrates including α-olefins, styrenes, and conjugated dienes are compatible with the catalysts.     

载气流速对高场不对称波形离子迁移谱的影响

载气流速是影响高场不对称波形离子迁移谱(FAIMS)的重要参数.以自制的高场不对称波形离子迁移谱仪为实验平台,在射频电场幅值3 kV/cm,频率500 kHz,占空比0.36的条件下,研究了载气流速对苯离子迁移谱谱峰强度和半峰宽的影响.实验结果表明: 载气流速为3.7 L/min时,苯样品的谱峰强度最大,仪器的灵敏度最高.随着载气流速的增加,谱峰半峰宽变宽,仪器的分辨率下降.载气流速为3 .0～3.7 L/min时仪器综合性能最佳.此结果对于控制迁移谱仪载气流速有重要的参考意义.     

Xe离子束辐照硼硅酸盐玻璃和石英玻璃效应对比研究

玻璃固化体作为放射性废物地质处置的第一道安全屏障,它的耐辐照性能研究至关重要.玻璃固化体主要网络结构硅氧四面体与石英玻璃的硅氧四面体是一致的,所以这里用石英玻璃代替玻璃固化体作为研究对象.本文采用Xe离子在相同条件下辐照石英玻璃和硼硅酸盐玻璃.利用纳米压痕技术和椭圆偏振仪表征了辐照前后样品的硬度、模量以及折射率的变化情况.结果表明:硼硅酸盐玻璃和石英玻璃的硬度均随着辐照剂量的增大而减小,硼硅酸盐玻璃的模量随着辐照剂量的增大而减小;石英玻璃的模量随着辐照剂量的增大而增大.模量的变化可能和密度的变化有关,这点与折射率的结果相符.     

Neutral Boryl Radicals in Mixed-Valent B(III)Br-B(II) Adducts

The general strategies to stabilize a boryl radical involve single electron delocalization by π-system and the steric hinderance from bulky groups. Herein, a new class of boryl radicals is reported, with intramolecular mixed-valent B^(III)Br-B^(II) adducts ligated by a cyclic (alkyl)(amino)carbene (CAAC). The radicals feature a large spin density on the boron center, which is ascertained by EPR spectroscopy and DFT calculations. Structural and computational analyses revealed that the stability of radical species was assisted by the CAAC ligand and a weak but significant B(III)Br-B(II) interaction, suggesting a cooperative avenue for stabilization of boryl radicals. Two-electron reduction of these new boryl radicals provides C−H insertion products via a borylene intermediate.     

Hydrothermal Synthesis and Crystal Structure of a Manganese（Ⅱ） Coordination Polymer with 1,1＇-Biphenyl-2,2＇,6,6＇-tetracarboxyl Acid and 2,2＇：6,2＇-Terpyridine Ligands

The title compound {[Mn（H2BPTC）（tpy）（H2O）]·（H2O）3}, （1, H4BPTC = 1,1＇- biphenyl-2,2＇,6,6＇-tetracarboxylic acid, tby = 2,2＇：6,2＇-terpyridine） has been synthesized by the hydrothermal reaction, and its s...     

Synthesis and Crystal Structure of Dissymmetrical Double Schiff Base Cu（Ⅱ） Homobinuclear and Cu（Ⅱ）-Mg（Ⅱ）-Cu（Ⅱ） Heterotrinuclear Complexes

Homobinuclear complex （HCuL）2 （1） （H3L： N-3-carboxylsalicylidene-N＇-salicylaldehyde-1,2-diaminoethane） was obtained from self-organization of the reported complex HCuL, and its crystal structure was determined through X-ray diffraction at room temperature. The crystal of complex 1 belongs to monolinic system, the space group Cc, a=2.5326（5） nm, b=0.88861（18） nm, c=1.3738（3） nm, β=96.95（3）°, Z=4, R1=0.0520, wR2=0.1185. （HCuL）2 is a dimeric molecule and has extended phenolic oxygen-bridged structure. In addition, using mononuclear complex HCuL as building blocks, Cu（Ⅱ）-Mg（Ⅱ）-Cu（Ⅱ） heterotrinuclear complex 2 was synthesized, and its crystal structure also has been determined by X-ray analysis. The crystal of complex 2 is of monoclinic system, space group Pc, a=1.1816（2） nm, b=1.5599（3） nm, c=1.9642 （4） nm, β=98.22°, Z=2, R1=0.0701, wR2=0.1498. Each dissymmetricai cell unit of complex 2 contains two heterotrinucler neutral molecules： {[CuL（H2O）]Mg[CuL（CH3OH）]} and {[CuL]Mg[CuL（H2O）]}.