K/LiCoO2的制备及其同时催化去除碳烟和NOx的性能研究

采用溶液燃烧法和浸渍法制备了铜铁矿结构的钴酸锂(LiCoO2)及其负载K的系列催化剂样品,并通过XRD、NOx-TPD、H2-TPR、程序升温反应等对其进行了结构表征与性能评价.结果表明LiCoO2是一种能有效同时去除碳烟(PM)和NOx的催化剂;K负载可提高其催化活性,其中10%K/LiCoO2具有最低的PM起燃温度(246℃)和最大NOx→N2转化率(35.9%);催化剂表面生成的O2-/O-活性氧物种以及较强的NOx吸附存储能力可能是K/LiCoO2催化活性提高的原因.     

湿式催化氧化处理含高浓度甲醛的草甘膦废水

草甘膦结晶母液经蒸发或纳滤浓缩回收后,产生大量含有高浓度甲醛的废水,常规的废水处理方法难以达到回用或排放要求.以过量溶液浸渍法制备的Pt-Bi-CeO2/AC为催化剂,采用湿式催化氧化法处理2.5%的HCHO溶液,HCHO去除率高达99.9%以上,COD去除率达到96.6%.采用Pt-Bi-CeO2/AC催化剂对含低浓度草甘膦(PMG,50 mg/L)的生产废水直接进行湿式催化氧化处理,催化剂使用23次后,HCHO去除率稳定在85%左右,COD去除率稳定在87%左右,催化剂具有良好的稳定性.湿式催化氧化处理后的废水可直接回用于PMG生产.采用固定床湿式催化氧化装置处理HCHO溶液以及PMG生产废水,处理效果也非常理想,连续使用720 h,催化剂的稳定性能良好.通过XRD、N2吸附-脱附、HRTEM、ICP-OES和XPS等分析手段对催化剂进行了系统表征.     

Ni-La/CexZr1-xO2对甲烷部分氧化/CH4-CO2重整耦合制合成气的催化剂制备及反应性能

通过共沉淀法制备铈锆固溶体作为载体,采用等体积、分步浸渍的方法制备了一系列10% Ni-3% La/CexZr1-xO2（X=0、0.16、0.5、0.75、1）催化剂,并将其应用到甲烷部分氧化和甲烷二氧化碳重整耦合制合成气的反应中。对不同Ce/Zr比的催化剂性能展开研究,采用XRD、H2-TPR、SEM手段对载体及催化剂进行了表征。结果表明,铈锆固溶体的形成不仅提高了催化剂表面活性组分的分散度,使催化剂表面NiO晶粒尺寸从26.5 nm减到13.7 nm;而且能够加强活性组分与载体之间的相互作用,提高催化剂的热稳定性能;随着Ce/Zr比的增加,催化剂的转化率、选择性及稳定性随之增强,其关系为：Ni-La/Ce0.75Zr0.25O2 > Ni-La/Ce0.5Zr0.5O2 > Ni-La/Ce0.16Zr0.84O2。     

Surface and Catalytic Properties of K/V Catalysts Coating on Porous Al2O3 Substrate

The morphology of different ratio K/V catalysts supported on porous α‐alumina substrate was investigated by atomic force microscopy (AFM). Changes in the particle size distribution, pore size distribution were analyzed respectively using AFM software. In addition, their catalytic activities and compositions for carbon oxidation were studied by x‐ray diffraction (XRD), differential scanning calorimetry (DSC), and temperature‐programmed reactions (TPR). As a result, with the increase of K concentration, the mean particle size gradually increased and the mean pore size decreased. According to the catalytic activity studies, the catalytic activity of the KVO₃ and K₃V₅O₁₄ phases are more effective than KCl.     

一种生物柴油代用品在HZSM-5分子筛催化剂上的催化热解

为了深入了解生物柴油在ZSM-5沸石上的催化反应机理,在常压的流动反应器中进行了生物柴油代用品丁酸甲酯在氢型ZSM-5(HZSM-5)催化剂上的热解和催化热解. 热解产物使用气相色谱-质谱法定性和定量测量. 动力学模型和实验表明,气相中氢提取反应是热解过程中丁酸甲酯分解的主要途径,但在HZSM-5上,丁酸甲酯则主要通过解离生成烯酮和甲醇消耗;与无催化反应相比,丁酸甲酯在HZSM-5上的初始分解温度降低了约300 K. 并且通过Arrhenius方程获得了在催化热解和均相热解条件下丁酸甲酯消耗的表观活化能. 明显降低的表观活化能证实了HZSM-5对丁酸甲酯热解的催化性能. 此外催化剂的活化温度对HZSM-5的某些催化性能具有一定的影响. 该研究对进一步的实际生物柴油燃料的催化燃烧具有一定的指导意义.     

基于低场核磁共振的抚顺油页岩孔隙连通性演化研究

油页岩原位注热开采过程中，储层内部孔隙结构的连通性直接影响载热介质的流动行为和传热效率，同时对油气产物的扩散和流动行为起控制作用.本文利用低场核磁共振（LF NMR）技术，考察了不同热解终温（23~650℃）处理时，饱和水及束缚水状态下抚顺油页岩的T₂谱，分析了可动流体T₂截止值、束缚流体孔隙度、饱和流体孔隙度、渗透率等NMR孔隙参数，定量研究了随热解终温升高，抚顺油页岩孔隙结构的连通性演化规律.研究结果表明热解终温对抚顺油页岩孔隙连通性及渗透率的变化起控制作用，且可动流体孔隙度对总孔隙度的增加起主要促进作用，这说明热解终温升高加大了渗透率及油气产物的输运能力.本文为深入认识油页岩原位热解过程中孔隙结构的演化提供了依据.     

Sensing and photocatalytic properties of nanosized Cu(I)CN organotin supramolecular coordination polymer based on pyrazine

Orange prismatic crystals of the supramolecular coordination polymer (SCP) _∞³[Cu(CN)₂(Me₃Sn)(Pyz)], SCP 1 , were synthesized using a self‐assembly method under ambient conditions. Nanosized 1 was obtained using the same molar ratio in water by ultrasonic irradiation. SCP 1 was characterized using single‐crystal X‐ray diffraction, elemental analysis, thermal analysis and Fourier transform infrared spectroscopy. SCP 1 and its nanosized 1 particles were also examined using powder X‐ay diffraction and scanning electron microscopy. The luminescence emission of SCP 1 was studied as well as its use as a sensor for the detection of common organic solvents and metal ions. Also, the catalytic activities of nanosized 1 towards various organic dyes were investigated under ambient conditions, UV irradiation and ultrasonic irradiation. Nanosized 1 as a heterogeneous nanoparticle catalyst exhibits high catalytic activity for the degradation of eosin‐Y and acid blue dyes. The mechanism of degradation investigated using various scavenger techniques is proposed and discussed. The catalytic oxidation process is mainly caused by ?OH radicals.     

Synthetic Studies on Spirolides A and B: Formation of the Upper Carbon Framework Based on a Lewis Acid Template-Catalyzed Diels–Alder Reaction

The upper fragment of spirolides A and B, which are marine phycotoxins that exhibit strong antagonistic activities on nicotinic acetylcholine receptors, was constructed. The functionalized cyclohexene in spirolides was stereoselectively synthesized from the bicyclic lactone, which could be readily accessed by the Lewis acid template-catalyzed asymmetric Diels–Alder reaction of the pentadienol and methyl acrylate.     

Design of pincer complexes based on (methylsulfanyl)acetic/propionic acid amides with ancillary S‐ and N‐donors as potential catalysts and cytotoxic agents

Pincer complexes featuring readily tunable tridentate ligand frameworks comprise one of the most actively studied classes of organometallic and metal–organic compounds and find extensive use in catalysis, organic synthesis, materials science, and other fields of chemistry and allied disciplines. Currently growing attention is devoted to non‐classical ligand scaffolds, such as functionalized carboxamides, which offer multiple options for directed structural modifications. In this study, the reactions of (methylsulfanyl)acetyl and propanoyl chlorides with 2‐(aminomethyl)pyridine, 2‐(2‐aminoethyl)pyridine, 8‐aminoquinoline and 2‐(diphenylthiophosphoryl)aniline afford a series of new pincer‐type ligands based on functionalized carboxamides. The ligands obtained readily undergo direct cyclopalladation under the action of PdCl₂(NCPh)₂ in dichloromethane at room temperature, resulting in Pd(II) pincer complexes with N,N,S‐ and S,N,S‐donor sets. Importantly, some of the cyclopalladated derivatives can also be produced efficiently under solvent‐free conditions according to the approach recently developed by our group. The complexes obtained have been tested for cytotoxicity against several human cancer cell lines and catalytic activity in the model Suzuki reaction. The results have been compared to those for the related Pd(II) pincer complexes to define the main structure–activity relationships and to outline the most promising structures for further investigations.