镁掺杂氧化铈整体式催化剂催化CO2和CH3OH直接合成碳酸二甲酯

采用共沉淀法成功地合成了不同Mg掺杂量的Ce_1-xMg_xO₂(x=0.05、0.10、0.15、0.20)固溶体催化材料,并运用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附测试、拉曼光谱、X射线光电子能谱(XPS)、CO₂程序升温脱附(CO₂-TPD)等技术对这些材料进行了表征。结果发现,通过调控CeO₂晶格中Mg的含量,可以调控所制备的Ce_1-xMg_xO₂催化材料的粒径、比表面积、表面缺陷等。其中Ce_0.90Mg_0.10O₂展现了最佳的表面性质,具有最小的平均粒径(约5.8 nm),最大的比表面积(约136 m2·g^-1)以及最高的表面氧含量(31.98%)。将Ce_1-xMg_xO₂催化材料涂覆在堇青石蜂窝陶瓷上制成整体催化剂,考察其对CO₂和CH₃OH直接合成碳酸二甲酯的催化性能。在140℃、2.4 MPa、反应2 h的条件下,Ce_0.90Mg_0.10O₂整体催化剂上碳酸二甲酯的收率高达20.21%,催化效果明显优于CeO₂和其余的Ce_1-xMg_xO₂(x=0.05、0.15、0.20)催化材料。     

铁基分子筛活性位点的制备控制及对NH3-SCR活性的影响

采用离子交换法,通过不同制备条件制备Fe-beta分子筛,并探讨不同制备条件对催化剂活性位点和NH3-SCR活性的影响。通过UV-Vis分析,将不同位置的吸收峰归属于不同的铁活性位点,300nm以下的高能谱区可以归属于孤立的Fe3+位点,300nm-400nm间归属于低聚的FexOy簇,而400nm以上为Fe2O3大颗粒聚合物。对比不同催化剂的SCR活性发现,孤立的Fe3+和低聚态的Fe3+是主要的活性位点,这两种物种的所占比例高低直接影响了催化剂的活性。而大尺度的Fe2O3为非活性位点,因尽量控制并降低其所占比例。另外低聚态的Fe3+所占比例越高,N2O的生成量越高,N2的选择性越差。因此,在制备过程中,除了控制大尺度的Fe2O3的含量,同时要尽量降低低聚态的Fe3+的含量,以增加N2的选择性。采用离子交换法制备Fe-beta催化剂,pH、交换温度、前驱体种类、硅铝比、煅烧条件等制备条件会对Fe-beta的活性位点造成影响,从而导致活性差异。根据实际应用需求,调控制备条件,可有效控制活性物种的分布,制备具有高效NH3-SCR活性的铁基分子筛催化剂。     

丝网印刷电极及其在重金属快速检测中的应用

利用简单、快速、高灵敏的方法对食品中的重金属进行检测具有重要意义。丝网印刷电极（SPE）因具有小巧便携、样品用量少、成本低等优点,在电化学快速分析领域具有明显优势,可实现食品中重金属等污染物质的快速现场分析。该文主要介绍了丝网印刷电极的概念、制作工艺、制备材料和修饰材料,综述了丝网印刷电极在重金属快速检测方面的应用进展,并讨论了其目前形势及未来发展趋势。     

表面活性剂修饰ZnIn2S4光催化甲苯选择性氧化

采用溶剂热合成法,借助十六烷基三甲基溴化铵（CTAB）和十八烷基三甲基溴化铵 （STAB）的修饰合成了富含硫缺陷的ZnIn2S4-CTAB和ZnIn2S4-STAB光催化剂. 通过透射电镜、X射线衍射、紫外可见漫反射光谱、电子顺磁共振和光电化学性能测试对所有样品进行了表征,并通过光催化甲苯氧化反应测试样品的催化活性. 活性结果表明ZnIn2S4-CTAB和ZnIn2S4-STAB上甲苯转化速率分别达到795 μmol gcat-1 h-1和1053 μmol gcat-1 h-1,是未修饰ZnIn2S4-Blank催化剂的4倍和5倍,同时目标产物苯甲醛选择性均大于92%. 机理研究发现,表面活性剂修饰后的ZnIn2S4-CTAB和ZnIn2S4-STAB较ZnIn2S4-Blank,具有更高浓度的硫缺陷. 硫缺陷通过捕获电子促进了光生载流子的分离与利用,显著提高了ZnIn2S4-CTAB和ZnIn2S4-STAB的光催化甲苯选择性氧化制苯甲醛活性.     

N-Doped Carbon Nanofibers Encapsulating CoO@Co9S8 Nanoparticles: Preparation from S-Rich Co32 Coordination Cluster Precursors by Electrospinning and Application for Superior Li-ion Storage

Thiacalixarene-supported Co₃₂nanoclusters encapsulated in polyacrylonitrile nanofibers(Co₃₂@PAN-NFs) by electrospinning have been utilized as precursors to fabricate N-doped CoO@Co₉S₈ carbon nanofibers(CoO@Co₉S₈@CNFs) for superior Li-ion storage. The S-rich Co₃₂ clusters capped by organic sheets afforded the well dispersed cobalt oxide/sulfide nanoparticles embedded in carbon nanofiber composites by direct calcination. The N-doped CoO@Co₉S₈@CNFs nanocomposites have been utilized as anode materials for lithium ion battery with the reversible capabilities being of 1051.8, 967.6, 894.7, 782.7, 669.5 and 525.4 mA·h/g at 0.1, 0.2, 0.5, 1, 2 and 3 A/g, respectively. The CoO@Co₉S₈@CNFs also showed a relatively high stable capacity of 551.7 mA·h/g at the current density of 1 A/g after 200 cycles of rate experiments. The as-obtained N-doped CoO@Co₉S₈@CNFs nanocomposites exhibited superior reversible capacity, rate performance, Coulomb efficiency(74.5% vs. 63.9%) and cyclic stability comparing with the CoO@Co₉S₈@C derived from simple annealing of Co₃₂ templates.     

Pore Engineering for Covalent Organic Framework Membranes

Membrane technology is of particular significance for the sustainable development of society owing to its potential capacity to tackle the energy shortage and environmental pollution. Membrane materials are the core part of membrane technology. Researchers have always been pursuing predictable structures of advanced membrane materials, which provides a possibility to fully unlock the potential of membranes. Covalent organic frameworks(COFs), with the advantage of controllable pore microenvironment, are considered to be promising candidates to achieve this design concept. The customizable function of COF membranes through pore engineering does well in the enhancement of selective permeability performance, which offers COF membranes with great application potentials in separation and transportation fields. In this context, COF-based membranes have been developed rapidly in recent years. Herein, we present a brief overview on the strategies developed for pore engineering of COF membranes in recent years, including skeleton engineering, pore surface engineering, host-guest chemistry and membrane fabrication. Moreover, the features of transmission or separation of molecules/ions based on COF membranes and corresponding applications are also introduced. In the last part, the challenges and prospects of the development of COF membranes are discussed.     

Rational Design of a Near-infrared Fluorescent Material with High Solid-state Efficiency,Aggregation-induced Emission and Live Cell Imaging Property

Near-infrared(NIR) fluorescent materials with high photoluminescent quantum yields(PLQYs) have wide application prospects. Therefore, we design and synthesize a D-A type NIR organic molecule, TPATHCNE, in which triphenylamine and thiophene are utilized as the donors and fumaronitrile is applied as the acceptor. We systematically investigate its molecular structure and photophysical property. TPATHCNE shows high T_gof 110℃ and T_d of 385℃ and displays an aggregation-induced emission(AIE) property. A narrow optical bandgap of 1.65 eV is obtained. The non-doped film of TPATHCNE exhibits a high PLQY of 40.3% with an emission peak at 732 nm, which is among the best values of NIR emitters. When TPATHCNE is applied in organic light-emitting diode(OLED), the electroluminescent peak is located at 716 nm with a maximum external quantum efficiency of 0.83%. With the potential in cell imaging, the polystyrene maleic anhydride(PMSA) modified TPATHCNE nanoparticles(NPs) emit strong fluorescence when labeling HeLa cancer cells, suggesting that TPATHCNE can be used as a fluorescent carrier for specific staining or drug delivery for cellular imaging. TPATHCNE NPs fabricated by bovine serum protein(BSA) are cultivated with mononuclear yeast cells, and the intense intracellular red fluorescence indicates that it can be adopted as a specific stain for imaging.     

钯催化Csp-Csp3偶联反应的13C NMR定量研究

利用NOE（Nuclear Overhauser Effect）增强的¹³C NMR方法对钯催化C_sp-C_sp3偶联反应过程进行实时、定量监测. 通过制作浓度曲线的方法定量分析了反应过程中各组分的浓度变化. 实验表明,同一物质各个共振峰的NOE增强倍数基本不变. 结果证实了几个主要反应物和产物的含量变化之间具有相关性,提示这些物质同属一个反应过程,为早期提出的反应机理（Zhao Y S, et al. J Am Chem Soc, 2006, 128: 15 048-15 049）提供了实验证据. 说明¹³C NMR能准确地提供反应体系中各物质的浓度变化信息,是化学反应机理的有效研究手段.     

泡沫塑料富集-火焰原子吸收光谱法测定金矿石中金

采用聚氨酯泡塑富集硫脲洗脱-火焰原子吸收光谱法测定金矿石中金。对样品称样量、硫脲洗脱时间、磷酸三丁酯的吸附效果和铁元素的干扰等工作条件进行了优化,解决了泡沫塑料吸附效率低和铁元素的干扰等技术性难题,提高了分析结果的精密度和准确度,弥补了传统的泡沫塑料富集-火焰原子吸收光谱法测定金矿石中金量的不足,方法检出限为0.06 μg/g,测定范围为 0.2 μg/g～100 μg/g,测定结果与标准值符合性较好,无显著性差异,精密度(RSD, n = 9) 小于2%。方法具有快速、简便、实用等优点,分析误差满足常规化学分析法的要求,能满足金矿石中金量的快速、准确测定。     

电感耦合等离子体原子发射光谱（ICP-AES）法测定高镍铜液体样品中金、钯、铂

为实现中控液体物料中金、钯、铂元素的精准定量分析,为工艺生产定向富集和高效提取提供数据支持,本文建立了ICP—AES法测定中控冶炼系统中高镍铜液体样品中金、铂和钯3种元素含量的测定方法。确定了试液用碲共沉淀,贵金属进入滤渣,经火试金分离富集得到贵金属合粒,合粒经王水溶解后,于王水介质中在电感耦合等离子光谱仪上同时测定金钯铂的量。该方法金、铂、钯的测定范围为 0.014mg/L～5mg/L,回收率为92.2%～104.4%, RSD为3.21%～10.58%,方法满足高镍、铜液体样品中金、钯、铂元素的测定。