自掺杂SnO2微球的水热合成及其可见光催化性能

本研究采用水热法,以柠檬酸为螯合剂,通过控制n(Sn⁴⁺)/n(Sn²⁺)的数值,合成了由具有丰富氧空位的SnO₂纳米晶体组装成的微球。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线光电子能谱(XPS)及UV-Vis漫反射光谱对SnO₂纳米微球进行表征分析,结果表明:在酸性水热条件和柠檬酸的螯合作用下,二氧化锡纳米晶体聚集形成微球;在Sn⁴⁺/Sn²⁺摩尔比例为3:7时,其微球尺寸最小,整体分散性较好;同时适量二价锡离子的掺杂使得该样品氧空位浓度达到最佳,氧空位的存在将使得样品光吸收范围拓展至可见光,因而该样品显示出较强的可见光催化效率,在8 min内完全降解甲基橙。     

中空介孔SiO2纳米球的制备、改性及其对Al3+荧光识别研究

中空介孔SiO2由于中空多孔的结构而常用作功能材料的基底.将中空介孔SiO2进行官能团修饰,并应用为荧光传感材料是中空介孔SiO2一个重要的研究领域.本论文采用聚丙烯酸(PAA)为中空模板,聚醚F127为造孔剂,正硅酸乙酯(TEOS)为硅源,氨水为催化剂在乙醇体系中制备了中空介孔SiO2纳米球.系统研究了搅拌速度和聚醚F127引入量对中空介孔SiO2纳米球形貌及比表面积的影响.通过透射电镜、N2-等温吸附脱附曲线等表征说明该合成方法具有很好的普适性,通过调节F127的引入可以实现对比表面积的有效控制.通过氨基化、席夫碱反应进行荧光修饰,进一步研究表明荧光修饰后的中空介孔SiO2纳米球在水溶液中能够实现对Al3+的有效检测,检测限为1.19×10 -7M.     

复合电极La-Ni-B的制备及电催化偏硼酸钠的性能

为进一步提高对偏硼酸钠电催化还原的效率,采用化学镀的方法,以铜片为基体,PdCl2乙醇胶体溶液为活化剂,乙醇为化学镀溶剂,制备了稀土复合电极La-Ni-B.并采用XRD、SEM、EDS方法对催化剂进行表征分析,结果表明稀土合金以纳米颗粒的形式附着在基体表面,所得合金膜是非晶态的.通过循环伏安法研究了复合电极La-Ni-B用于电解偏硼酸钠制备硼氢化钠的可行性.以硼氢化钠实际生产量为指标,探讨了直流、脉冲两种不同供电方式、脉冲电流频率、电解时间对电解行为的影响.结果表明稀土镧对电解偏硼酸钠有催化作用,以20 mL镀液制备的复合电极,在脉冲频率阳极时间T1=1 s,阴极时间T2=1 s时,最佳电解时间为4h.复合电极在重复使用3次的情况下,硼氢化钠产量降低15;,催化剂的重复使用性能良好.     

Development of an ultra-performance liquid chromatography-electrospray ionization-Orbitrap mass spectrometry method for determination of xanthopurpurin in rat plasma and its application to pharmacokinetic study

A rapid and sensitive method was developed and validated for the quantitative determination of xanthopurpurin (XPP) in rat plasma using ultra-performance liquid chromatography-electrospray ionization-Orbitrap mass spectrometry. XPP inhibits IgE production and prevents peanut-induced anaphylaxis. The XPP and emodin (internal standard) were determined in negative ion mode with m/z 239.0350 → 211.0400 and 269.0455 → 241.0507, respectively. The separation process was achieved using an ACQUITY UPLC HSS T₃ column with acetonitrile and 0.1% formic acid in water (85:15). The linear range was 0.5–100 ng/mL, and the correlation coefficient (r²) was > 0.993. The inter-day and intra-day precision was within an acceptable range of 15%. The extraction recovery and matrix effect were 78.9–87.2% and 94.3–98.5%, respectively. Under different conditions, the XPP was stable in the range of 5.6–10.6%. This method was successfully applied to study the pharmacokinetics of XPP with an oral dose of 10.0 mg/kg and intravenous dose of 2.0 mg/kg in rats. The absolute oral bioavailability of XPP was 4.6%.     

Enantioselective Total Synthesis of Pseudopteroxazole and Ileabethoxazole

Enantioselective total syntheses of pseudopteroxazole ( 1 ) and ileabethoxazole ( 2 ) are presented. The two original stereocenters were constructed in excellent enantioselectivity and good diastereoselectivity through Carreira's asymmetric dual catalytic allylation, which shows potential for accessing diastereoisomers at C2 and C3 of 1 and 2 . Cationic cyclizations of 13 and 24 demonstrated an effective pathway for the construction of the opposite configurations at C1 in 1 and 2 . Additionally, an approach for the introduction of methyl at C4 is a feasible solution for structural modifications at C4 in 1 and 2 .     

Co3+-Rich Na1.95CoP2O7 Phosphates as Efficient Bifunctional Catalysts for Oxygen Evolution and Reduction Reactions in Alkaline Solution

Implementing sustainable energy conversion and storage technologies is highly reliant on crucial oxygen electrocatalysis, such as the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). However, the pursuit of low cost, energetic efficient and robust bifunctional catalysts for OER and ORR remains a great challenge. Herein, the novel Na-ion-deficient Na_2−xCoP₂O₇ catalysts are proposed to efficiently electrocatalyze OER and ORR in alkaline solution. The engineering of Na-ion deficiency can tune the electronic structure of Co, and thus tailor the intrinsically electrocatalytic performance. Among the sodium cobalt phosphate catalysts, the Na_1.95CoP₂O₇ (NCPO5) catalyst exhibits the lowest ΔE (E_J10,OER−E_J−1,ORR) of only 0.86 V, which favorably outperforms most of the reported non-noble metal catalysts. Moreover, the Na-ion deficiency can stabilize the phase structure and morphology of NCPO5 during the OER and ORR processes. This study highlights the Na-ion deficient Na_2−xCoP₂O₇ as a promising class of low-cost, highly active and robust bifunctional catalysts for OER and ORR.     

Rational Construction of an Exceptionally Stable MOF Catalyst with Metal-Adeninate Vertices toward CO2 Cycloaddition under Mild and Cocatalyst-Free Conditions

CO₂ is considered as the primary greenhouse gas, resulting in a series of serious environmental problems that affect people's life and health. Carbon capture and sequestration has been implemented as one of the most appealing pathways to control and use CO₂. Here, we rationally integrate various functional sites within the confined nanospace of a microporous metal–organic framework (MOF) material, which is constructed by mixed-ligand strategy based on metal-adeninate vertices. It not only exhibits excellent stability but also can efficiently transform CO₂ and epoxides to cyclic carbonates under mild and cocatalyst-free conditions. Additionally, this catalyst shows extraordinary recyclability for the CO₂ cycloaddition reaction.     

Crystal structures of silicon-rich lithium silicides at high pressure

Silicon (Si) is one of the most essential elements, as it is indispensable for modern electronic technology. The standard Si structure at ambient conditions is the cubic diamond structure, and it has an indirect band gap, which prevents it from being considered as a next-generation platform for semiconductor technologies. Therefore, the search for new allotropes of silicon has attracted great attention. Herein, first principles swarm-intelligence structure searches coupled with density-functional theory were performed to explore the stable high-pressure phases of silicon-rich lithium containing compounds, LiSi_x ($x=4\text{–}8$). The LiSi₄ stoichiometry was predicted to be stable, and it was found to assume one of the following space groups, P4/mnc, Cmmm, and C2/m within the pressure range of 0 to 50 GPa. By removing the Li atoms from these compounds, three silicon allotropes were obtained that were metastable at ambient pressures. Our work illustrates how novel silicon allotropes can be predicted using the CALYPSO method.