Fe2O3/Al2O3氧载体用于甲烷化学链燃烧：负载量与制备方法的影响

以不同方法制备了系列Fe₂O₃/Al₂O₃氧载体,采用XRD、H₂-TPR、CH₄-TPR、O₂-TPD和BET等分析技术对氧载体进行了表征。研究了不同Fe₂O₃负载量氧载体的甲烷化学链燃烧性能,考察了不同制备方法对Fe₂O₃/Al₂O₃氧载体结构、反应性和产物选择性的影响。结果表明,Fe₂O₃负载量对氧载体活性及产物中CO₂选择性的影响较大,负载量较低时氧载体活性较低且引起甲烷部分氧化产物CO含量增加。制备方法亦对氧载体与甲烷的反应活性有所影响,整体上共沉淀法制备的质量分数60％Fe₂O₃/Al₂O₃氧载体具有较高的氧化活性和化学链循环稳定性。其在反应温度850℃、反应时间15 min、30次循环后甲烷转化率及产物中CO₂选择性均未见明显降低。     

Mechanistic Insights into Copper‐Catalyzed Sonogashira–Hagihara‐Type Cross‐Coupling Reactions: Sub‐Mol % Catalyst Loadings and Ligand Effects

An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp²)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations.     

2,2,2-三硝基乙基-N-硝基甲胺的热安全性

为评价2,2,2-三硝基乙基-N-硝基甲胺(TNMA)的热安全性, 得到计算TNMA热安全性参数用的基本数据, 用经验式估算了TNMA的比热容(C_p)和热导率(λ). 用键能贡献于生成热Q_f的加和法, 估算了TNMA的标准生成焓Δ_cH_m^θ(TNMA, s, 298.15 K). 用热力学公式计算了TNMA的标准燃烧焓ΔU_m^θ(TNMA, s, 298.15 K)和标准燃烧能Δ_cH_m^θ(TNMA, s, 298.15 K). 用Kamlet-Jacobs 公式估算了爆速、爆压和爆热. 用经验式估算了分解热(Q_d). 通过差示扫描量热(DSC)曲线和高灵敏度布鲁顿玻璃薄膜压力计测得的逸出气体标准体积(V_H)-时间(t)曲线, 得到了TNMA放热分解反应的动力学参数. 用上述基本数据得到了评价TNMA的热安全性参数: 自加速分解温度(T_SADT), 热爆炸临界温度(T_be0和T_bp0), 绝热至爆时间(t_TIad), 撞击感度50%落高(H₅₀), 热点起爆临界温度(T_cr), 被300 K环境包围的半厚和半径为1 m的无限大平板、无限长圆柱和球形TNMA的热感度概率密度函数S(T), 相应于S(T)-T关系曲线最大值的峰温(T_S(T)max), 安全度(SD), 临界热爆炸环境温度(T_acr)和热爆炸概率(P_TE). 结果表明: (1) TNMA有较好的热安全性和对热抵抗能力, 与环三亚甲基三硝胺(RDX)相比, TNMA易从热分解过渡到热爆炸; (2) 不同形状大药量TNMA 热安全性降低的次序为: 球>无限长圆柱>无限大平板; (3)TNMA有高的燃烧能、高的爆轰化学能(爆热)和接近环四亚甲基四硝胺(HMX)的爆炸性能, 其对冲击敏感, 冲击感度与季戊四醇四硝酸酯(PETN)和特屈尔接近, 可用作混合炸药主组分.     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

Loading characteristics and chemical stability of headgroup‐functionalized poly(ethylene glycol)‐lipid ligand tethers on polypropylene capillary‐channeled polymer fibers

Polypropylene capillary‐channeled polymer fibers have been modified by adsorption of headgroup‐functionalized poly(ethylene glycol)‐lipids to generate a species‐specific stationary phase. In order to study ligand binding characteristics, a fluorescein‐labeled poly(ethylene glycol)‐lipid was used as a model system. Breakthrough curves and frontal analysis were employed to characterize the surface loading characteristics across a range of lipid concentrations and mobile phase flow rates. Efficient mass transfer and fluid transport yield a linear adsorption isotherm up to the maximum loading concentration of 3 mg/mL, at a linear velocity of 57.1 mm/s. Under these conditions, the dynamic binding capacity was found to be 1.52 mg/g of fiber support. Variation of the linear velocity from 8.6 to 57.1 mm/s showed only small changes in breakthrough volume. The maximum capacity of 1.8 mg/g is found under conditions of a load velocity of 34.2 mm/s and a concentration of 3 mg/mL lipid. Exposure of the lipid modified fibers to several challenge solvents reveals a chemically robust system, with only 50% acetonitrile and hexanes able to disrupt the lipid adsorption. The straightforward capillary‐channeled polymer fiber surface modification with headgroup‐functionalized lipids provides both a diverse yet practically robust ligand tethering system.     

循环荷载作用下心墙掺砾土动应力应变孔压模型

动力荷载作用下,心墙掺砾土的累积塑性变形和孔隙水压力的发展对心墙防渗体的安全至关重要.基于Bouc-Wen光滑滞回模型,考虑滞回圈捏拢效应,结合非关联流动法则,建立本构模型,模拟循环过程中土体产生的累积塑性应变和增长的孔压.通过糯扎渡心墙掺砾土均压固结和偏压固结状态的循环三轴试验,研究其动应力应变关系及孔压响应.将模型曲线与试验曲线进行对比分析,验证模型描述掺砾土动应力应变关系的合理性和有效性.     

高分散还原态Pt基催化剂的制备及其NO氧化的催化性能

Pt⁰被认为是NO氧化的活性物种,而催化剂的制备方法对活性物种的含量起着决定性作用。本文采用非惰性气氛保护的改性醇还原-浸渍法(MARI)合成了高分散高Pt⁰含量的1% (w, 质量分数) Pt/SiO₂-Al₂O₃催化剂(MA-Pt/SA)。X射线粉末衍射(XRD)、CO-漫反射傅里叶变换红外吸收光谱(CO-DRIFTS)和透射电镜(TEM)表征证实在550 ℃焙烧3 h后催化剂的Pt颗粒仅有3.8 nm。同时,X射线光电子能谱(XPS)和H₂-程序升温还原(H₂-TPR)结果表明催化剂具有高Pt⁰含量(60.3%)。模拟柴油车尾气气氛进行活性测试,并与传统浸渍法制备的1% (w) Pt/SiO₂-Al₂O₃催化剂(C-Pt/SA)对比,结果显示MA-Pt/SA具有优异的催化氧化性能,其NO最大转化率高达74%,比C-Pt/SA的NO转化率高了23%。经670 ℃高温老化15 h后,老化的MA-Pt/SA的NO转化率仍然高达69%。此外NO + O₂共吸附原位漫反射傅里叶变换红外吸收光谱(in situ DRIFTS of NO + O₂ co-adsorption)表明高的Pt分散度和高Pt⁰含量能够促进中间物种桥式硝酸盐的生成及分解,进而导致了优异的NO氧化活性。最后,利用同样方法将Pt的负载量降低至0.5% (w)制备催化剂,NO转化率仍达64%。这种制备方法能够获得低贵金属高性能的Pt基催化剂。     

基于氮掺杂活性炭催化氧化合成氮甲基氧化吗啉的研究

以三聚氰胺为氮源,商用活性炭为研究对象,通过“浸渍吸附+高温热处理”的方式制得系列氮掺杂活性炭,并用于催化氧化合成氮甲基氧化吗啉（NMMO）。采用N₂吸附/脱附、Raman、XPS等对氮掺杂活性炭的孔结构和表面性质进行了表征。结果表明：随着三聚氰胺负载量的增大,氮掺杂活性炭的表面碱性含氮官能团含量增大,进而体现出更好的催化氧化合成NMMO活性。最佳催化剂（ACO850-20N）在催化剂加量为0.02 wt%,反应温度70 ℃和反应时间4 h的工艺条件下,氮甲基吗啉的转化率和NMMO收率可达99.76%和94.31%。      

物理化学教学中安全工程教育的融合与内化实例*

如何强化安全工程教育是化学化工类专业高等教育的一个重要课题。通过对蒸汽锅炉爆炸、火灾爆燃事故以及锈蚀危害等3个实例的详细讲述,指出在物理化学的教学中,若适时融入相关的安全工程教育,可以使学生深刻理解安全事故发生及防范所依赖的物理化学原理,从而起到安全意识的内化作用。教学中现代教育技术的引入可以增强这一效果。     

Robust nickel silicate catalysts with high Ni loading for CO2 methanation

CO₂ is the main component of greenhouse gases and also an important carbon source. The hydrogenation of CO₂ to methane using Ni-based catalysts can not only alleviate CO₂ emissions but also obtain useful fuels. However, Ni-based catalysts face one major problem of the sintering of Ni nanoparticles in the process of CO₂ methanation. Thus, this work has synthesized a series of efficient and robust nickel silicate catalysts (NiPS−X) with different nickel content derived from nickel phyllosilicate by the hydrothermal method. It was found that the Ni loading plays a critical role in the structure and catalytic performance of the NiPS−X catalysts. The catalytic performance gradually increases with the increase of Ni loading. In particular, the highly dispersed NiPS-1.6 catalyst with a high Ni loading of 34.3 wt% could obtain the CO₂ conversion greater than 80%, and the methane selectivity was close to 100% for 48 h at 330 °C and the GHSV of 40,000 mL g⁻¹ h⁻¹. The excellent catalytic property can be assigned to the high dispersion of Ni nanoparticles and the strong interaction between the active component and the carrier, which is derived from a unique layered silicate structure with lots of nickel phyllosilicate and a large number of Lewis acid sites.