Zirconium-based intermetallics as heterogeneous catalysts for the fischer-tropsch reaction: I. Zr-Ni-Co catalysts

Alloys of the general formula Zr₅₀Ni_xCO_50-x, where 0 ≦x≧ 50, have been prepared and used in the temperature range 300–400°C, in the pressure range 1–9 barg in a microtubular reactor for the reaction of hydrogen with carbon monoxide to give hydrocarbons. The alloys or intermetallic materials were prepared by argon arc melting, powdered by hydrogen decrepitation and characterised by means of optical microscopy (metallography), scanning electron microscopy with surface analysis and magnetic susceptibility measurements. The selectivity towards higher hydrocarbons increased with (i) increase in the total pressure and (ii) decrease in hydrogen content of the feed gases. The kinetics were found to be of the form: where m = 1.0 ± 0.2 and n = 0. The apparent energy of activation (E_a) lay in the range of 80–130 kJ mole^?1 and there appeared to be a compensation effect between E_a and the pre-exponential factor A. The turnover numbers for the reaction exhibited an activity maximum for alloys of composition around Zr₅₀Ni₄₀Co₂₀ and Zr₅₀Ni₃₀Co₂₀. Magnetic susceptibility measurements indicated that alloys changed their nature from moderately paramagnetic to strongly paramagnetic or even ferromagnetic after use and this is attributed to the conversion of zirconium to zirconium oxide during reaction with the attendant production of free 3d-transition metals. Derived catalysts prepared by air treatment of the hydrogen-decrepitated intermetallics behaved almost identically to the latter materials and gave similar magnetic susceptibility values to used hydrided materials.     

高温钎料PdCu-Ti在氧化铝陶瓷上的润湿性及界面反应

本文采用座滴法试验研究了合金系统ＰｄＣｕ－Ｔｉ在Ａｌ２Ｏ３上润湿性的变化规律，探讨了界面冶金及结合等行为，运用热力学理论对结果进行了分析，随Ｔｉ含量的增加及Ｐｄ含量的减少润湿角逐渐降低，Ｔｉ的加入使界面发生了一个双重变化；液相侧富氧，钛吸收层的生成及随后的固相侧氧化钛的生成，只有界面上生成一氧化钛，才能有较好的润湿行为和较强的结合力。     

木质素单体模化物的热解与产物分析

采用苯酚、邻苯二酚、愈创木酚和紫丁香酚为木质素单体模化物,利用两段裂解反应器-在线气相色谱仪（GCs）进行热解实验和产物分析,采用多色谱柱对无机气体（IGs）、C₁~C₅烃（C₁~C₅ LHs）、非芳基含氧化合物、酚和芳烃进行定量分析,以确定羟基和甲氧基对木质素热解过程中开环反应及产物分布的影响. 结果显示：羟基和甲氧基可以提高模化物的转化率,且羟基和甲氧基的存在影响芳基开环反应、芳基取代反应和重排反应间的竞争关系,使热解产物分布存在明显差异. 4种模化物热解产物主要是芳环的开环反应产物,包括IGs（质量分数为27.29%~33.56%）和C₁~C₅烃（20.46%~39.51%）. 一氧化碳产率（23.82%~29.18%）随羟基数增加而升高,随甲氧基数增加而降低;二氧化碳产率（0.19%~9.61%）随甲氧基数增加而升高. 羟基和甲氧基的存在降低了C₁~C₅烃的质量选择性,促进了烷基苯、大分子化合物和焦炭的形成.     

Reaction process of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2

The decomposition reactions of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2 were studied by means of TG-DTA and XRD. The results show that the process of the minerals decomposed by CaO involves two steps. The first step occurs in the temperature range of 425-540 ℃, and the main reactions are bastnaesite decomposition, i.e. REOF reacts with CaO to produce RE2O3 and CaF2, and Ce2O3 is oxidized to CeO2. During this step, CaCO3 is formed at about 500 ℃. The second step takes place in the temperature range of 610-700 ℃, and the reactions are monazite decomposition into RE2O3, Ca5F（PO4）3 and Ca3（PO4）2 by CaO and CaF2. In this process, the decomposition ability is improved because CaO from CaCO3 decomposing has high chemical activity. In calcining process, the new formed Ca5F（PO4）3 restrains fluorine that can escape in form of gaseous compound. The decomposition ratio of the mixed rare earth minerals reaches 90.8% at 700 ℃.     

N、S共掺杂碳基高效氧还原催化剂的制备

杂原子掺杂碳基氧还原（ORR）催化剂具有代替Pt基催化剂的巨大潜力。以硫掺杂g-C₃N₄（S-doped g-C₃N₄, S-g-C₃N₄）作为硫源和氮源,以三嵌段共聚物P123作为碳源,通过简单的高温热解法成功制备了N、S共掺杂碳（N, S co-doped carbon, NSC）催化剂,并考察了热解温度对制备的NSC催化剂ORR性能的影响。材料表征结果显示:温度为1 000 ℃时制备的催化剂NSC-1000具有较高的氮含量和硫含量及最大的比表面积;电化学测试结果显示:NSC-1000具有最佳的ORR性能,在0.1 mol/L KOH溶液中半波电位（half-wave potential, E1/2）高达0.888 V,且经10 000圈循环伏安扫描后E1/2仅负移12 mV,表现出极佳的活性和稳定性。此外,旋转环盘电极测试结果显示:NSC-1000催化剂主要以四电子反应路径催化ORR的发生。本实验为制备N、S共掺杂碳基高效ORR催化剂提供了新的思路。     

等温核酸放大技术在重金属检测方面的应用

等温核酸放大技术是一种可以实现重金属污染物痕量分析的高灵敏性检测方法,在分析检测中有着广泛且重要的作用。本文综述了几种不同的等温核酸放大技术及其在重金属检测方面的应用,阐述分析了各方法的检测原理,为之后建立更加灵敏、快速、准确的检测方法提供了参考。虽然等温核酸放大技术目前主要停留在实验室阶段,并且检测目标有限,但是由于该技术的高灵敏性、特异性以及与其他学科紧密的联系性,具有潜在的应用前景。     

丁腈橡胶硫化反应动力学研究

设计了促进剂A 4种不同用量的丁腈橡胶配方;基于配方,先利用密炼机将丁腈橡胶、硬脂酸和ZnO混炼,再利用开炼机加入硫黄、促进剂和防老剂,再利用无转子硫化仪分别测试了160℃、170℃和180℃下胶料硫化曲线;基于硫化曲线计算出了每组配方胶料硫化反应速率常数K和活化能Ea。结果表明,在焦烧期时,NBR硫化反应为非一级反应,真正的一级反应开始于硫化速率达到最大时,即tdis;焦烧期后的反应可分为2个阶段且遵循一级动力学反应规律。     

多孔普鲁士蓝类似物的合成及电催化析氧性能

采用一种简单易行的共沉淀法合成了前驱体镍铁普鲁士蓝类似物NiFe-PBA（NF）,然后通过溶剂热处理获得了镍铁普鲁士蓝纳米多孔材料（NFP）。通过XRD、SEM、TEM、XPS、BET及电化学方法对所得材料进行了结构表征和析氧性能测试。结果表明,NFP相对于前驱体NF,电化学比表面积增大、催化活性位点增多,电催化析氧反应（OER）性能显著提高。在浓度1 mol/L KOH水溶液中,达到10 mA/cm2电流密度时,NFP所需过电位仅为260 mV,比NF（320 mV）前驱体低18.75%,也优于大多数已报道的非贵金属催化剂和商用贵金属催化剂,显示出良好的应用前景。     

磷酸二苯酯催化的2-吲哚甲烷胺衍生物的合成

以磷酸二苯酯为催化剂,3-甲基吲哚类化合物与亚胺通过Friedel-Crafts加成反应一步合成了具有广泛药理活性的2-吲哚基甲烷胺类化合物,对反应条件进行优化。结果表明,当n(3-甲基吲哚类)∶n(亚胺)∶n(磷酸二苯酯)=1.0∶2.0∶0.1,其中,磷酸二苯酯0.0025 mmol,1 mL无水二氯甲烷作溶剂,室温下反应0.5 h时,即可得到高收率2-吲哚基甲烷胺类衍生物（85%~90%）。产物经 1HNMR、13CNMR 和 HRMS 进行了结构确定。     

The Synthesis of Covalent Triazine-Based Frameworks via Friedel–Crafts Reactions of Cyanuric Chloride with Thienyl and Carbazolyl Derivatives for Fluorescence Sensing to Picric Acid,Iodine and Capturing Iodine

A multifunctional thiophene-based covalent triazine framework (TTPATTh) with triphenylamine as core is synthesized by Friedel–Crafts reaction of cyanuric chloride with thienyl derivative for the first time. The yield of TTPATTh (99.59%) is far higher than that of the carbazole-based CTF (TTPATCz, 47.03%). TTPATTh and TTPATCz possess high BET surface areas with 1235 and 2501 m² g^–1 as well as high pore volumes with 1.60 and 2.23 cm³ g^–1, respectively. TTPATTh and TTPATCz have high thermal stability with high thermal decomposition temperatures of 514 and 598 °C in nitrogen atmosphere. With the introduction of triazine rings, the fluorescence sensing sensitivities of TTPATTh and TTPATCz to picric acid and iodine are improved significantly. Especially for TTPATTh, the K_sv values reach 5.95 × 10⁵ and 1.61 × 10⁴ L mol^–1, and LODs reach 1.02 × 10^–12 and 1.86 × 10^–12 mol L^–1. To the best of the knowledge, this is the most sensitive value among thiophene-based porous organic polymers to PA and I₂. Furthermore, TTPATTh and TTPATCz can also adsorb iodine in vapor phase, cyclohexane solution and aqueous solution, and release iodine by heating or in ethanol solution. The efficiency of controlling the release of iodine is higher than that in ethanol.