[Mo2O2S2(S2)2][2-]的振动光谱研究

本文测定了原子簇化合物[Mo2O2S2(S2)2][2-]的红外和拉曼光谱,并在乙腈溶液中测得其共振拉曼光谱和退偏振比。利用X光晶体结构数据,对此阴离子的伸缩振动作了简化的正则坐标分析计算。所得结果可以帮助分析和归属一些Mo-Fe-S原子簇化合物的振动光谱。     

1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮与甲基膦酸二(1-甲基庚基)酯对Pb(Ⅱ)、Cd(Ⅱ)和Cu(Ⅱ)的萃取机理研究

本文用两相滴定法研究了1-苯基-3-甲基-4-苯甲酰基-5-吡唑酮(PMBP,简写为HA)与甲基膦酸二(1-甲基庚基)脂(P₃₅₀,简写为B)对Pb²⁺、Cd₂₊和Cu²⁺离子在不同的有机溶剂中的萃取机理.确定了萃合物的组成分别为:MA₂(M=Pb²⁺、Ca²⁺、Cu²⁺);MA₂·HA(M=Cd²⁺);MA₂·B(M=Pb²⁺、Cd²⁺)和MA₂·2B(M=Cd²⁺),同时求得了相应的萃合常数β值.     

锆助剂对低温液相合成甲醇用铜铬硅催化剂性能的影响

考察了含锆的铜铬硅催化剂低温液相合成甲醇性能，并进行了BET、TPR-H2、TPD-H2、TPD-CO、XRD和XPS表征。结果表明，锆作为结构助剂及电子助剂对催化剂在低温液相合成甲醇反应中具有显著的促进作用，反应活性可提高32.25 ％。锆助剂能有效提高催化剂的比表面积，促进催化剂中铜铬组分的分散及表面富集。ZrO2加入在催化剂表面产生的Cu+与催化活性的改善密切相关，Zr4+、Cr3+、Cu+可形成复合中心，为价态的稳定性提供微环境，在H2活化及C O键的断裂等反应步骤中起重要作用。     

Ln(η6-m-C6H4Me2)(AlCl4)3, (Ln=Pr,Er)的合成及Pr配合物的晶体结构

LnCl₃(Ln=Pr,Er)与AlCl₃在二甲苯中反应，合成了η⁶-(m-Me₂C₆H₄)Ln(AlCl₄)₃这两个新配合物并对其进行了元素分析、红外光谱和质谱的表征。测定了Pr配合物的晶体结构。该配合物具有扭曲的五角双锥几何构型。二甲苯和一个氯原子处于两个顶点，Pr配合物属单斜晶系，空间群P相似文献   

手性胶束的不对称诱导作用不对称苯偶姻缩合反应

胶束体系是模拟酶的简单模型之一。手性胶束对反应有手性诱导作用。在表面活性剂(1R，2S)-(-)-N-十二烷基-N-甲基麻黄素溴化物和(1R，2S)-(-)-N-十六烷基-N-甲基麻黄素溴化物形成的胶束体系中进行的苯偶姻缩合反应，生成了光学活性的α-羟基酮。     

CO2＋H2制含氧化合物的研究

作为自然界中含有丰富碳源的CO_2,经过催化加氢制含氧化合物的研究,近年来为人们所关注,特别是CO_2加氢制甲醇.从CO_2出发制含氧化合物其前景是诱人的,则可利用碳和氧得到化学品,二则减少了自然界中的CO_2含量,有益于环境保护.本文对Cu-Zn系和Rh-V系催化剂进行初步考察.     

化合物结构／性质相关的研究／拓扑指数法（Ⅰ）

本文提出一种新的拓扑指数－ＥＡ系列指数，它是从表示分子图形的邻接矩阵出发，结合图形中顶点的度构造成ＥＡ矩阵，计算ＥＡ矩阵的本征值，求出本征值绝对值和指数ＥＡΣ及本征值绝对值最大值指数ＥＡｍａｘ，实验表明，ＥＡ系列指数具有良好的唯一性和相关性。     

环硫雄醇的改进合成

环硫雄醇的化学名为2α,3α-环硫-5α-雄甾17β-醇(4),具有抗雌激素、抗生育和明显的抗癌活性。文献报道,以△~2-雄甾烯-17-酮(1)为原料,经五步可合成4,其中由环氧物3经两步法(开环,环硫化)合成环硫雄醇4时,需用易燃的有毒溶剂,收率仅58%。Lightner等曾用KCNS在乙醇等溶剂中迴流48～100h,可使2α,3α-环氧胆甾烷一步     

双功能型嵌入镍纳米颗粒的碳棱柱状微米棒电极用于电化学甲醇氧化助力的节能产氢

With the rapid development of human society, clean energy forms are imperative to sustain the normal operations of various mechanical and electrical facilities under a cozy environment. Hydrogen is considered among the most promising clean energy sources for the future. Recently, electrochemical water splitting has been considered as one of the most efficient approaches to harvest hydrogen energy, which generates only non-pollutant water on combustion. However, the sluggish anodic oxygen evolution reaction significantly restricts the efficiency of water splitting and requires a relatively high cell voltage to drive the electrolysis. Therefore, seeking a thermodynamically favorable anodic reaction to replace the sluggish oxygen evolution reaction by utilizing highly active bifunctional electrocatalysts for the anodic reaction and hydrogen evolution are crucial for achieving energy-efficient hydrogen production for industrial applications. Nevertheless, it is known that the oxygen evolution reaction can be replaced with other useful and thermodynamically favorable reactions to reduce the electrolysis voltage for realizing energy-efficient hydrogen production. Therefore, in this study, we present a bifunctional nickel nanoparticle-embedded carbon (Ni@C) prism-like microrod electrocatalyst synthesized via a two-step method involving the synthesis of a precursor metal-organic framework-74 and subsequent carbonization treatment for methanol oxidation and hydrogen evolution. The interfacial structure consisting of a nickel and carbon skeleton was realized via in situ carbonization. However, the dispersed nickel nanoparticles do not easily aggregate owing to the partition by the surrounding carbon as it would sufficiently expose the active Ni sites to the electrolytes, ensuring fast charge transfer between the catalyst and electrolytes by accelerating the electrochemical kinetics. In the anodic methanol oxidation, the products were detected as carbon dioxide and formate with faradaic efficiencies of 36.2% and 62.5%, respectively, at an applied potential of 1.55 V. Meanwhile, the Ni@C microrod catalyst demonstrated high activity and durability (2.7% current decay after 12 h of continuous operation) toward methanol oxidation, which demonstrates that methanol oxidation precedes oxidation under voltage forces. Notably, the bifunctional catalyst not only exhibits excellent performance toward methanol oxidation but also yields a low overpotential of 155 mV to drive 10 mA∙cm⁻² toward hydrogen evolution in 1.0 mol∙L⁻¹ KOH aqueous solution with 0.5 mol∙L⁻¹ methanol at room temperature, which guarantees the hydrogen production efficiency. More importantly, the constructed two-electrode electrolyzer produced a current density of 10 mA∙cm⁻² at a low cell voltage of 1.6 V, which decreased by 240 mV after replacing the oxygen evolution reaction with methanol oxidation.     

有机化合物中硫元素的微量库仑分析

含硫有机化合物在竖式石英燃烧管中,于氧气流下经950℃高温燃烧分解,生成的二氧化硫(或三氧化硫)通过含双氧水的石英棉转化管,转化为硫酸。硫酸泵入电解池后,进行酸-碱库仑滴定。本法操作按时间程序控制进行,每次分析时间为15分钟,分析绝对误差为±0.5％对含磷的有机硫化合物及含钠、铁、铜、钼、镍、镧等金属的有机硫化合物,如在样品上复盖一层三氧化钨进行燃烧分解,也可获得满意的结果。