甲醛法测定铵盐中氮含量实验的改进

对铵盐中氮含量的测定(甲醛法)实验进行了改进,不仅减少了环境污染,降低了对操作者的影响,而且操作方便。改进后的方法已用于基础化学分析实验。     

Heterocyclization of gem-dichlorocyclopropanes: “Fine tuning” of reactivity towards nitronium triflate

The heterocyclization of gem-dichlorocyclopropanes upon treatment with nitronium triflate in organic nitriles was studied and the influence of the medium on the reaction pathway was shown. While in anhydrous solvent 5-chloroisoxazole was the only product, the admixture with water promoted a three-component heterocyclization affording 4-chloropyrimidine N-oxides. This phenomenon was rationalized using DFT calculations.     

Azidoimidazolinium Salts: Safe and Efficient Diazo‐transfer Reagents and Unique Azido‐donors

2‐Azido‐1,3‐dimethylimidazolinium chloride (ADMC) and its corresponding hexafluorophosphate (ADMP) were found to be efficient diazo‐transfer reagents to various organic compounds. ADMC was prepared by the reaction of 2‐chloro‐1,3‐dimethylimidazolinium chloride (DMC) and sodium azide. ADMP was isolated as a crystal having good thermal stability and low explosibility. ADMC and ADMP reacted with 1,3‐dicarbonyl compounds under mild basic conditions to give 2‐diazo‐1,3‐dicarbonyl compounds in high yields, which were easily isolated in virtue of the high water solubility of the by‐products. ADMP showed high diazo‐transfer ability to primary amines even in the absence of metal salt such as Cu(II). Using this diazotization approach, various alkyl/aryl azides were directly obtained from their corresponding primary amines in high yields. Furthermore, naphthols reacted with ADMC to give the corresponding diazonaphthoquinones in good to high yields. In addition, 2‐azido‐1,3‐dimethylimidazolinium salts were employed as azide‐transfer and migratory amidation reagents.     

A simple method for measuring excess adsorption isotherms of organic eluent components on reversed‐phase packing materials

A simple frontal analysis method has been developed for the reliable measurement of excess adsorption isotherms of an organic component on reversed‐phase adsorbents in a series of programmed concentration steps. In the present method, a peak, which is produced by refractive index change in column eluate, is detected at 589 nm; it represents the elution volume of the boundary. The method is applied to the measurement of the excess adsorption isotherms of organic eluent components from water on commercially available reversed‐phase stationary phases. The results are in good agreement with the previously reported isotherms. We also measure the excess adsorption isotherms of organic eluent components from solutions containing electrolytes. There are not any interference peaks on the elution traces. The method is thus reliably applicable to the evaluation of the excess adsorption of organic eluent components in practical systems.     

BiOI@La(OH)3纳米棒异质结制备及其增强可见光催化去除NO性能

一维La(OH)3纳米棒具有特殊的电子结构和多功能特性,特别是作为半导体光催化剂引起了人们极大的兴趣.但La(OH)3禁带宽度较大,且只能吸收紫外光,所以光催化效率较低,可见光利用能力较差,限制了La(OH)3的实际应用.因此,需要开发一种高效的改进方法来提高La(OH)3的可见光催化性能.本课题组发展了一种有效的改进La(OH)3方法,通过简易的方法将BiOI纳米颗粒沉积在La(OH)3纳米棒上,有效增强了对可见光的吸收能力和光生载流子的分离能力.本文采用X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)、光电子能谱(XPS)、电子自旋共振(ESR)、N2吸附和元素分析等手段研究了BiOI@La(OH)3纳米棒异质结的构建原理及增强可见光催化性能的原因.XRD和XPS结果表明,通过简易化学沉积法原位构建了BiOI@La(OH)3异质结,并且在异质结中没有杂相生成.由SEM图像可见,原始La(OH)3由分散的一维纳米棒组成,平均直径为30–50 nm.通过BiOI与La(OH)3表面的紧密接触成功构建异质结,但BiOI纳米颗粒未改变La(OH)3纳米棒的形貌.由TEM和HRTEM图像可见,La(OH)3纳米棒的平均长度为30–50 nm,并且在BiOI@La(OH)3异质结中可以清晰看出BiOI和La(OH)3之间紧密接触的界面和晶格间距.N2物理吸附结果显示,随着BiOI量的增加,BiOI@La(OH)3异质结的比表面积增加,但孔体积未现明显变化.UV-Vis DRS结果显示,引入BiOI后明显促进了La(OH)3对可见光的吸收能力和利用效率,从而有利于增强可见光催化活性.通过理论计算分别得到BiOI和La(OH)3的价带和导带位置,表明具有非常匹配的能带结构可以促进BiOI光生电子的有效转移.可见光催化去除NO测试结果表明,BiOI@La(OH)3异质结的光催化活性高达50.5%,明显优于BiOI和La(OH)3.ESR测试结果显示,BiOI@La(OH)3异质结可见光催化活性中起主要作用的活性物种是?OH.结合表征结果,BiOI@La(OH)3纳米棒异质结可见光催化性能增强的原因主要有三个:(1)BiOI@La(OH)3异质结增大的比表面积有利于反应物和产物在催化剂表面扩散,同时可提供更多活性位点参与光催化反应;(2)禁带宽度影响光催化效率,当BiOI与La(OH)3达到合适比例时,既可以促进可见光吸收,也可以使光生电子具有较强还原能力;(3)BiOI@La(OH)3异质结有利于光生载流子的分离,从而显著提高其光催化活性.     

激光溅射法生成金属掺杂氮原子团簇CuNn 、ZnNn 和ScNn

以高纯氮气为载气,通过激光分别轰击Cu/BN、Zn/BN和Sc/BN压制成的样品,首次生成了相应团簇CuNn 、ZnNn 和ScNn ,得到了团簇质谱图,确定了CuNn 、ZnNn 和ScNn 团簇中最稳定的组成分别为CuN4 、ZnN6 和ScN12 。     

3‐Nitramino‐4‐nitrofurazan: Enhancing the Stability and Energetic Properties by Introduction of Alkylnitramines

Nitration of 3‐amino‐4‐nitrofurazan with N₂O₅ yielded the corresponding nitramine. 3‐Nitramino‐4‐nitrofurazan is a very promising explosive regarding detonation performance but it suffers from its hygroscopicity, low thermal stability, and high sensitivity to external stimuli. The introduction of other nitramine groups either by alkylation with 1‐chloro‐2‐nitrazapropane or by combination of two 3‐nitramino‐4‐nitrofurazans yielded the corresponding more stable and non‐hygroscopic open‐chain nitramines. Their molecular structures were investigated by single‐crystal X‐ray diffraction. The remarkable difference of their impact sensitivities were evaluated by calculation of their electrostatic potential of the molecular surfaces. Furthermore, the detonation parameters and combustion parameters of the open‐chain nitramines were computed with the EXPLO5 (v. 6.02) computer code.     

Synthesis,Structural and Energetic Properties of Copper(II) Perchlorate Complex with Aminoguanidine

The complexation of copper(II) perchlorate with aminoguanidine hemesulfate (AGHS) yield related mononuclear complex bis(aminoguanidine)copper(II) perchlorate; [Cu(AG)₂](ClO₄)₂ ( I ). The characterization of complex I was done by elemental analysis, electronic spectra, IR studies, and X‐ray diffraction. From analytical data, a stoichiometry of 1:2 of metal to ligand was determined for the complex. The structure consists of centrosymmetric square planar [Cu(AG)₂]²⁺ cations and perchlorate counterions. The Cu^II atom is four‐coordinate by two imine N atoms and two amine N atoms from two aminoguanidine ligands, forming a slightly distorted square‐planar coordination. In the crystal structure, molecules are linked through intermolecular N–H ··· O hydrogen bonds, forming a network. The thermal decomposition process of this complex was investigated through differential scanning calorimetry (DSC) and the sensitivities toward impact and friction were assessed using a BAM drophammer and a BAM friction tester.     

Cr改性钒基催化剂对NH3低温选择性催化还原NOx的影响

火电厂和机动车辆等的NOx排放量与日俱增, NOx的治理已成为环境保护的重要组成部分.以NH3作为还原剂的选择性催化还原(SCR)技术是目前消除NOx最为高效的方法之一.该反应最为典型的催化剂是V2O5–WO3(MoO3)/TiO2,催化活性窗口为250–400 oC.国外通常将SCR系统置于省煤器之后,此时烟气温度在300 oC以上,催化剂能保持较高的活性,但易受到烟气中高浓度烟尘、SO2和碱金属等的影响,寿命相对较短.此外,高温工艺中副产物硫酸铵的堵塞也是一个不可忽视的问题.因此,将SCR脱硝装置设在脱硫除尘之后成为一种优选技术之一,但烟气温度会降至250 oC以下,而常规的钒基催化剂不能满足低温活性要求.通过添加助剂或改变载体可改善钒基催化剂的低温活性,同时保持其高效的抗硫能力.
　　本文以Cr和V为活性组分, TiO2为载体,采用浸渍法制备了铬钒钛(Cr–VOx/TiO2)系列催化剂,考察了它们的低温脱硝活性和抗水抗硫性,并通过N2吸附-脱附、X射线衍射、NH3程序升温脱附(NH3-TPD)、H2程序升温还原(H2-TPR)和X射线光电子能谱等手段对催化剂进行了表征,分析了Cr–V催化剂的作用机制.
　　结果显示,当n(Cr)：n(V)为0.2：0.8,活性组分负载量为10 wt%时, Cr–VOx/TiO2催化剂表现出最佳的低温催化活性;当反应温度为160°C时, NOx转化率达到90%以上,明显优于其他催化剂,同时活性窗口(160–300°C)得到拓宽. NH3-TPD结果表明, VOx/TiO2催化剂表面呈中弱酸性,随着Cr的添加,钒基催化剂的NH3脱附峰向高温拓宽,说明其表面强酸量有所增加, Cr0.2–V0.8/TiO2在160–300°C范围内均出现了NH3的脱附峰,此时催化剂表面弱酸量最大.当n(Cr)：n(V)大于0.2：0.8时,催化剂表面出现强酸位,这种强酸位不利于NH3脱附,从而不利于SCR反应的进行.因此适量Cr的添加有助于提高钒基催化剂表面弱酸及中性酸量. H2-TPR结果发现,助剂Cr的添加使得催化剂表面氧量增加,这可能是由于Cr的添加形成了较多的氧空穴和未饱和的化学键.催化剂表面化学吸附氧是氧化还原反应最活跃的氧物种,在SCR反应中,表面氧可作为NO的吸附介质参与到催化剂表面反应中,可有效提高SCR反应速率.通过考察活性组分负载量对催化剂活性的影响,发现不同负载量催化剂的催化活性依次为10 wt%>20 wt%>50 wt%>5 wt%. XPS分析发现,当负载量为10 wt%时,催化剂表面非计量的钒离子和化学性质活跃的自由电子最多,因此表现出最佳的SCR活性;当负载量过高时,大量氧化物堆积烧结形成V2O5和Cr2V4O13,覆盖了钒离子活性位点,降低了催化剂脱硝效率.
　　催化剂在220°C表现出良好的抗硫性,在通入100 ppm SO212 h后NOx的转化率仍可达99%以上,并未出现硫中毒现象.同时该催化剂也表现出较好的抗水性,在通入10 vol%水蒸气12 h后, NOx转化率仍能达85%以上.     

氮自掺杂暴露（001）晶面TiO2微米片的可见光光催化CO2还原性能增强

化石能源的使用可产生大量CO2,带来严重的温室效应。光催化CO2还原生产太阳燃料技术既有望缓解温室效应,又可以将低能量密度的太阳能转化为高能量密度的化学能储存起来方便使用。高效光催化材料的开发是发展光催化技术的关键。迄今,在已开发的所有半导体光催化材料中, TiO2仍是广泛研究的明星材料。在实际使用中, TiO2的光催化效率仍受限于其极弱的可见光利用率和较高的电子-空穴复合几率。近年来,越来越多的研究表明TiO2的结构与形貌特征极大地影响其光催化效率。尤其, TiO2的外露晶面设计与晶面效应研究引起了广泛关注。由于具有较高表面能和较多表面不饱和键,起初大多数理论和实验研究认为锐钛矿TiO2(001)晶面是光催化活性晶面。后来,越来越多研究表明并非锐钛矿TiO2(001)晶面的暴露比例越高其光催化活性就越高。最近,我们发现锐钛矿TiO2(001)晶面与(101)晶面在调控光催化CO2还原性能上具有良好的协同效应。密度泛函理论计算表明,锐钛矿TiO2的(001)晶面与(101)晶面的能带结构有差异,(001)晶面的导带位置相对于(101)晶面而言较高,而(101)晶面的价带位置相对于(001)晶面而言较低。基于此我们提出,具有合适比例的锐钛矿TiO2的(001)晶面与(101)晶面的交界处可以形成最佳的表面异质结或晶面异质结。表面异质结的形成导致光生电子倾向于向(101)扩散,光生空穴倾向于向(001)扩散,从而促进光生电子-空穴分离,降低光生电子-空穴复合几率。在此工作基础上,我们直接以氮化钛为原料,氢氟酸为添加剂,通过简单的水热反应一步合成了氮自掺杂的TiO2微米片。利用X射线粉末衍射、扫描电镜、X射线光电子能谱、紫外-可见漫反射光谱、氮气吸附-脱附以及电化学阻抗谱等方法手段对所制备的光催化剂进行了基本结构与理化性质表征分析,并研究了其可见光光催化CO2还原性能。电镜照片结果表明,我们所制备的氮自掺杂锐钛矿TiO2微米片的(001)晶面与(101)晶面比例分别为65%和35%。基于我们前期研究结果, TiO2微米片的(001)晶面与(101)晶面可以形成表面异质结,具有良好的电荷分离效率,这也得到了电化学阻抗谱研究结果的证明。同时,由于N的原位掺杂,所制备的TiO2微米片具有优异的可见光捕获能力。由于可见光利用效率增强与光生电子-空穴分离效率提高这两方面的综合作用,所制备的氮自掺杂TiO2微米片具有非常好的可见光光催化CO2还原制甲醇性能,比商用P25及氮掺杂TiO2纳米粒子等参考样品的可见光光催化性能更优异。研究表明,通过原位自掺杂方法与晶面设计方法相结合,可以同时改善TiO2的可见光利用效率和光生电子-空穴分离效率,优化TiO2的可见光光催化性能,这也为后续开发新型高效光催化材料提供了新思路。