La_(1.8)Ca_(0.2)Mg_(14)Ni_3合金在甲苯溶液中球磨改性后的储氢性能

采用在甲苯介质中球磨以改善La1.8Ca0.2Mg14Ni3的储氢性能。随着球磨时间的增加,合金的吸放氢性能得到显著地提高,在20 h达到最高。其在513 K,4.0 MPa氢压下初次活化时,吸氢质量分数达到了3.95%,在3次活化后,300 K时的吸氢质量分数达到3.85%,在613 K,一个大气压的放氢质量分数在900 s内达到了4.92%。通过XRD和SEM分析,球磨后合金颗粒粒径明显减小且有非晶化趋势。在球磨过程中形成了电子络合体(electrondonor-acceptor,EDA)体系。合金颗粒粒径、非晶化程度和EDA共同作用使球磨20 h的合金表现出最优异的吸放氢性能。     

Alkylation of toluene with 1‐dodecene over HFAU zeolite. Deactivation and regeneration

The alkylation of toluene with 1dodecene was carried out over a HFAU zeolite (total and framework Si/Al ratio = 25) under the following conditions: fixedbed reactor, 90°C, molar toluene/dodecene ratio of 3, WHSV =10 h^–. Monododecyltoluenes are selectively formed, bidodecyltoluenes appearing only in low amounts at a complete conversion of dodecene. Tridodecyltoluenes are also formed inside the supercages but cannot desorb from the zeolite. These compounds, mainly located in the outer part of the crystallites are responsible for catalyst deactivation. However, tridodecyltoluenes can be completely removed by treatment under toluene flow, which allows a complete regeneration of the catalyst. This removal occurs by transalkylation between tridodecyltoluenes and toluene molecules with a final formation of monododecyltoluenes. At least, the first transalkylation steps occur between toluene in the liquid phase and tridodecyltoluenes in the zeolite pores (pore mouth catalysis).     

HAT-097B甲苯歧化催化剂反应性能的研究

研究了以β沸石为主体的HAT-097B催化剂在催化甲苯和C₉芳烃歧化与烷基转移反应中，反应空速、温度及原料中C₁₀芳烃含量对反应性能的影响。结果表明，该催化剂在重量空速2.5h^-1，反应温度380℃时反应转化率高达47%，并可使用C₁₀芳烃含量达8%的反应原料，可综合利用芳烃资源，具有良好的工业化前景。     

[bupy]BF4-AlCl3离子液体上甲苯和间戊二烯的烷基化反应

The alkylation of toluene with 1,3-pentadiene to produce pentyltoluene was carded out to obtain 2,6-dimethylnaphalene, which is an important intermediate during the production of 2,6-naphthalene dicarboxylic acid. Based on our previous work using anhydrous AlCl3 as catalyst, [bupy]BF4-AlCl3 ionic liquids were employed to catalyze the reaction of 1,3-pentadiene with toluene. The experimental results show that [bupy]BF4-AlCl3 ionic liquids are suitable for the reaction especially when the molar ratio of AlCl3 to [bupy]BF4 is 1.75 ： 1, and the reaction could proceed at the temperature as low as 0℃. It could be as active as pure AlCl3, but much more environmentally friendly.     

Functionally substituted tetramethylcyclopentadienes: Synthesis of 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene and its use in the synthesis of an organometallic polymer

Reaction of 2,3,4,5-tetramethylcyclopent-2-enone (1) withp-LiC₆H₄OC-Me₂OMe, followed by treatment with aqueous acid afforded 1-(p-hydroxyphenyl)-2,3,4,5-tetramethylcyclopentadiene (2). This new ligand was then used in the synthesis of the functionally substituted organomolybdenum reagent (⁵-C₅Me₄-p-C₆H₅OH)Mo(CO)₂(NO) (3). Treatment of a preformed 1/1 styrene/maleic anhydride copolymer ( ) with 5 mol% 3 led to chemical incorporation of the organometallic species into the polymer. The final product contained 3 mol% of the organometallic moiety.     

Absolute measurement of the thermal conductivity of propylene carbonate by the AC transient hot-wire technique

The paper describes a new apparatus for measuring the thermal conductivity of liquids based on a transient hot-wire method. The apparatus has been used to measure the thermal conductivity of propylene carbonate (C₄H₆O₃). The measurements have been carried out in the temperature range 284–313 K and at saturation pressure. The accuracy of the data is within ±1.5%.     

生物质炭对气态挥发性有机污染物的吸附性能及机理

为探究生物质炭对气态有机污染物的吸附能力及作用机理,以核桃壳和椰子壳为原料制备生物质炭.采用元素分析仪、傅里叶红外光谱仪、Boehm滴定和比表面积及孔隙率分析仪分析生物质炭理化特征,并利用吸附柱实验考察生物质炭对气态挥发性有机污染物(苯和甲苯)的吸附行为.结果表明:相同制备条件下,椰壳生物质炭吸附性能高于核桃壳生物质炭.在实验温度范围内(400~700℃),随着制备温度的升高,生物质炭吸附性能增大.低温下制备的生物质炭(400℃)吸附行为符合准二级动力学模型,高温下制备的生物质炭(700℃)的吸附过程符合准一级动力学模型.在吸附温度30℃时,生物质炭对苯和甲苯的等温吸附过程符合Toth模型,计算得到生物质炭最大的理论饱和吸附量为18.98 mg/g苯和61.73 mg/g甲苯.生物质炭的表面酸性官能团和孔道结构在吸附过程中起关键作用,影响吸附质在生物质炭的表面吸附和粒内扩散吸附过程.     

基于微纳电离的有毒有害气体传感器

为了有效避免有害气体浓度的超标对经济效益和人类生命财产安全造成损害,提出并设计了一种新型检测方法,通过对微纳电离型传感器进行一系列的测试,设计的传感器展现了较强的抗弯能力及较快的响应-恢复能力。在室温常压、相对湿度75%的实验条件下,对多个浓度的苯、甲苯气体展开了测试,并基于特征噪声强度识别气体的浓度,构建了对应的识别模型。实验结果表明：传感器对有害气体检测时的测量值和真实值的拟合度可达99%以上,体现了较高的检测精度,且在检测有害气体时传感器处于可逆电离平衡状态,重复性良好,不需要进行预热、安全无毒,因此适合于应用到苯类气体的检测中,能够满足效率、精度的要求,具备了一定的实用性。     

纳米掺锶羟基磷灰石的制备及其吸附性能研究

采用溶胶-凝胶-超临界流体干燥法制备了粒径在100 nm以下的纳米掺锶羟基磷灰石(SrHAP),以牛血清白蛋白(BSA)为吸附目标,研究了纳米SrHAP的吸附性能.结果发现在偏酸性条件下,纳米SrHAP比纳米HAP对BSA的吸附量大,表明掺锶后吸附性能提高;但在碱性条件下,纳米SrHAP对BSA的吸附量减小.纳米SrHAP对BSA的吸附是个快速吸附过程,增加Sr/[Ca Sr]原子比XSr和BSA的起始浓度有利于吸附,升高温度不利于吸附.     

联吡啶钌配合物对末端炔烃的催化

以6,6＇-二甲基-2,2＇-联吡啶为配体合成了二水合氯化顺一二氯·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）配合物,进一步用三氟甲基磺酸银脱氯得到三（三氟甲基）磺酸顺一二水·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）配合物．研究了后者对1-己炔、苯乙炔和丙炔酸乙酯环三聚反应的催化作用．实验结果显示环三聚产物具有区域选择性：产物只有1,2,4一三取代苯与1,3,5-三取代苯两种同分异构体,且主要为1,2,4一三取代苯．催化机理研究表明,三（三氟甲基）磺酸顺一二水·二（6,6＇-二甲基-2,2＇联吡啶）合钌（Ⅲ）中的两个水分子配体首先被两分子炔烃取代生成π-炔基配合物,然后通过氧化偶联反应得到钌杂环戊二烯配合物;第三个炔烃分子经由插入反应或双烯加成反应生成钌杂环庚三烯或7一钌杂双环[2．2．1]-2,5-庚二烯中间体,随后发生还原消除反应得到三取代苯．