Enhanced photocatalytic activity of zeolite-encapsulated TiO2 clusters by complexation with organic additives and N-doping.

In the literature it was found that titanium oxide clusters of a few metal atoms encapsulated inside the micropores of zeolite Y exhibit large blue shifts in the Ti-O ligand-to-metal charge-transfer band as compared to non-encapsulated bulk titanium dioxide particles. This blue shift of the Ti-O absorption band is believed to have a negative effect on the photocatalytic activity of zeolite-encapsulated TiO2. We report here on circumventing this problem and increasing visible-light absorption by means of a red shift of the absorption band caused by addition of some organic molecular modifiers containing acidic OH groups that can strongly bind with titanol groups TiOH. In the studied series of zeolite-encapsulated TiO2 samples, the red shift of the optical spectrum follows the order: catechol > 4-aminobenzoic acid > benzoic acid. Also N-doping of zeolite-encapsulated TiO2 clusters by thermal treatment with urea leads to a red shift of the TiO2 absorption band that depends on the annealing and hydration conditions. By comparison to the degradation of phenol in aqueous solution, we have demonstrated that these changes in the absorption spectrum on addition of the organic modifier are also reflected in the photocatalytic activity of the samples; a greater increase in photocatalytic activity (about 30%) was observed for the additive catechol.     

Kinetic and computational studies on aminolysis of bicyclic carbonates bearing alicyclic structure giving alicyclic hydroxyurethanes

Aminolysis of bicyclic carbonates, which consist of five-membered cyclic carbonate and five- or six-membered alicyclic groups, was examined. Kinetic studies revealed that the aminolysis of the bicyclic carbonate with cyclohexane ring proceeded more smoothly than that of the bicyclic carbonate with cyclopentane ring. Computational calculation suggested that the different reaction rates originate from the distinct ring-strain of the cyclic carbonate groups affected by the conformation of the alicyclic groups.     

Synthesis of oligosaccharides catalyzed by thermostable β-glucosidase fromPyrococcus furiosus

Focusing on CO₂ fixation, photoautotrophic cultivation of the red algaPorphyridium cruentum was investigated by means of a batch culture under a 5% CO₂-enriched atmosphere. The algal growth kinetics was successfully described with a logistic model, and simulation of a continuous culture under the optimum growth conditions (30°C, 12 klux and 1.18 g-cells/L) showed that the algal CO₂-fixation activity could reach 0.66 g-CO₂/(L X d). Under the same growth conditions, eicosapentaenoic acid (20:5 n-3, EPA) and arachidonic acid (20:4 n-6, ARA) yields were similarly calculated to be 3.6 mg-EPA/(L X d) and 6.5 mg-ARA/(L X d), respectively.     

Ti接枝MCM-41催化剂的结构设计及化学亲和选择性研究

 用二氯化钛茂作为活性物种的来源，利用Si－MCM－41催化剂表面羟基的反应性，得到了Ti接枝MCM－41催化剂的两种结构模型．结构表征结果表明，Ti接枝MCM－41催化剂不仅长程结构好，孔径分布均一，而且催化剂表面活性中心含量高．两种结构模型催化剂上芳烃羟化反应性能表明，Ti接枝MCM－41催化剂表面的亲水／憎水性可以在较宽的范围内调变，从而可实现控制芳烃羟化的化学亲和选择性．另外，研究结果还表明，Ti接枝MCM－41催化剂具有很好的活性稳定性．     

金属离子掺杂对TiO2光催化性能的影响

TiO₂光催化反应过程涉及光生电荷、电荷迁移、电荷在TiO₂表面的反应和溶液体相反应4个顺序相接并相互影响的步骤.在TiO₂中掺杂金属离子对以上4个步骤均有重要影响,合理的掺杂可有效地提高其光催化性能.本文综合了国内外此方面的最新研究成果,从提高TiO₂光催化性能和优化光催化反应的角度出发,在材料吸光能力、电荷扩散、表面反应、粒径和晶型等方面,全面地分析总结了金属离子掺杂的影响效果和规律性认识,并对TiO₂基光催化材料的金属离子掺杂改性研究的未来发展方向提出了建议.文中还简要介绍了相关的掺杂方法和材料表征手段.     

One-phase supported titanium-based catalysts for polymerization of ethylene. III. ESR spectra of the ternary system Sio2—R3Al—TiCl4

The ternary catalyst systems based on activated silica, aluminum alkyl, and titanium tetrachloride were polymerized in an ethylene gas-phase polymerization process, and further studied using ESR spectroscopy. Two types of titanium (III) ESR-active centers were observed and a linear dependence between the concentration of that characterized by a rhombic anisotropic signal with g₁ = 1.962, g₂ = 1.945, and g₃ = 1.913 values and catalyst productivity was found. © 1993 John Wiley & Sons, Inc.     

甲烷氧化细菌催化二氧化碳生物合成甲醇的研究

甲烷氧化细菌中包含的甲烷单加氧酶(MMO)、甲醇脱氢酶(ADH)、甲醛脱氢酶(FaldDH)、甲酸脱氢酶(FateDH)经过一系列反应能够把甲烷深度氧化生成二氧化碳，并生成一定的能量物质．把二氧化碳还原为甲醇是一个需要能量的过程，目前还没有已知的有机体在温和条件下完成这一反应．研究发现，甲基弯菌Methylosi-nus trichosporium IMV 3011可以催化二氧化碳生物转化生成甲醇．在休眠的悬浮细胞中充人二氧化碳后，反应一段时间在反应液中检测到了甲醇．二氧化碳转化成甲醇是一个需要能量推动的反应，为了补充反应所消耗的能量．反应一段时间后需要用甲烷进行再生，以恢复细胞中的还原当量NADH．我们进行了反应再生的交替连续批式反应，甲醇积累量能够维持在一个比较稳定的水平．理论上，反应不会增加温室效应，这是一个有效的、环境友好的、可恢复的反应过程．     

聚乳酸纳米复合材料的研究进展

聚乳酸是一种重要的可生物降解/吸收高分子材料,广泛地用作可降解塑料、纤维和生物材料,市场前景广阔.它具有与聚烯烃相当的力学强度和加工性能,但耐热性和抗冲性较差.为满足各种应用的需要,其热性能、力学性能和气体阻隔性等尚需进一步提高.通过与无机纳米材料复合的方法,可以明显地提高聚乳酸的性能.本文介绍了近年来聚乳酸有机-无机纳米复合材料的制备、结构与性能等方面的研究进展,对三者的相互关系进行了评述,并对今后的研究方向进行了展望.     

形态结构和光电特性对纳米TiO2光催化性能的影响

采用sol-gel法制备了系列纳米TiO2光催化剂,运用X射线衍射、BET比表面测定、紫外漫反射吸收光谱和表面光电压谱等手段对催化剂进行表征,并以乙烯作为光催化反应的指标反应分子,研究了TiO2纳米晶的性质对于光催化活性的影响.随着焙烧温度的升高,TiO2的晶粒逐渐增大,比表面积下降,晶相由锐钛矿向金红石转变,其吸收带边与光伏响应阈值向长波方向移动,氧化－还原能力降低,降解乙烯的转化率迅速下降.     

氩气中一氧化碳、二氧化碳、甲烷、乙烷混合气体标准样品的研制

介绍气体报警仪标定和检测使用的氩气中一氧化碳、二氧化碳、甲烷、乙烷气体标准样品的制备,以气相色谱法对其均匀性和稳定性进行考核,对定值结果的不确定度进行了评定。标准气体定值范围:一氧化碳为500～1000μmol/mol,不确定度2%;二氧化碳为1000～5000μmol/mol,不确定度2%;甲烷为300～500μmol/mol,不确定度3%;乙烷为300～500μmol/mol,不确定度3%。