钴基费-托合成催化剂上CO、H_2的吸附行为

采用程序升温脱附及FT-IR技术考察了CO、H2在钴基催化剂上的吸附行为.H2-TPD表明,Co/SiO2催化剂有两类脱附氢,引入锆助剂后,低温脱附氢量明显增加,高温吸附氢量下降.CO-TPD及吸附态CO的红外光谱表明锆助剂使CO在钴催化剂上的吸附强度减弱,但其吸附量增大.钴基催化剂的费-托合成反应性能可以用吸附态物种的变化来解释.     

铜,钾助剂对铁基催化剂吸附—脱附性能的影响

气-固相催化反应活性很大程度上依赖于反应组分在催化剂表面上的吸附与脱附行为,因此,研究反应组分在催化剂表面的吸附与脱附性质对了解催化剂表面活性部位分布、催化活性、反应机理等具有重要意义。本文用程序升温脱附(TPD)及稳态化学吸附研究了具有良好催化活性的F-T合成铁基催化剂对CO和H_2的吸附、脱附特性,并讨论了Cu、K助剂的影响。     

丁烯-1在MoO3.Bi2O3.P2O5/SiO2催化剂上的程序升温脱附

本文采用程序升温脱附技术,考察了MoO_3·Bi_2O_3·P_2O_5/SiO_2催化剂晶格氧的逸出和丁烯-1在催化剂上的程序升温脱附特性和表面反应。 实验结果表明:程序升温脱附峰T_M值随丁烯-1吸附量的增加而逐渐增高。从脱附物组成的色谱分析证实,在程序升温脱附过程中吸附的丁烯-1在表面晶格氧参与下发生复杂的催化反应,不单有丁烯异构物、聚合物、丁二烯,还有含氧化合物的生成。丁烯1和其产物的总包脱附活化能随丁烯-1吸附量的增加而增大。采用在不同脱附温度下切割程序升温脱附溜出物和改变程序升温脱附前的抽空条件然后进行色谱分析,初步对丁烯-1在催化剂上的表面反应活性中心进行了分类,并估算了各类反应中心的数目。当温度低于120℃时,发生异构化和双聚反应,高于120℃时有显著的氧化和氧化脱氢反应。还从吸附等温线计算了不同复盖度时丁烯的等容吸附热。并根据本文实验结果和松浦等从经典吸附法求得的丁烯吸附热值进行了讨论。     

钴基费-托合成催化剂上CO、H2的吸附行为

采用程序升温脱附及FT IR技术考察了CO、H2在钴基催化剂上的吸附行为.H2 TPD表明,Co/SiO2催化剂有两类脱附氢,引入锆助剂后,低温脱附氢量明显增加,高温吸附氢量下降.CO TPD及吸附态CO的红外光谱表明锆助剂使CO在钴催化剂上的吸附强度减弱,但其吸附量增大.钴基催化剂的费 托合成反应性能可以用吸附态物种的变化来解释.     

多级孔WO3/ZrO2固体酸催化剂的制备与表征

采用复合模板表面活性剂辅助水热法一步合成了WO3/ZrO2多级孔固体酸催化剂,并应用X射线衍射、低温N2吸附-脱附、拉曼光谱及NH3程序升温脱附对催化剂进行了表征.结果表明,WO3的引入使得WO3/ZrO2催化剂的比表面积增大,表面的酸中心明显增加.在乙酸和正丁醇的酯化反应中,WO3/ZrO2多级孔固体酸催化剂表现出较...     

氧在Co3O4催化剂上的化学吸附

测定了氧在氨氧化催化剂Co_3O_4上于100—400℃下的吸附动力学和室温-600℃的热脱附谱,并与离子探针质谱测定的结果进行了比较。动力学曲线指出氧具有快速和慢速不同类型的吸附,热脱附谱显示有相应的脱附曲线。快速吸附对应于两个脱附峰,峰的极大值温度各为165℃,380—420℃;相应的吸附氧粒子可指定为O_2~-,O~-;脱附活化能分别为13.3千卡/克分子,26.7千卡/克分子。慢速吸附服从Elovich吸附规律,吸附过程可能是快速吸附的氧粒子在催化剂表面上迁移生成O~(2-)并入氧化物表面晶格,脱附温度高于500℃时可由表面晶格中逸出。吸附中心可能是表面Co~(2+)离子。讨论了氧吸附与氨催化氧化反应之间的关系。     

粘土孔结构及添加铈对于催化剂上苯吸附-脱附-催化氧化性能的影响

采用3种不同孔结构的粘土材料,即Na型-蒙脱土(Na-mmt)、Al柱撑粘土(Al-PILC)和AlCe复合柱撑粘土(AlCe-PILC),以上述材料为载体,负载Mn和MnCe作为易挥发有机物(VOC)苯的氧化催化剂。利用N2吸附、程序升温还原(TPR)和程序升温表面反应(TPSR)等手段对催化剂的织构-结构、氧化-还原和吸附-脱附等性能进行了表征和分析。结果表明对于具有高比表面积和大孔径的改性粘土材料,添加适量的Ce有利于催化剂对低浓度苯的吸附,吸附量显著增加、脱附温度提高,上述条件都有利于对低浓度苯的深度氧化。同时,这一研究结果对改善"吸附-催化"一体化的低温吸附、高温脱附及氧化性能有极其重要的意义。     

载体焙烧温度对稀燃天然气汽车尾气净化Pd/Zr0.5Al0.5O1.75催化剂性能的影响

以不同温度焙烧得到的Zr0.5Al0.5O1.75复合氧化物为载体,制备了系列1.5%Pd/Zr0.5Al0.5O1.75催化剂样品.采用N2吸附-脱附、X射线衍射、H2程序升温还原、O2程序升温脱附及CO化学吸附等手段对催化剂进行了表征,并测试了催化剂在模拟稀燃天然气汽车尾气中的活性和抗H2O中毒性能.结果表明,载体...     

焙烧温度对Nb2O5/α-Al2O3催化剂结构及催化性能的影响

 制备了Nb2O5/α-Al2O3催化剂并用于环氧乙烷水合反应制乙二醇,采用X射线衍射,热重-差热分析,红外光谱,吸附氨的程序升温脱附,吸附环氧乙烷的程序升温脱附,扫描电镜和透射电镜研究了焙烧温度对催化剂物理化学性质及催化性能的影响. 结果表明,焙烧温度明显影响氧化铌催化剂的结构、酸量及酸强度. 催化剂的结构不同,环氧乙烷在催化剂表面的吸附强度存在明显差别,而催化剂的酸量和酸强度影响其催化性能.     

磷钨酸“瓶中船”型催化剂的合成、表征及催化分解NOx性能

采用原位合成的方法 ,在微波辐射条件下制备了样品NH4PW-NaY,并通过FTIR、XRD、低温氮吸附-脱附等手段确认了该样品为磷钨酸铵(NH4PW)存在于NaY沸石超笼中的"瓶中船"型催化剂。通过NH4PW与NOx反应生成磷钨酸(HPW)的方式将NH4PW-NaY转化为HPW-NaY,并通过红外及红外吡啶吸附等表征手段证实了NaY沸石超笼中只含有磷钨酸的"瓶中船"型催化剂HPW-NaY被首次制备。随后研究了该催化剂对NOx的吸附-脱附性能,结果表明,在吸附温度为170℃时,HPW-NaY对浓度为1 696 mg.m-3的NOx吸附容量为2.38 mgNOx.gcat-1,在通水蒸汽条件下,催化剂温度降至100℃时所吸附的NOx发生脱附,脱附后的催化剂可重复使用。最后通过程序升温脱附-质谱(TPD-MS)研究了HPW-NaY对NOx的催化分解性能,结果发现NOx在以NaY沸石为载体的HPW上的分解过程中有O2产生,且氧的产生滞后于N2O及N2,HPW-NaY催化分解NOx的转化率及N2选择性分别为61%与75%,均高于单纯HPW催化剂。     

Study of thermal and mechanical properties of composites based on arc-grown carbon nanotubes and heat-resistant cyanoether binder

Multi-walled carbon nanotubes synthesized by means of arc evaporation of graphite were used to prepare composites with a heat-resistant binder based on cyanoether. To increase the homogeneity of distribution of nanotubes in the polymer matrix, the carbon material was cleaned of graphite particles and amorphous carbon with a potassium permanganate solution in concentrated sulfuric acid. By means of X-ray photoelectron spectroscopy, it was shown that the proposed purification procedure leads to the grafting of oxygen-containing groups to the surface of carbon nanotubes. By means of differential scanning calorimetry, it was revealed that the oxide overcoat on the nanotube surface exerts an influence on the character of binder polymerization. The mechanical properties of a carbon-reinforced plastic with different nanotubes contents were measured. It was shown that the admixture of 0.25–0.50% carbon nanotubes improves the mechanical characteristics of carbon-reinforced plastics by 10–20%.     

Properties of a Fireproofing Formulation Based on Liquid Glass and Mechanically Activated Aluminum Oxide

Moistening of filler particles with binder, curing, and high-temperature synthesis were studied in a liquid-glass formulation based on aluminum oxide. Selected kinetic parameters of these processes were determined. The influence exerted by the phase composition and mechanical activation on the adhesion, yield of the synthesis product, and basic properties of the formulation were analyzed.     

Laser-induced breakdown spectroscopy for determination of uranium in thorium-uranium mixed oxide fuel materials

Laser-induced breakdown spectroscopy (LIBS) has been developed for determining the percentage of uranium in thorium-uranium mixed oxide fuel samples required as a part of the chemical quality assurance of fuel materials. The experimental parameters were optimized using mixed oxide pellets prepared from 1:1 (w/w) mixture of thorium-uranium mixed oxide standards and using boric acid as a binder. Calibration curves were established using U(II) 263.553 nm, U(II) 367.007 nm, U(II) 447.233 nm and U(II) 454.363 nm emission lines. The uranium amount determined in two synthetic mixed oxide samples using calibration curves agreed well with that of the expected values. Except for U(II) 263.553 nm, all the other emission lines exhibited a saturation effect due to self-absorption when U amount exceeded 20 wt.% in the Th-U mixture. The present method will be useful for fast and routine determination of uranium in mixed oxide samples of Th and U, without the need for dissolution, which is difficult and time consuming due to the refractory nature of ThO₂. The methodology developed is encouraging since a very good analytical agreement was obtained considering the limited resolution of the spectrometer employed in the work.     

Diol—Based Sol–Gel as a Novel Binder for Barium Titanate Ceramics

The relative merits of using a diol-based sol–gel precursor as a binder in the fabrication of barium titanate ceramics made by die-pressing a mixed oxide starting powder have been investigated. The characteristics of powder compacts were compared to samples prepared using a conventional PVB organic binder. The green strength of pellets with the PVB binder was higher than for samples containing the gel, but strength after binder burnout from gel samples was double that of pellets made with PVB. The gel led to improvements in densification during sintering, but these were most noticeable at low sintering temperatures and at intermediate stages of densification. After sintering for 2 h at 1150C, the gel-containing samples reached 75% of theoretical density, some 5% more than for the organic polymer binder. Sintering at 1300C for 2 h, gave a sintered density of ~96% of theoretical density using the gel additive, which was only 2% higher than for the conventional PVB binder system. The decomposition characteristics of the gel were investigated by TGA, FTIR and GC-MS techniques.     

A Sol-Gel Precursor as a Powder Binder for PZT Ceramic Fabrication

A lead zirconate titanate (PZT) precursor sol was prepared by a diol sol-gel route and used as a binder for assisting the uniaxial die pressing of PZT powders. The powders, of composition Pb(Zr_0.52Ti_0.48) O₃, were prepared by a two step mixed oxide route using lead carbonate, zirconia and titania starting powders. The densification characteristics of the powders, which were not milled after the final calcination step, were compared to samples prepared using PVA as a conventional binder. Improved sintering behaviour was observed for the novel sol-gel binder system. For example, using a sol concentration, equivalent to 7 wt% of PZT derived from the binder, pellets of 95% theoretical density were obtained after firing at 1150°C for 4 h, whereas for the same firing conditions, samples blended with PVA resulted in a density of only 78% theoretical.     

Synthesis and Characterization of Nano‐sized Zinc Oxide Coating on Cellulosic Fibers: Photoactivity and Flame‐retardancy Study

We have investigated the effect of zinc oxide as a photocatalyst and durable flame‐retardant on cellulosic fibers. Zinc oxide nanocrystals were successfully synthesized and deposited onto cellulosic fibers using sol‐gel process at low temperature. The samples were characterized by means of several techniques such as scanning electron microscopy, transmission electron microscopy, diffuse reflectance spectroscopy, X‐ray diffraction and thermogravimetric analysis. The photocatalytic activity was tested by measuring the photodegradation of methylene blue under UV‐Vis illumination. Moreover, flame‐retardancy was tested by vertical flame spread test. The optimum add‐on value for donating flame‐retardancy onto cellulosic fabric was obtained to be in the range of 15.24 to 23.20 g of the ZnO per 100 g of fabric. Thermogravimetric analysis of pure and flame‐retarded samples were accomplished and discussed. The results obtained are in agreement with Wall effect theory and Coating theory. The originality of this work on introducing photoactive flame‐retarded fibers is highly valuable for industrial implementation.     

Preparation and characterization of inorganic hollow fiber membranes

Inorganic hollow fiber membranes were prepared by spinning a polymer solution containing suspended aluminum oxide (Al₂O₃) powders to a hollow fiber precursor, which is then sintered at elevated temperatures. In spinning these hollow fiber precursors, polyethersulfone (PESf), N-methyl-2-pyrrolidone (NMP), and polyvinyl pyrrolidone (PVP) were used as a polymer binder, a solvent, and an additive, respectively. The inorganic hollow fiber membranes prepared were characterized using scanning electron microscope (SEM), gas permeation techniques Coulter porometer, and gravimetric analysis. Some primary factors affecting the structure and performance of the membranes such as the sintering temperature and the ratio of the aluminum oxide to the PESf polymer binder were studied extensively. The prepared inorganic membranes show an asymmetric structure, which is similar to the conventional polymeric membranes prepared from the same phase-inversion technique. The inorganic hollow fiber membrane with a higher porosity and better mechanical strength could be prepared by blending the spinning solution with a smaller amount of aluminum oxide powder.     

聚吡咯/氧化石墨烯层状复合材料的制备及其在超级电容器中的应用(英文)

通过将吡咯单体在低温下与氧化石墨烯进行原位聚合,获得聚吡咯/石墨烯(Ppy/CRGO)复合材料.采用场发射电子显微镜(FESEM)、红外(FT-IR)和热重分析(TGA)对复合物的表面形貌、结构进行表征.FESEM结果表明,通过控制氧化石墨烯(GO)和吡咯单体的质量比例,可以对复合物的层状和厚度进行调控.FT-IR和TGA结果表明,聚吡咯(Ppy)是通过化学键合的方式与氧化石墨烯复合在一起.通过机械冷压法将粉末状Ppy/CRGO复合物压成圆片电极,并探讨了石墨烯和聚吡咯复合比例、反应时间、烘干温度和孔隙率等因素对Ppy/CRGO复合物电极的电学和电化学性能的影响.结果表明,Ppy与CRGO质量比为10∶1所制得的Ppy/CRGO复合物的电容量为421 F·g-1,通过在电极中引入孔隙,电容量能进一步提升为509 F·g-1.     

Development of technology to introduce carbon nanotubes into a polyester-binder composition

Technological regimes of introducing carbon nanotubes (CNTs) into a polyester matrix composite are considered, and the properties of the obtained composition are studied. It is established that agglomerates that cannot be broken up by a mechanical stirring are formed at the moment of CNT wetting with the polyester binder. The use of an ultrasound disperser makes it possible to get rid of agglomerates but leads to enhanced porosity, with additional technological operations being necessary for reducing the latter.     

聚醚环酰胺固体推进剂用键合剂的合成及使用性能

以丙三醇、环氧乙烷、环氧丙烷、氯化亚砜、异氰脲酸等为原料,合成了聚醚环酰胺键合剂。将其应用到推进剂(GAP/HMX/Al/AP)配方中,对成型后的推进剂进行力学性能测试和断面电子显微镜分析。结果表明,此类键合剂可以改善与推进剂中氧化剂的界面粘结性能,有效地提高成型后的推进剂在不同温度下的最大延伸率,但对抗拉伸强度的提高作用不明显。